Design of Ratiometric Fluorescent Probes Based on Arene–Metal‐Ion Interactions and Their Application to Cd<sup>II</sup> and Hydrogen Sulfide Imaging in Living Cells

Takashima, Ippei; Kinoshita, Miyuki; Kawagoe, Ryosuke; Nakagawa, Saika; Sugimoto, Manabu; Hamachi, Itaru; Ojida, Akio

doi:10.1002/chem.201304181

Cited by 30 publications

(18 citation statements)

References 40 publications

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“…Due to its simplicity and rapidity, TDDFT is currently the most convenient and popular method for calculating VTEs. It can provide direct excited‐state information and show good agreement with experimental spectral results for fluorescent probes, as exemplified in several previous studies . VTE calculation can allow attribution of UV/Vis and fluorescence bands based on the S 0 and S 1 geometries, respectively, and then get contributions of FMOs.…”

Section: Methodssupporting

confidence: 66%

The sensing mechanism studies of the fluorescent probes with electronically excited state calculations

Han

2017

WIREs Comput Mol Sci

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Recent research has indicated that fluorescent probes have tremendous potential for the selective detection of chemical and biological species. Over the past decade, researchers have proposed a series of fluorescence‐based sensing mechanisms of such probes by the calculation of their electronic excited states. Investigations of sensing mechanisms have been based on deep insights into the interactions between probe molecules and their target species, as well as their fluorescence properties. Advances in calculation methods, modeling software, and computational power have enabled researchers to use excited‐state theoretical calculations to reproduce experimental fluorescence phenomena and then provide molecular‐level explanations thereof. In this advanced review, we describe the evolution of theoretical studies on excited‐state sensing mechanisms for fluorescent probes that respond to target species. Focusing on calculation methods that facilitate investigation of the photophysical properties and excited‐state dynamics of probes, we emphasize sensing mechanisms mainly reported by our group. Most of these studies have been supported by theoretical predictions based on time‐dependent density functional theory. For this most popular excited‐state calculation method, vertical excitation energy, excited‐state geometrical optimization and a scan of the excited‐state potential energy surface should be noted in the calculation of electronic and molecular differences between the excited‐state probe and its reaction product with the target analyte. These state‐of‐the‐art calculations are of great importance for unraveling details of fluorescence‐based sensing mechanisms, including photochemical reactions (such as twist intramolecular charge transfer and excited‐state proton transfer) and excited‐state electronic processes (such as intramolecular charge transfer and photoinduced electron transfer). These studies have generated new and inspirational mechanistic proposals and have provided a systematic approach for the development of efficient fluorescent sensors. WIREs Comput Mol Sci 2018, 8:e1351. doi: 10.1002/wcms.1351 This article is categorized under: Structure and Mechanism > Computational Biochemistry and Biophysics Theoretical and Physical Chemistry > Spectroscopy

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Section: Methodssupporting

confidence: 66%

The sensing mechanism studies of the fluorescent probes with electronically excited state calculations

Han

2017

WIREs Comput Mol Sci

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“…These results demonstrated that AM-contact sensing works in living cells to enable ratio imaging of the metal ions. Our previous results 17,22 and reports by Czarnik 27 and Hancock 20,28,29 suggested that the contactinduced emission shift was limited to rather large 4d-and 5d-block metal ions such as Cd(II) and Ag(I). In this paper, we demonstrated for the first time that AM-contact sensing could also work with the smaller 3d-block metal ions such as Zn(II) and Cu(II).…”

Section: Ratio Imaging Of Metal Ions In Live Cellsmentioning

confidence: 65%

“…A set of the AMcontact probes provided a multicolor fluorescence sensing system, which enabled us to distinguish several metal ions by one-pot single titration and principal component analysis (PCA) We previously reported that a Type-I probe serves as the ratiometric fluorescent chemosensor for metal ions based on AM-contact sensing (Figure 1). 17 For example, probe 1, bearing two sets of 2,2′-dipicolylamine (i.e., R = 2-pyridyl), exhibited a large emission red-shift upon binding with Cd(II), which was induced by forming van der Waals contact between the C9 carbon of the fluorophore and the metal ion in a 1:1 binding complex. However, while Type-I probes fluorescently responded to 4d-and 5d-block metal ions such as Cd(II), Ag(I), and Hg(II), they did not show an emission shift with 3d-block metal ions such as Zn(II).…”

mentioning

confidence: 99%

Arene–Metal-Ion Contact: A Multicolor and Ratiometric Fluorescence Sensing Platform for Metal Ions

