A General Strategy for Through‐Bond Energy Transfer Fluorescence Probes Combining Intramolecular Charge Transfer: A Silyl Ether System for Endogenous Peroxynitrite Sensing

Abstract

Ag eneral strategy is reported for developing through-bond energy transfer (TBET) fluorescence probes by combining intramolecular charge transfer (ICT). The strategy uses ac oplanard onor-p-bridge-acceptor system (SiOPh-PyOH) without spirolactam. The off-on switcho fT BET and ICT is controlledb yc oplanar structurec hanges in the sensing process insteado fs pirolactam ring-opening in traditional TBET probes. DFT calculations showed that the energy and charget ransfers from SiOPh to PyOH are prohibited.Since the SiOPh has no fluorescence, the probe SiOPh-PyOH shows fluorescence propertiess imilart ot hat of pyrene.After sensing ONOO À ,t he silyl ether is removed and the probec hanges into À OPh-PyO À .E lectron-donating ICT from À OPh to PyO À inducesalarge redshift of emission to 594 nm (179 nm shift). TBET from À OPht oP yO À ensures the probe exhibits al arge pseudo-Stokes shift of 213 nm. Furthermore, the probe was successfully used in endogenousO NOO À detection. This study offersanew strategy for the construction of TBET probes emitting in the red region without spirolactam ring-opening, an ew ONOO À sensing system using silyl ether as ar eaction site, and am ethod for the deprotection of silyl ethers with ONOOH under mild conditions.[a] Dr.

Near‐infrared Fluorescent Probes with Long‐acting Cyclic Monitoring and Effectively Eliminating Peroxynitrite

“…Therefore, HOPyNa‐6‐OH can form an ionization equilibrium with ONOO − to give − OPyNa‐6‐OH and ONOOH (Scheme 3), and this equilibrium can be promoted by the decomposition of ONOOH to give more − OPyNa‐6‐OH , which is a weak fluorescent structure. Then, due to the further promotion by the decomposition of ONOOH, − OPyNa‐6‐OH can be further ionized to give − OPyNa‐6‐O − , which is a strong fluorescent system proved in the previous report, [9a] to achieve the ONOO − sensing. The density functional theory (DFT) calculations were carried out to confirm these fluorescence changes (Figure 5).…”

A Silyl Ether Based Fluorescent Probe for Rapid Monitoring of Endogenous Peroxynitrite Concentration and Imaging in Living Cells through Multicolor Emission

“…In our previous report, we confirmed that ONOOH is a good reagent to remove silyl ether protection and give − ONNO − in the presence of excessive ONOO − (>6 eq. ), which give a green fluorescence emission (Figure a, d). When the concentration of ONOO − is 2–6 eq., the probe emits an orange or yellow fluorescence emission, a mixed color by pink and green (Inset in Figure c).…”