One-step synthesis of a fluorescein derivative and mechanistic studies

Cook, Michael; Ando, Shinji; Koide, Kazunori

doi:10.1016/j.tetlet.2012.07.084

Cited by 10 publications

(7 citation statements)

References 32 publications

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“…Of all the known antennae a few stand out as particularly attractive: Fluorescein and rhodamine are good sensitizers for the near infrared (NIR) emitting Yb and Nd,5 and strategies exist to transpose the rich chemistry of fluorescein‐based responsive probes into the lanthanide probes domain 6. A major drawback is the awkward synthesis of fluorescein derivatives 7. Additionally, most laboratories are not equipped to perform NIR emission spectroscopy, and fluorescein does not sensitize the visible‐emitting lanthanides (Eu, Tb).…”

Section: Introductionmentioning

confidence: 99%

A Versatile Long‐Wavelength‐Absorbing Scaffold for Eu‐Based Responsive Probes

Szíjjártó

Pershagen

Ilchenko

et al. 2013

Chemistry A European J

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Coumarin-sensitized, long-wavelength-absorbing luminescent Eu(III)-complexes have been synthesized and characterized. The lanthanide binding site consists of a cyclen-based chelating framework that is attached through a short linker to a 7-hydroxycoumarin, a 7-B(OH)(2)-coumarin, a 7-O-(4-pinacolatoboronbenzyl)-coumarin or a 7-O-(4-methoxybenzyl)-coumarin. The syntheses are straightforward, use readily available building blocks, and proceed through a small number of high-yielding steps. The sensitivity of coumarin photophysics to the 7-substituent enables modulation of the antenna-absorption properties, and thus the lanthanide excitation spectrum. Reactions of the boronate-based functionalities (cages) with H(2)O(2) yielded the corresponding 7-hydroxycoumarin species. The same species was produced with peroxynitrite in a ×10(6)-10(7)-fold faster reaction. Both reactions resulted in the emergence of a strong ≈407 nm excitation band, with concomitant decrease of the 366 nm band of the caged probe. In aqueous solution the methoxybenzyl caged Eu-complex was quenched by ONOO(-). We have shown that preliminary screening of simple coumarin-based antennae through UV/Vis absorption spectroscopy is possible as the changes in absorption profile translate with good fidelity to changes in Eu(III)-excitation profile in the fully elaborated complex. Taken together, our results show that the 7-hydroxycoumarin antenna is a viable scaffold for the construction of turn-on and ratiometric luminescent probes.

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Section: Introductionmentioning

confidence: 99%

A Versatile Long‐Wavelength‐Absorbing Scaffold for Eu‐Based Responsive Probes

Szíjjártó

Pershagen

Ilchenko

et al. 2013

Chemistry A European J

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“…Fluorescein is also relatively susceptible to photobleaching. 10 These limitations are less apparent in certain halogenated analogues [11][12][13] such as Oregon Green (10; 2′,7′difluorofluorescein). 6 The fluorine substituents in 10 decrease the pK a of the phenol to 4.8 and markedly enhance the photostability of the compound.…”

Section: Introductionmentioning

confidence: 99%

Efficient and Scalable Synthesis of 4-Carboxy-Pennsylvania Green Methyl Ester: A Hydrophobic Building Block for Fluorescent Molecular Probes

Woydziak¹,

Fu²,

Peterson³

2013

Synthesis

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Fluorinated fluorophores are valuable tools for studies of biological systems. However, amine-reactive single-isomer derivatives of these compounds are often very expensive. To provide an inexpensive alternative, we report a practical synthesis of 4-carboxy-Pennsylvania Green methyl ester. Derivatives of this hydrophobic fluorinated fluorophore, a hybrid of the dyes Oregon Green and Tokyo Green, are often cell permeable, enabling labeling of intracellular targets and components. Moreover, the low pKa of Pennsylvania Green (4.8) confers bright fluorescence in acidic cellular compartments such as endosomes, enhancing its utility for chemical biology investigations. To improve access to the key intermediate 2,7-difluoro-3,6-dihydroxyxanthen-9-one, we subjected bis-(2,4,5-trifluorophenyl)methanone to iterative nucleophilic aromatic substitution by hydroxide on scales of > 40 g. This intermediate was used to prepare over 15 grams of pure 4-carboxy-Pennsylvania Green methyl ester in 28% overall yield without requiring chromatography. This compound can be converted into the amine reactive N-hydroxysuccinimidyl ester in essentially quantitative yield for the synthesis of a wide variety of fluorescent molecular probes.

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“…Compound 4 (23) cannot form a spirocyclic structure and, thus, was considered a desirable probe for use in studying the effect of the spirocyclization. We found that this compound was quenched by HSA more prominently than 1 .…”

mentioning

confidence: 99%

“…The on–off fluorescent sensor can readily be available via a one-step chemical synthesis. 23 The assay protocol is simple, with a fluorometer or fluorescence plate reader as the only instrument. The method is not time sensitive, an advantage for potential high throughput screenings and reproducibility.…”

mentioning

confidence: 99%

“…At this stage, we hypothesized that DCF and compounds 1 , 2 , and 3 could be quenched by protonation on the phenolic hydroxy group or spirocyclization (Figure 1 , equilibrium for 1 ). Compound 4 ( 23 ) cannot form a spirocyclic structure and, thus, was considered a desirable probe for use in studying the effect of the spirocyclization. We found that this compound was quenched by HSA more prominently than 1 .…”

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confidence: 99%

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Time-Insensitive Fluorescent Sensor for Human Serum Albumin and Its Unusual Red Shift

et al. 2014

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The concentration of human serum albumin (HSA) indicates the health state of individuals and is routinely measured by UV spectroscopy with bromocresol. However, this method tends to overestimate HSA, and more critically, depends highly on the timing, in seconds, of the measurements. Here, we report an analog of 2′,7′-dichlorofluorescein that can be used as a fluorescent sensor to quantify HSA in human sera. The accuracy of this new method proved superior to that of bromocresol when an international standard serum sample was analyzed. This method is more convenient than the bromocresol method because it allows for fluorescence measurements during a >15 min period. Colorimetric analysis was also performed to further investigate the effects of the binding of the sensor to HSA. These spectroscopic studies suggest that absorption and emission changes upon HSA binding may be due to the dehydration of the dye and/or stabilization of the tritylic cation species.

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One-step synthesis of a fluorescein derivative and mechanistic studies

Cited by 10 publications

References 32 publications

A Versatile Long‐Wavelength‐Absorbing Scaffold for Eu‐Based Responsive Probes

A Versatile Long‐Wavelength‐Absorbing Scaffold for Eu‐Based Responsive Probes

Efficient and Scalable Synthesis of 4-Carboxy-Pennsylvania Green Methyl Ester: A Hydrophobic Building Block for Fluorescent Molecular Probes

Time-Insensitive Fluorescent Sensor for Human Serum Albumin and Its Unusual Red Shift

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