Mechanistic Investigation on Chemiluminescent Formaldehyde Probes

Wang

2023

JoF

Fungal bioluminescence is widely distributed in the terrestrial environment. At a specific stage of growth, luminescent fungi shine green light at the fruiting body or mycelium. From the viewpoint of chemistry, fungal bioluminescence involves an in vivo cycle of caffeic acid. The complete cycle is composed of three stages: biosynthesis of luciferin from caffeic acid, luminescence process from luciferin to oxidized luciferin, and regeneration of caffeic acid from oxidized luciferin. Experimental studies roughly proposed this cycle but not the detailed reaction process and mechanism. Our previous theoretical study clearly described the mechanism of the middle stage. The present article attempts to describe the reaction processes and mechanisms of the other two stages by theoretical calculations. A complete theoretical study on the chemistry in the entire process of fungal bioluminescence is helpful to deeply understand fungal bioluminescence.

Section: Computational Model and Methodsmentioning

confidence: 99%

Chemistry in Fungal Bioluminescence: Theoretical Studies on Biosynthesis of Luciferin from Caffeic Acid and Regeneration of Caffeic Acid from Oxidized Luciferin

Wang

2023

JoF

“…Commonly used materials include luminophores (e. g., fluorescent dyes, fluorescent proteins), luminous substrates (e. g., oxides, sulfides), and fluorescent probes. [20]…”

Section: Diagnostic Technologiesmentioning

confidence: 99%

Near‐Infrared‐II Nanomaterials for Activatable Photodiagnosis and Phototherapy

Jiang,

Lin,

et al. 2024

Chemistry A European J

Near‐Infrared‐II (NIR‐II) spans wavelengths between 1,000 to 1,700 nanometers, featuring deep tissue penetration and reduced tissue scattering and absorption characteristics, providing robust support for cancer treatment and tumor imaging research. This review explores the utilization of activatable NIR‐II photodiagnosis and phototherapy based on tumor microenvironments (e.g., reactive oxygen species, pH, glutathione, hypoxia) and external stimuli (e.g., laser, ultrasound, photothermal) for precise tumor treatment and imaging. Special emphasis is placed on the advancements and advantages of activatable NIR‐II nanomedicines in novel therapeutic modalities like photodynamic therapy, photothermal therapy, and photoacoustic imaging. This encompasses achieving deep tumor penetration, real‐time monitoring of the treatment process, and obtaining high‐resolution, high signal‐to‐noise ratio images even at low material concentrations. Lastly, from a clinical perspective, the challenges faced by activatable NIR‐II phototherapy are discussed, alongside potential strategies to overcome these hurdles.

“…Besides the above cases, the nearly degenerate 1 (σ, σ*) and 1 (n, σ*) states in uncatazlyed CL and two crossings between the diabatic non-ET and ET states in ET-catalyzed CL were also found for many other 1,2-dioxetanes , and 1,2-dioxetanones. ,,− However, these S 0 /S 1 CIs were not directly optimized due to the computational costs and difficulties. Moreover, conventional density functional theory (DFT) and linear-response (LR) time-dependent (TD) DFT (LR-TDDFT) with an open-shell reference state used by some of these studies could not correctly describe the S 0 /S 1 energy gaps due to the heavy spin-contaminations (see Appendix).…”

Section: Conical Intersectionsmentioning

confidence: 99%

Conical Intersection in Chemiluminescence of Cyclic Peroxides

Yue

2022

J. Phys. Chem. Lett.

Self Cite

Chemiluminescence (CL) utilizing chemiexcitation for energy transformation is one of the most highly sensitive and useful analytical techniques. The chemiexcitation is a chemical process of a ground-state reactant producing an excited-state product, in which a nonadiabatic event is facilitated by conical intersections (CIs), the specific molecular geometries where electronic states are degenerated. Cyclic peroxides, especially 1,2-dioxetane/dioxetanone derivatives, are the iconic chemiluminescent substances. In this Perspective, we concentrated on the CIs in the CL of cyclic peroxides. We first present a computational overview on the role of CIs between the ground (S 0 ) state and the lowest singlet excited (S 1 ) state in the thermolysis of cyclic peroxides. Subsequently, we discuss the role of the S 0 /S 1 CI in the CL efficiency and point out misunderstandings in some theoretical studies on the singlet chemiexcitations of cyclic peroxides. Finally, we address the challenges and future prospects in theoretically calculating S 0 /S 1 CIs and simulating the dynamics and chemiexcitation efficiency in the CL of cyclic peroxides.