Synthesis and properties of water-soluble 1,9-dialkyl-substituted BF<sub>2</sub> azadipyrromethene fluorophores

doi:10.1007/s11705-019-1828-x

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (1) : 97-104 https://doi.org/10.1007/s11705-019-1828-x

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Synthesis and properties of water-soluble 1,9-dialkyl-substituted BF₂ azadipyrromethene fluorophores

Dan Wu, Gonzalo Durán-Sampedro, Donal F. O’Shea(

)

Department of Chemistry, Royal College of Surgeons in Ireland (RCSI), Dublin 2, Ireland

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Abstract

Bis-alkylsulfonic acid and polyethylene glycol (PEG)-substituted BF₂ azadipyrromethenes have been synthesized by an adaptable and versatile route. Only four synthetic stages were required to produce the penultimate fluorophore compounds, containing either two alcohol or two terminal alkyne substituents. The final synthetic step introduced either sulfonic acid or polyethylene glycol groups to impart aqueous solubility. Sulfonic acid groups were introduced by reaction of the bis-alcohol-substituted fluorophore with sulfur trioxide, and a double Cu(I)-catalyzed cycloaddition reaction between the bis-alkyne fluorophore and methoxypolyethylene glycol azide yielded a neutral bis-pegylated derivative. Both fluorophores exhibited excellent near-infrared (NIR) photophysical properties in methanol and aqueous solutions. Live cell microscopy imaging revealed efficient uptake and intracellular labelling of cells for both fluorophores. Their simple synthesis, with potential for last-step structural modifications, makes the present NIR-active azadipyrromethene derivatives potentially useful as NIR fluorescence imaging probes for live cells.

Keywords NIR-fluorophores live cell imaging NIR-AZA

Corresponding Author(s): Donal F. O’Shea

Just Accepted Date: 30 August 2019 Online First Date: 30 October 2019 Issue Date: 20 January 2020

Cite this article:

Dan Wu,Gonzalo Durán-Sampedro,Donal F. O’Shea. Synthesis and properties of water-soluble 1,9-dialkyl-substituted BF₂ azadipyrromethene fluorophores[J]. Front. Chem. Sci. Eng., 2020, 14(1): 97-104.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1828-x
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I1/97

Fig.1 Different substituent patterns and corresponding spectroscopic characteristics in CHCl₃ for NIR-AZA fluorophores.

Fig.2 Bis-alcohol and bis-alkyne substituted NIR-AZA targets 1a and 1b.

Fig.3 Scheme 1 Synthesis of azadipyrromethene precursors.

Fig.4 Scheme 2 Synthesis of NIR-AZA fluorophores 1a and 1b.

Tab.1 Spectroscopic properties of 1a and 1b compounds

Fig.5 Absorption and emission spectra of 1a (red) and 1b (black) at a concentration of 5 µm.

Fig.6 Scheme 3 Synthesis of water-soluble NIR-AZA derivatives.

Tab.2 Spectroscopic properties of 6a, 6b, and MB^a)

Fig.7 Absorption and emission spectra of 6a (red), 6b (black), and MB (blue) in PBS at a concentration of 5 µm. Inset: Emission image of cuvette containing 6a in PBS.

Fig.8 Widefield microscopy images of live HeLa cells upon incubation with 6a and 6b for 1 h. Top: fluorescence images of cells stained with 6a (5 µmol/L); Bottom: fluorescence images of 6b (5 µmol/L) in HeLa cells. The right panels in each row display enlargements of the areas within the red boxes shown in the left panels. Scale bars= 20 mm.

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[1]	FCE-18105-OF-WD_suppl_1	Download
[2]	FCE-18105-WD-Cell_vesicles_stained_with_6a	Download
[3]	FCE-18105-WD-Cell_vesicles_stained_with_6b	Download
[4]	FCE-18105-WD-Z-stack_of_cell_with_6a	Download
[5]	FCE-18105-WD-Z-stack_of_cell_with_6b	Download
[6]	FCE-18105-WD-Z-stack_of_cell_with_6a	Download

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