Organic Nucleation: Water Rearrangement Reveals the Pathway of Ibuprofen.

The organic nucleation of the pharmaceutical ibuprofen is investigated, as triggered by the protonation of ibuprofen sodium salt at elevated pH. The growth and aggregation of nanoscale solution species by Analytical Ultracentrifugation and Molecular Dynamics (MD) simulations is tracked. Both approaches reveal solvated molecules, oligomers, and prenucleation clusters, their size as well as their hydration at different reaction stages. By combining surface-specific vibrational spectroscopy and MD simulations, water interacting with ibuprofen at the air-water interface during nucleation is probed. The results show the structure of water changes upon ibuprofen protonation in response to the charge neutralization. Remarkably, the water structure continues to evolve despite the saturation of protonated ibuprofen at the hydrophobic interface. This further water rearrangement is associated with the formation of larger aggregates of ibuprofen molecules at a late prenucleation stage. The nucleation of ibuprofen involves ibuprofen protonation and their hydrophobic assembly. The results highlight that these processes are accompanied by substantial water reorganization. The critical role of water is possibly relevant for organic nucleation in aqueous environments in general.

Passively Stabilized Phase-Resolved Collinear SFG Spectroscopy Using a Displaced Sagnac Interferometer.

Sum-frequency generation (SFG) vibrational spectroscopy is a powerful technique to study interfaces at the molecular level. Phase-resolved SFG (PR-SFG) spectroscopy provides direct information on interfacial molecules' orientation. However, its implementation is technologically demanding: it requires the generation of a local oscillator wave and control of its time delay with sub-fs accuracy. Commonly used noncollinear PR-SFG provides this control naturally but requires very accurate sample height control. Collinear PR-SFG spectroscopy is less demanding regarding sample positioning, but tuning the local oscillator time delay with this beam geometry is challenging. Here, we develop a collinear PR-SFG setup using a displaced Sagnac interferometer. This scheme allows full, independent control of the time delay and intensity of the local oscillator and provides long-time phase stabilization (better than 5° over 12 h) for the measured signal. This approach substantially reduces the complexity of an experimental setup and combines the advantages of collinear and noncollinear PR-SFG techniques.

Toward Understanding Bacterial Ice Nucleation.

Bacterial ice nucleators (INs) are among the most effective ice nucleators known and are relevant for freezing processes in agriculture, the atmosphere, and the biosphere. Their ability to facilitate ice formation is due to specialized ice-nucleating proteins (INPs) anchored to the outer bacterial cell membrane, enabling the crystallization of water at temperatures up to -2 °C. In this Perspective, we highlight the importance of functional aggregation of INPs for the exceptionally high ice nucleation activity of bacterial ice nucleators. We emphasize that the bacterial cell membrane, as well as environmental conditions, is crucial for a precise functional INP aggregation. Interdisciplinary approaches combining high-throughput droplet freezing assays with advanced physicochemical tools and protein biochemistry are needed to link changes in protein structure or protein-water interactions with changes on the functional level.

Specific Ion-Protein Interactions Influence Bacterial Ice Nucleation.

Ice nucleation-active bacteria are the most efficient ice nucleators known, enabling the crystallization of water at temperatures close to 0 °C, thereby overcoming the kinetically hindered phase transition process at these conditions. Using highly specialized ice-nucleating proteins (INPs), they can cause frost damage to plants and influence the formation of clouds and precipitation in the atmosphere. In nature, the bacteria are usually found in aqueous environments containing ions. The impact of ions on bacterial ice nucleation efficiency, however, has remained elusive. Here, we demonstrate that ions can profoundly influence the efficiency of bacterial ice nucleators in a manner that follows the Hofmeister series. Weakly hydrated ions inhibit bacterial ice nucleation whereas strongly hydrated ions apparently facilitate ice nucleation. Surface-specific sum-frequency generation spectroscopy and molecular dynamics simulations reveal that the different effects are due to specific interactions of the ions with the INPs on the surface of the bacteria. Our results demonstrate that heterogeneous ice nucleation facilitated by bacteria strongly depends upon the nature of the ions, and specific ion-protein interactions are essential for the complete description of heterogeneous ice nucleation by bacteria.

Interfacial Water Ordering Is Insufficient to Explain Ice-Nucleating Protein Activity.

Ice-nucleating proteins (INPs) found in bacteria are the most effective ice nucleators known, enabling the crystallization of water at temperatures close to 0 °C. Although their function has been known for decades, the underlying mechanism is still under debate. Here, we show that INPs from Pseudomonas syringae in aqueous solution exhibit a defined solution structure and show no significant conformational changes upon cooling. In contrast, irreversible structural changes are observed upon heating to temperatures exceeding ∼55 °C, leading to a loss of the ice-nucleation activity. Sum-frequency generation (SFG) spectroscopy reveals that active and heat-inactivated INPs impose similar structural ordering of interfacial water molecules upon cooling. Our results demonstrate that increased water ordering is not sufficient to explain INPs' high ice-nucleation activity and confirm that intact three-dimensional protein structures are critical for bacterial ice nucleation, supporting a mechanism that depends on the INPs' supramolecular interactions.

Photonic and Thermal Modelling of Microrings in Silicon, Diamond and GaN for Temperature Sensing.

Staying in control of delicate processes in the evermore emerging field of micro, nano and quantum-technologies requires suitable devices to measure temperature and temperature flows with high thermal and spatial resolution. In this work, we design optical microring resonators (ORRs) made of different materials (silicon, diamond and gallium nitride) and simulate their temperature behavior using several finite-element methods. We predict the resonance frequencies of the designed devices and their temperature-induced shift (16.8 pm K-1 for diamond, 68.2 pm K-1 for silicon and 30.4 pm K-1 for GaN). In addition, the influence of two-photon-absorption (TPA) and the associated self-heating on the accuracy of the temperature measurement is analysed. The results show that owing to the absence of intrinsic TPA-processes self-heating at resonance is less critical in diamond and GaN than in silicon, with the threshold intensity I th = α / ß , α and ß being the linear and quadratic absorption coefficients, respectively.

The world's longest human tooth extracted / Der längste extrahierte menschliche Zahn der Welt

A patient with an abscess of the canine fossa starting from the tooth 13 turned up at the dental office. Such an abscess requires immediate and consistent surgical intervention to avoid potential lethal complications for the patient. The highlying swelling reaching the infraorbital area was quite impressive in this case. The panoramic radiograph that was taken (Fig. 1) revealed a canine of considerable radiographic length. The upper canines of the human have the greatest mean length of all the teeth of the human dentition. A conservative tooth treatment can cause problems just as a surgical tooth preservation in the context of a root tip resection would. An alio loco trepanation and root canal preparation had previously been unsuccessful. The instrumen-tation of the tooth was impossible for the colleague due to its canal length. The difficult access to the root tip as well as the degree of destruction on the palatal side and the abscess spoke in this case against a resection and for the extraction of the tooth. After surgical removal and measurement of the tooth, it was confirmed that with 37.2 mm this was the longest tooth ever extracted by a human being.