Carbon Dots as a Fluorescence pH Nanosensor by Application of an Active Surface Preservation Strategy

In the environmental, industrial, and biomedical fields, pH monitorization is of the upmost importance. However, the most used type of pH sensors, glass pH-electrodes, still present limitations in their application in low volume samples and in cellular pH sensing, due to their size and invasive nature. Fluorescence-based sensors present a solution to such issues, providing a non-invasive solution to pH sensing. Herein, we report the rational development of carbon dots (CDs) as a pH nanosensor via an active surface preservation (ASP) method. Carbon dots (CDs) are carbon-based fluorescent nanoparticles with valuable properties such as high aqueous solubility, low cost and good biocompatibility, with remarkable fluorescence performance, been increasingly used as fluorescent nanosensors. Namely, these nanomaterials present advantages over molecular probes in terms of (photo)stability and water solubility, among others. By employing ASP strategies, the CDs will be prepared by using precursors with known active functional features. The ASP method allows the nanoparticles to retain the structural features of precursors, thus retaining their properties, without the need for costly and time-consuming post-synthesis functionalization procedures. In this work, we intend to provide a proof-of-concept of this type of strategy by utilizing the known pH-sensitivity of fluorescein to provide a pH-based response to CDs. The resulting CDs presented reversible response by fluorescence enhancement in the range of pH from 4 to 12. The nanoparticles exhibited excellent photostability, in different pH solutions. The studied CDs were also unaffected by, either variation of ionic strength or the presence of interferent species, while being compatible with human cancer cells. Finally, CDs were able to determine the pH of real samples. Thus, a selective pH fluorescent CDs-based nanosensor was developed.</jats:p

Combined Experimental and Theoretical Investigation into the Photophysical Properties of Halogenated Coelenteramide Analogs

Marine Coelenterazine is one of the most well-known chemi-/bioluminescent systems, and in which reaction the chemi-/bioluminophore (Coelenteramide) is generated and chemiexcited to singlet excited states (leading to light emission). Recent studies have shown that the bromination of compounds associated with the marine Coelenterazine system can provide them with new properties, such as anticancer activity and enhanced emission. Given this, our objective is to characterize the photophysical properties of a previously reported brominated Coelenteramide analog, by employing a combined experimental and theoretical approach. To better analyze the potential halogen effect, we have also synthesized and characterized, for the first time, two new fluorinated and chlorinated Coelenteramide analogs. These compounds show similar emission spectra in aqueous solution, but with different fluorescence quantum yields, in a trend that can be correlated with the heavy-atom effect (F > Cl > Br). A blue shift in emission in other solvents is also verified with the F-Cl-Br trend. More relevantly, the fluorescence quantum yield of the brominated analog is particularly sensitive to changes in solvent, which indicates that this compound has potential use as a microenvironment fluorescence probe. Theoretical calculations indicate that the observed excited state transitions result from local excitations involving the pyrazine ring. The obtained information should be useful for the further exploration of halogenated Coelenteramides and their luminescent properties