Coelenterazine, a member of the imidazopyrazinone class of chemiluminescent substrates, presents significant potential as a dynamic probe of reactive oxygen species in a biological environment, such as a superoxide anion, in which these species are important in cellular biology and pathology. The objective of the current study was to understand in what way the efficiency of singlet and triplet chemiexcitation could be modulated, towards a more efficient use of imidazopyrazinone-based compounds as dynamic chemiluminescent probes. To this end the thermolysis of imidazopyrazinone dioxetanone, substituted at the C-position with electron-donating or electron-withdrawing groups, was characterized with a theoretical approach based on density functional theory. Substituents with different electron-donating/withdrawing characters have only a limited effect on the singlet chemiexcitation of anionic dioxetanone. For neutral dioxetanone, both electron-withdrawing and weak electron-donating substituents increase singlet chemiexcitation, to the contrary of strong electron-donating groups. During their thermolysis reaction, all molecules presented regions of degeneracy with triplet states, thereby indicating the possibility of triplet chemiexcitation.

Carbon dots (CDs) are carbon-based nanoparticles with very attractive luminescence features. Furthermore, their synthesis by bottom-up strategies is quite flexible, as tuning the reaction precursors and synthesis procedures can lead to an endless number of CDs with distinct properties and applications. However, this complex variability has made the characterization of the structural and optical properties of the nanomaterials difficult. Herein, we performed a systematic evaluation of the effect of three representative bottom-up strategies (hydrothermal, microwave-assisted, and calcination) on the properties of CDs prepared from the same precursors (citric acid and urea). Our results revealed that these synthesis routes led to nanoparticles with similar sizes, identical excitation-dependent blue-to-green emission, and similar surface-functionalization. However, we have also found that microwave and calcination strategies are more efficient towards nitrogen-doping than hydrothermal synthesis, and thus, the former routes are able to generate CDs with significantly higher fluorescence quantum yields than the latter. Furthermore, the different synthesis strategies appear to have a role in the origin of the photoluminescence of the CDs, as hydrothermal-based nanoparticles present an emission more dependent on surface states, while microwave- and calcination-based CDs present an emission with more contributions from core states. Furthermore, calcination and microwave routes are more suitable for high-yield synthesis (~27–29%), while hydrothermal synthesis present almost negligible synthesis yields (~2%). Finally, life cycle assessment (LCA) was performed to investigate the sustainability of these processes and indicated microwave synthesis as the best choice for future studies.

Prior to further purification, carbon dots interact with the fluorescent impurities of their synthesis to produce hybrid luminescence.

Spent coffee grounds (SCGs) are known for containing many organic compounds of interest, including carbohydrates, lipids, phenolic compounds and proteins. Therefore, we investigated them as a potential source to obtain carbon dots (CDs) via a nanotechnology approach. Herein, a comparison was performed between CDs produced by SCGs and classic precursors (e.g., citric acid and urea). The SCG-based CDs were obtained via the one-pot and solvent-free carbonization of solid samples, generating nanosized particles (2.1–3.9 nm). These nanoparticles exhibited a blue fluorescence with moderate quantum yields (2.9–5.8%) and an excitation-dependent emission characteristic of carbon dots. SCG-based CDs showed potential as environmentally relevant fluorescent probes for Fe3+ in water. More importantly, life cycle assessment studies validated the production of CDs from SCG samples as a more environmentally sustainable route, as compared to those using classic reported precursors, when considering either a weight- or a function-based functional unit.

Environmental context The increasing use of sun-creams containing UV-filtering chemicals has led to increased inputs of these compounds to the aquatic environment. Chlorinated waters can convert these chemicals into chlorinated products whose toxic effects are of primary concern. To better understand the environmental fate of sun-cream chemicals, we studied the stability of two UV-filtering compounds under varying conditions of pH, chlorine concentration, temperature, dissolved organic matter and solar irradiation. Abstract The stability of the UV filters 2-ethylhexyl-4-methoxycinnamate (EHMC) and 4-tert-butyl-4′-methoxydibenzoylmethane (BDM) in chlorinated water was studied. High-performance liquid chromatography (HPLC)-UV-diode array detection (DAD) was used to follow the reaction kinetics of both UV filters and HPLC-tandem mass spectrometry (MS/MS) was used to tentatively identify the major transformation by-products. Under the experimental conditions used in this work both UV filters reacted with chlorine following pseudo-first order kinetics: rate constant k=0.0095±0.0007min–1 and half-life t1/2=73±4min for EHMC and rate constant k=0.006±0.001min–1 and half-life t1/2=119±14min for BDM (mean±standard deviation). The chemical transformation of the UV filters in chlorinated water led to the formation of chlorinated by-products that were tentatively identified as mono- and dichloro-substituted compounds that resulted from substitution of the hydrogen atoms in the benzene rings by one or two chlorine atoms. Experimental Box–Behnken designs were used to assess the effect of experimental factors: pH, temperature, chlorine concentration, dissolved organic matter and artificial sunlight irradiation on the transformation of the UV filters.