Stereochemistry‐Dependent Labeling of Organelles with a Near‐Infrared‐Emissive Phosphorus‐Bridged Rhodamine Dye in Live‐Cell Imaging

Wu, Qian; Taki, Masayasu; Tanaka, Yoshiki; Kesherwani, Manish; Phung, Quan Manh; Enoki, Sawako; Okada, Yasushi; Tama, Florence; Yamaguchi, Shigehiro

doi:10.1002/anie.202400711

Novel Dissymmetric Formal Quinoidal Molecules End‐Capped by Dicyanomethylene and Triphenylphosphonium

Shang,

Meng,

Chen

et al. 2024

Angewandte Chemie

0

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A number of quinoidal molecules with symmetric end‐capping groups, particularly dicyanomethylene units, have been synthesized for organic optoelectronic materials. In comparison, dissymmetric quinoidal molecules, characterized by end‐capping with different groups, are less explored. In this paper, we present the unexpected formation of new formal quinoidal molecules, which are end‐capped with both dicyanomethylene and triphenylphosphonium moieties. The structures of these dissymmetric quinoidal molecules were firmly verified by single crystal structural analyses. On the basis of the control experiments and DFT calculations, we proposed the reaction mechanism for the formation of these dissymmetric quinoidal molecules. The respective zwitterionic forms should make contributions to the ground state structures of these quinoidal molecules based on the analysis of their bond lengths and aromaticity and Mayer Bond Orbital (MBO) calculation. This agrees well with the fact that negative solvatochromism was observed for these quinoidal molecules. Although these new quinoidal molecules are non‐emissive both in solutions and crystalline states, they become emissive with quantum yields up to 51.4% after elevating the solvent viscosity or dispersing them in a PMMA matrix. Interestingly, their emissions can also be switched on upon binding with certain proteins, in particular with human serum albumin.

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Novel Dissymmetric Formal Quinoidal Molecules End‐Capped by Dicyanomethylene and Triphenylphosphonium

Shang,

Meng,

Chen

et al. 2024

Angew Chem Int Ed

1

0

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A number of quinoidal molecules with symmetric end‐capping groups, particularly dicyanomethylene units, have been synthesized for organic optoelectronic materials. In comparison, dissymmetric quinoidal molecules, characterized by end‐capping with different groups, are less explored. In this paper, we present the unexpected formation of new formal quinoidal molecules, which are end‐capped with both dicyanomethylene and triphenylphosphonium moieties. The structures of these dissymmetric quinoidal molecules were firmly verified by single crystal structural analyses. On the basis of the control experiments and DFT calculations, we proposed the reaction mechanism for the formation of these dissymmetric quinoidal molecules. The respective zwitterionic forms should make contributions to the ground state structures of these quinoidal molecules based on the analysis of their bond lengths and aromaticity and Mayer Bond Orbital (MBO) calculation. This agrees well with the fact that negative solvatochromism was observed for these quinoidal molecules. Although these new quinoidal molecules are non‐emissive both in solutions and crystalline states, they become emissive with quantum yields up to 51.4% after elevating the solvent viscosity or dispersing them in a PMMA matrix. Interestingly, their emissions can also be switched on upon binding with certain proteins, in particular with human serum albumin.

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High-Throughput Screening of Antioxidant Drug Candidates from Natural Antioxidants with a “Zero” Intrinsic Fluorescence Peroxynitrite Sensing Precursor

Zhang,

Zhu,

Xiang

et al. 2024

J. Med. Chem.

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The fluorescence high-throughput screening method is of importance for new antioxidant drug candidate discovery for the treatment of serious hepatorenal syndrome, which displayed an obvious upregulated peroxynitrite level. However, most of the current ONOO − probes possessed incomplete fluorescence quenching efficiency, which can result in non-negligible probe inherent fluorescence. Hence, we utilized the probe conjugated structure disruption strategy to construct hydrogenation phosphorus-substituted rhodamine (H−PRh) with "zero" probe inherent fluorescence character. Based on the precursor, a series of natural products were screened for identifying antioxidant drug candidates. Luteolin was screened out by activating the Sirt1-Nrf2-HO-1 signaling pathway to regulate the accumulation of ONOO − in the hepatorenal syndrome. Overall, the "zero" probe inherent fluorescence ONOO − sensor constructed here applies for a promising and versatile toolbox for illuminating the ONOO − -related pathological process in the hepatorenal syndrome. Besides, this strategy of constructing highly sensitive sensors could serve as a valuable reference for further fluorescent probes.

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Stereochemistry‐Dependent Labeling of Organelles with a Near‐Infrared‐Emissive Phosphorus‐Bridged Rhodamine Dye in Live‐Cell Imaging

Cited by 6 publications

References 34 publications

Novel Dissymmetric Formal Quinoidal Molecules End‐Capped by Dicyanomethylene and Triphenylphosphonium

Novel Dissymmetric Formal Quinoidal Molecules End‐Capped by Dicyanomethylene and Triphenylphosphonium

Novel Dissymmetric Formal Quinoidal Molecules End‐Capped by Dicyanomethylene and Triphenylphosphonium

High-Throughput Screening of Antioxidant Drug Candidates from Natural Antioxidants with a “Zero” Intrinsic Fluorescence Peroxynitrite Sensing Precursor

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