Novel nanographenes were prepared by a photochemical cyclodehydrochlorination (CDHC) reaction. Chlorinated precursors were irradiated in acetone in the presence of a base or in pure benzene and underwent multiple (up to four) regioselective cyclization reactions to provide rigid π-conjugated molecules. Pure compounds were recovered in good yields by simple filtration at the end of the reaction. The CDHC reaction showed compatibility with both electron-poor and electron-rich substrates, thus allowing the synthesis of pyridine- and thiophene-fused nanographenes. It also enabled the synthesis of sterically hindered contorted π-conjugated molecules without causing full aromatization. A kinetic study showed that the CDHC reaction under the conditions used is a very fast process, and some reactions are completed within minutes. The CDHC reaction thus shows great potential as an alternative to other reactions involving harsher conditions for the preparation of nanographenes.

To evaluate the structural stability of recoverin, a member of the neuronal calcium sensor family, the effect of temperature, myristoylation, and calcium:protein molar ratio on its secondary structure has been studied by transmission infrared spectroscopy. On the basis of the data, the protein predominantly adopts α-helical structures (∼50-55%) with turns, unordered structures, and β-sheets at 25 °C. The data show no significant impact of the presence of calcium and myristoylation on secondary structure. It is found that, in the absence of calcium, recoverin denatures and self-aggregates while being heated, with the formation of intermolecular antiparallel β-sheets. The nonmyristoylated protein (Rec-nMyr) exhibits a lower temperature threshold of aggregation and a higher intermolecular β-sheet content at 65 °C than the myristoylated protein (Rec-Myr). The former thus appears to be less thermally stable than the latter. In the presence of excess calcium ions (calcium:protein ratio of 10), the protein is thermally stable up to 65 °C with no significant conformational change, the presence of the myristoyl chain having no effect on the thermal stability of recoverin under these conditions. A decrease in the thermal stability of recoverin is observed as the calcium:protein molar ratio decreases, with Rec-nMyr being less stable than Rec-Myr. The data overall suggest that a minimal number of coordinated calcium ions is necessary to fully stabilize the structure of recoverin and that, when bound to the membrane, i.e., when the myristoyl chain protrudes from the interior pocket, recoverin should be more stable than in a Ca-free solution, i.e., when the myristoyl chain is sequestered in the interior.

Carbon nanoparticles (CNPs) are promising materials for optoelectronic and biomedical applications thanks to their optical properties, low production cost, and superior biocompatibility compared to traditional semiconductor quantum dots. The countless synthetic methods reported allow a library of diverse CNP structures and optical properties, guiding their subsequent applications. However, the current drawbacks lie mainly within these synthetic processes, as many of them require harsh conditions preventing control over morphology and often generating chemically inert nanoparticles. Thus, more advances on low temperature and controllable synthetic processes are desirable. In this study, we suggest a new strategy to synthesize CNPs with tunable size, while avoiding the use of harsh conditions and allowing easy surface functionalization. The metastable state of polyyne-containing materials appoints them as ideal precursors for low-temperature preparation of carbon-rich structures. Our approach is to synthesize octatetrayne-containing particles prompt to spontaneous reaction, including topochemical polymerization, followed by aromatization, to avoid harsh carbonization steps. For the particle synthesis, the well-known dispersion polymerization process has been adapted for homocoupling of terminal butadiynes, generating the octatetrayne-containing particles. The method was proven reproducible, scalable, and versatile, as the particles' size can be modulated between 50 and 170 nm. Surface functionalization via thiol-yne click chemistry was completed with a pyrene-modified thiol ligand to provide the CNPs with photoactive properties in the visible range. The functionalized particles exhibit fluorescence at 470 nm arising from excimer formation.

As one of the most toxic metal pollutants, mercury is the subject of extensive research to improve current detection strategies, notably to develop sensitive, selective, fast, and affordable Hg2+-responsive fluorescent probes. Comprehending the sensing mechanism of these molecules is a crucial step in their design and optimization of their performance. Herein, a new fluorescein-based thionocarbonate-appended Hg2+-sensitive probe was synthesized to study the hydrolysis reactions involved in the sensing process. Autohydrolysis was revealed as a significant component of the signal generation mechanism, occurring concurrently with Hg2+-catalyzed hydrolysis. This knowledge was used to investigate the effects of key experimental conditions (pH, temperature, chloride ions) on sensing efficiency. Overall, the chemical and physical properties of this new thionocarbonated dye and the insights into its sensing mechanism will be instrumental in designing reliable and effective portable sensing strategies for mercury and other heavy metals.