Kanegae¹,

Takata²,

Takashima³

et al. 2020

Preprint

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Despite continuous active development of fluorescent probes for metal-ions, their molecular design for ratiometric detection is limited owing to a narrow choice of available sensing mechanisms. We present herein a dual-emission sensing platform for metal ions based on contact interaction between a coordinated metal ion and the aromatic ring of a fluorophore (i.e., arene–metal-ion contact). Our structure-based ligand design provided a new probe possessing BPTN as the metal ion binding unit, which was flexibly concatenated to a tricyclic fluorophore. This molecular architecture allowed us to fluorescently sense various metal ions such as Zn(II), Cu(II), Cd(II), Ag(I), and Hg(II) with the red-shifted emissions. This probe design was applicable to a series of tricyclic fluorophores, enabling ratiometric detection of the metal ions across the blue to near-infrared wavelength region. X-ray crystallography and theoretical computational calculation indicated that the coordinated metal ion has van der Waals contact with the fluorophore, which perturbs its electronic structure and ring conformation to induce the emission red-shift. A set of the arene–metal-ion contact probes was used for the differential sensing of eight metal ions in a one-pot single titration via PCA analysis. Furthermore, the probe was applicable to the ratio imaging of metal ions under live-cell conditions.

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“…2, the fluorescence chemosensor FP displayed strong green fluorescence at 515 nm in HEPES aqueous buffer with pH 7.4. By the addition of 3×10 -4 M of Fe 3+ , the fluorescence intensity of FP (10 µM) was completely quenched (the quenching efficiency at 515 nm was 94%), which could be 80 ascribed to the paramagnetic quenching effect of Fe 3+ and/or ligand to metal charge transfer (LMCT). 13 Job's plot analysis confirmed that FP-Fe 3+ ensemble was formed according to a 1:1 stoichiometry (Fig.…”

Section: Fluorescence Emission Spectrum Studies Of Fp With Various Mementioning

confidence: 99%

A new fluorescent chemosensor for highly selective and sensitive detection of inorganic phosphate (Pi) in aqueous solution and living cells

et al. 2015

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In this work, a new fluorescence chemosensor, FP-Fe 3+ was developed for the detection of Pi in aqueous solution and living cells. The unique ligand, FP displayed a high affinity to Fe 3+ (K a = 1.40×10 6 M -1 ) in the presence of other competing cations, accompanied with a dramatic fluorescence quenching. The specific interaction of Pi and FP-Fe 3+ ensemble led to the liberation of fluorophore, FP, and thus the 10 fluorescence was recovered. The dose-dependent fluorescence enhancement of FP-Fe 3+ showed a good linearity with a detection limit of 300 nM for Pi. The extraordinary performance of the present chemosensor, including high sensitivity, selectivity, and good biocompatibility enable the investigation of fluorescent response for Pi in living cells by confocal microscope. Quantitative monitoring of intracellular Pi was achieved by the flow cytometry analysis. 15 65 ensemble. Herein, a unique ligand, FP, which shows selective fluorescence quenching by Fe 3+ via forming a FP-Fe 3+ complex was designed and facilely synthesized. In the presence of Pi, the Journal Name, [year], [vol], 00-00 | 5 65 treated with 10 µM Fe 3+ ions for another 20 min, (d) and then incubated with Pi (30 µM) for another 20 min.Fig. 13 Confocal bright-field (top), and fluorescence (bottom) imaging of Pi in living MDA-MB-231 cells. (A) Cells stained with FP-Fe 3+ (1 µM) at 70 37 o C in a 5% CO2 incubator for 30 min, (B) MDA-MB-231 cells treated

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Design of Ratiometric Fluorescent Probes Based on Arene–Metal‐Ion Interactions and Their Application to Cd^II and Hydrogen Sulfide Imaging in Living Cells

Cited by 30 publications

References 40 publications

The sensing mechanism studies of the fluorescent probes with electronically excited state calculations

The sensing mechanism studies of the fluorescent probes with electronically excited state calculations

Arene–Metal-Ion Contact: A Multicolor and Ratiometric Fluorescence Sensing Platform for Metal Ions

A new fluorescent chemosensor for highly selective and sensitive detection of inorganic phosphate (Pi) in aqueous solution and living cells

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Design of Ratiometric Fluorescent Probes Based on Arene–Metal‐Ion Interactions and Their Application to CdII and Hydrogen Sulfide Imaging in Living Cells

Cited by 30 publications

References 40 publications

The sensing mechanism studies of the fluorescent probes with electronically excited state calculations

The sensing mechanism studies of the fluorescent probes with electronically excited state calculations

Arene–Metal-Ion Contact: A Multicolor and Ratiometric Fluorescence Sensing Platform for Metal Ions

A new fluorescent chemosensor for highly selective and sensitive detection of inorganic phosphate (Pi) in aqueous solution and living cells

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Design of Ratiometric Fluorescent Probes Based on Arene–Metal‐Ion Interactions and Their Application to Cd^II and Hydrogen Sulfide Imaging in Living Cells