Molecular-Dimension-Dependent ESIPT Break for Specific Reversible Response to GSH and Its Real-Time Bioimaging

Glutathione (GSH) plays many important roles in maintaining intracellular redox homeostasis, and determining its real-time levels in the biological system is essential for the diagnosis, treatment, and pathological research of related diseases. Fluorescence imaging has been regarded as a powerful tool for tracking biomarkers in vivo, for which specificity, reversibility, and fast response are the main issues to ensure the real-time effective detection of analytes. The determination of GSH is often interfered with by other active sulfur species. However, in addition to the common features of nucleophilic addition, GSH is unique in its large molecular scale. 2-(2-Hydroxyphenyl) benzothiazole (HBT) was often formed in the ESIPT process. In this study, HBT was installed with α,β-unsaturated ketone conjugated coumarin derivates or nitrobenzene, which were used to adjust the reactivity of α,β-unsaturated ketone. Experimental and theoretical calculations found ESIPT to be favorable in HBT-COU but not HBT-COU-NEt2 or HBT-BEN-NO2 due to the higher electronic energies in the keto form. Thus, for HBT-COU, in the presence of GSH, the hydrogen-bonding interaction between CN of the HBT unit and carboxyl of GSH would inhibit the process, simultaneously promoting the Michel addition reaction between α,β-unsaturated ketone and GSH. As a consequence, probe HBT-COU could exhibit a rapid reversible ratiometric response to GSH. Small structures of Hcy and Cys are passivated for such reactions. Cell imaging demonstrated the specific response of the probe to GSH, and the probe was successfully used to monitor fluctuations in GSH concentration during cells apoptosis in real-time

Restriction of Twisted Intramolecular Charge Transfer Enables the Aggregation-Induced Emission of 1‑(<i>N</i>,<i>N</i>‑Dialkylamino)-naphthalene Derivatives

Understanding the mechanisms of aggregation-induced emission (AIE) is essential for the rational design and deployment of AIEgens toward various applications. Such a deep mechanistic understanding demands a thorough investigation of the excited-state behaviors of AIEgens. However, because of considerable complexity and rapid decay, these behaviors are often not experimentally accessible and the mechanistic comprehension of many AIEgens is lacking. Herein, utilizing detailed quantum chemical calculations, we provide insights toward the AIE mechanism of 1-(N,N-dialkylamino)-naphthalene (DAN) derivatives. Our theoretical analysis, corroborated by experimental observations, leads to the discovery that modulating the formation of the twisted intramolecular charge transfer (TICT) state (caused by the rotation of the amino groups) and managing the steric hindrance to minimize solid-state intermolecular interactions provides a plausible explanation for the AIE characteristics of DAN derivatives. These results will inspire the deployment of the TICT mechanism as a useful design strategy toward AIEgen development

Force-Induced Near-Infrared Chromism of Mechanophore-Linked Polymers

A near-infrared (NIR) mechanophore was developed and incorporated into a poly­(methyl acrylate) chain to showcase the first force-induced NIR chromism in polymeric materials. This mechanophore, based on benzo­[1,3]­oxazine (OX) fused with a heptamethine cyanine moiety, exhibited NIR mechanochromism in solution, thin-film, and bulk states. The mechanochemical activity was validated using UV–vis–NIR absorption/fluorescence spectroscopies, gel permeation chromatography (GPC), NMR, and DFT simulations. Our work demonstrates that NIR mechanochromic polymers have considerable potential in mechanical force sensing, damage detection, bioimaging, and biomechanics

Auxochrome Dimethyl-Dihydroacridine Improves Fluorophores for Prolonged Live-Cell Super-Resolution Imaging

Superior photostability, minimal phototoxicity, red-shifted absorption/emission wavelengths, high brightness, and an enlarged Stokes shift are essential characteristics of top-tier organic fluorophores, particularly for long-lasting super-resolution imaging in live cells (e.g., via stimulated emission depletion (STED) nanoscopy). However, few existing fluorophores possess all of these properties. In this study, we demonstrate a general approach for simultaneously enhancing these parameters through the introduction of 9,9-dimethyl-9,10-dihydroacridine (DMA) as an electron-donating auxochrome. DMA not only induces red shifts in emission wavelengths but also suppresses photooxidative reactions and prevents the formation of triplet states in DMA-based fluorophores, greatly improving photostability and remarkably minimizing phototoxicity. Moreover, the DMA group enhances the fluorophores’ brightness and enlarges the Stokes shift. Importantly, the “universal” benefits of attaching the DMA auxochrome have been exemplified in various fluorophores including rhodamines, difluoride-boron complexes, and coumarin derivatives. The resulting fluorophores successfully enabled the STED imaging of organelles and HaloTag-labeled membrane proteins