Search

Brown carbon is a type of carbonaceous aerosol with strong light absorption in the ultraviolet and visible wavelengths that leads to radiative forcing. However, it is difficult to correlate the chemical composition of brown carbon with its atmospheric light absorption properties, which translates into significant uncertainty. Thus, a time-dependent density functional theory (TD-DFT) approach was used to model the real-world absorption properties of 14 polycyclic aromatic hydrocarbons (PAHs) over three regions of the Basque Country (Spain): Bilbao, Urretxu, and Azpeitia. The data were corrected for atmospheric concentration. The results show that the absorption spectra over each region are qualitatively identical, with the absorption intensities being significantly higher over Bilbao than over Azpeitia and Urretxu. Furthermore, it was found that the light absorption by PAHs should be more relevant for radiative forcing when it occurs at UVA and (sub)visible wavelengths. Finally, among the 14 studied PAHs, benzo[b]fluoranthene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene and benzoperylene were identified as the molecules with larger contributions to radiative forcing.

Reactive oxygen species (ROS), including superoxide anion, are involved in regulating various signaling pathways and are also responsible for oxidative stress. Sensing superoxide anion is of particular importance due to its biological significance. One potential approach is to use Coelenterazine as a chemiluminescent probe for the dynamic sensing of this ROS. In this study, we investigated the superoxide anion-triggered chemiluminescence of native Coelenterazine and two halogenated analogs and found that they showed a ~100-fold enhancement of light emission in aqueous solution, which was significantly reduced in methanol and nonexistent in aprotic solvents. In fact, Coelenterazine showed more intense light emission in aprotic solvents and, interestingly, although the light emission of the analogs seemed relatively unaffected by the solvents, their chemiluminescence was significantly quenched in water compared to methanol and, especially, to aprotic media. This suggests that the quenching effect observed for Coelenterazine is responsible for the differences in aqueous media, rather than an intrinsic enhanced emission by the analogs. In summary, we present Coelenterazine analogs that could serve as a basis for enhanced sensing of superoxide anion, providing information that could further our understanding of this chemiluminescent system.

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.

Cancer is a challenging disease to treat, regarding treatment efficiency and side-effects [...]

Superoxide anion is a reactive oxygen species (ROS) of biological interest. More specifically, it plays a role in intra- and intercellular signaling, besides being associated with conditions such as inflammation and cancer. Given this, efforts have been made by the research community to devise new sensing strategies for this ROS species. Among them, the chemiluminescent reaction of marine Coelenterazine has been employed as a sensitive and dynamic probing approach. Nevertheless, chemiluminescent reactions are typically associated with lower emissions in aqueous solutions. Herein, here we report the synthesis of a new Coelenterazine derivative with the potential for superoxide anion sensing. Namely, this novel compound is capable of chemiluminescence in a dose-dependent manner when triggered by this ROS species. More importantly, the light-emission intensities provided by this derivative were relevantly enhanced (intensities 2.13 × 101 to 1.11 × 104 times higher) in aqueous solutions at different pH conditions when compared to native Coelenterazine. The half-life of the chemiluminescent signal is also greatly increased for the derivative. Thus, a new chemiluminescence molecule with significant potential for superoxide anion sensing was discovered and reported for the first time.

Photodynamic therapy (PDT) is an anticancer therapeutic modality with remarkable advantages over more conventional approaches. However, PDT is greatly limited by its dependence on external light sources. Given this, PDT would benefit from new systems capable of a light-free and intracellular photodynamic effect. Herein, we evaluated the heavy-atom effect as a strategy to provide anticancer activity to derivatives of coelenterazine, a chemiluminescent single-molecule widespread in marine organisms. Our results indicate that the use of the heavy-atom effect allows these molecules to generate readily available triplet states in a chemiluminescent reaction triggered by a cancer marker. Cytotoxicity assays in different cancer cell lines showed a heavy-atom-dependent anticancer activity, which increased in the substituent order of hydroxyl < chlorine < bromine. Furthermore, it was found that the magnitude of this anticancer activity is also dependent on the tumor type, being more relevant toward breast and prostate cancer. The compounds also showed moderate activity toward neuroblastoma, while showing limited activity toward colon cancer. In conclusion, the present results indicate that the application of the heavy-atom effect to marine coelenterazine could be a promising approach for the future development of new and optimized self-activating and tumor-selective sensitizers for light-free PDT.