Search

meso-methyl-BODIPY photocages release a leaving group upon visible light irradiation but often lack thermal stability. In turn, our thermally-stable, red-shifted BODIPY phototether allows oligonucleotide cyclization, preventing complementary strand hybridization. Hybridization resumes upon red-NIR irradiation, disconnecting the phototether by oxidative cleavage, which is easily monitored by a blue shift in fluorescence. [ABSTRACT FROM AUTHOR]

4,4‐Difluoro‐4‐borata‐3a‐azonia‐4a‐aza‐s‐indacene (BODIPY) dyes are extensively used in various applications of their triplet states, ranging from photoredox catalysis, through triplet sensitization to photodynamic therapy. However, the rational design of BODIPY triplet chromophores by ab initio modelling is limited by their strong interactions of spin, electronic and vibrational dynamics. In particular, spin‐vibronic coupling is often overlooked when estimating intersystem crossing (ISC) rates. In this study, a combined experimental and theoretical approach using spin‐vibronic coupling to correctly describe ISC in BODIPY dyes was developed. For this purpose, seven π‐extended BODIPY derivatives with iodine atoms in different positions were examined. It was found that the heavy‐atom effect of iodine atoms is site specific, causing high triplet yields in only some positions. This site‐specific ISC was explained by El‐Sayed rules, so both the contribution and character of the molecular orbitals involved in the excitation must be considered when predicting the ISC rates. Overall, the rational design of BODIPY triplet chromophores requires using (i) the high‐quality electronic structure theory, including both static and dynamical correlations; and (ii) the two‐component wave function Hamiltonian, and rationalizing; and (iii) ISC based on the character of the molecular orbitals of heavy atoms involved in the excitation, expanding El‐Sayed rules beyond their traditional applications. [ABSTRACT FROM AUTHOR]

In this work, we developed a water‐soluble caging group based on a π‐extended BODIPY scaffold able to release carboxylate‐containing cargo upon red light illumination (λirr=633 nm). We performed mechanistic studies showing new insights into the principles of the photoreactivity of these cages and demonstrated a significant influence of the structure of a carboxylate cargo on the rate and efficiency of the uncaging process and its side reactions. We used it for selective delivery, visualisation, and photorelease of a signaling lipid in cell plasma and internal membranes. With this approach, we successfully induced Ca2+ release in cells expressing the GPR40 receptor. [ABSTRACT FROM AUTHOR]

Many serious diseases are associated with degenerative changes caused by oxidative stress triggered by elevated concentrations of reactive oxygen species (ROS) in cells. Therefore, the development of suitable probes for monitoring such processes is of great importance. Here, we introduce a series of sulfur- and selenium-substituted BODIPY derivatives as reversible redox sensors for ROS and enzymatic redox processes. Significant differences in emission maxima and fluorescence quantum yields between the reduced and oxidized forms make them excellent ratiometric turn-on/off probes. Installation of polar sulfonate groups improved their aqueous solubility while retaining their sensing properties, which allowed the probes to monitor the enzymatic activity of enantioselective methionine sulfoxide reductase. [ABSTRACT FROM AUTHOR]

Keywords: BODIPY; Photocages; Selective Delivery; Signaling Lipids; Uncaging EN BODIPY Photocages Selective Delivery Signaling Lipids Uncaging 1 1 1 08/18/22 20220822 NES 220822 B Gewebetransparentes rotes Licht b wird verwendet, um Ölsäure, ein signalgebendes Lipid, innerhalb von Zellen freizusetzen, was Ca SP 2+ sp -Oszillationen auslöst, die mit einer Fluoreszenzantwort einhergehen. Innentitelbild: Red-Shifted Water-Soluble BODIPY Photocages for Visualisation and Controllable Cellular Delivery of Signaling Lipids (Angew. BODIPY, Photocages, Selective Delivery, Signaling Lipids, Uncaging. [Extracted from the article]

Keywords: BODIPY; Photocages; Selective Delivery; Signaling Lipids; Uncaging EN BODIPY Photocages Selective Delivery Signaling Lipids Uncaging 1 1 1 08/19/22 20220822 NES 220822 B Tissue-transparent red light b is used to release oleic acid, a signaling lipid, into cells, which induces Ca SP 2+ sp oscillations accompanied by a turn-on fluorescence response. Inside Cover: Red-Shifted Water-Soluble BODIPY Photocages for Visualisation and Controllable Cellular Delivery of Signaling Lipids (Angew. BODIPY, Signaling Lipids, Photocages, Selective Delivery, Uncaging. [Extracted from the article]