Efficient Thermally Activated Delayed Fluorescence Materials with Aggregation-Induced Emission for Lipid Droplet Imaging

doi:10.6023/cjoc202403038

Abstract

Thermally activated delayed fluorescence (TADF) materials with aggregation-induced emission (AIE) properties are promising for autofluorescence-free bioimaging. However, efficient AIE-TADF luminogens that can specifically target lipid droplets and enable high-quality fluorescence imaging are very limited. 3 new organic luminophores were successfully developed by introducing diphenylamine, 9,10-dihydro-9,9-diphenylanthracene, and 9,10-dihydro-9,9-dimethylanthracene, respectively, onto the phthalimide moiety, along with a lipid droplet-targeting group, morpholine. These compounds exhibited excellent AIE properties with fluorescence quantum yields up to 46.5% in the solid state. Moreover, 5-(diphenylamine)- 2-(2-morpholinoethyl)isoindoline-1,3-dione (1) and 5-(9,9-diphenylacridine-10(9H)-yl)-2-(2-morpholinoethyl) isoindoline-1,3- dione (2) only displayed prompt fluorescence, while 5-(9,9-dimethylacridine-10(9H)-yl)-2-(2-morpholinoethyl)isoindoline- 1,3-dione (3) demonstrated intense TADF. More importantly, 3 exhibited good biocompatibility and the ability to enter cells and specifically target lipid droplets, enabling high-brightness fluorescence imaging. The Pearson’s correlation coefficient between 3 and the commercially available lipid droplet dye Bodipy reached 0.87 in the imaging area. This work provides a new approach for the development of high-performance AIE-TADF molecules for bioimaging applications.

Key words: aggregation-induced emission, thermally activated delayed fluorescence, lipid droplet, bioimaging

Cite this article

Kaihang Huang, Li Yin, Qingyun Jiang, Qian Wang, Guang Shi, Bingjia Xu. Efficient Thermally Activated Delayed Fluorescence Materials with Aggregation-Induced Emission for Lipid Droplet Imaging[J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2479-2486.

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Fig. & Tab. 7

Scheme 1. Synthetic routs to the target compounds

Figure 1. PL spectra of 1, 2 and 3 in (a) tetrahydrofuran (THF) and (b) solid state (concentration: 10 μmol/L; excitation: 330 nm)

Figure 2. (a) PL spectra of 3 in the water/DMSO mixtures with different water fractions (the insets are the fluorescence images of 3 in pure DMSO and water/DMSO mixture with 99% water fraction under the illumination of 365 nm UV light) and (b) UV-vis absorption spectra of 3 in the water/DMSO mixtures with different water fractions (concentration: 50 μmol/L)

Compd.	λ_abs,sl^a/nm	λ_em,sl^b/nm	λ_em,s^c/nm	τ_flu.^d/ns	τ_TADF^e/μs	Φ_PL,s^f/%	α_AIE^g	ΔE_ST^h/eV
1	396	548	519	11.26	N/A	24.1	42.6	0.59
2	390	606	540	14.65	N/A	24.0	130.9	0.18
3	394	640	547	47.60	4.60	46.5	57.8	0.05

Table 1. Some important photophysical parameters of 1, 2, and 3

Figure 3. (a) Emission decay curves for the solid powder of 3 at room temperature under vacuum and in the air and (b) emission decay curves for the solid powder of 3 at different temperatures under vacuum

Figure 4. Viability of A549 cancer cells after incubating with different concentrations of 3 nanoaggregates for 4 h (by CCK8 assay)

Figure 5. LSCM images of 3 in A549 cancer cells (concentration: 10 μmol/L; excitation: 405 nm) (a) Fluorescent image of the lipid droplets stained by Bodipy (green pseudocolor), (b) fluorescent image of the lipid droplets stained by 3 (yellow pseudocolor), and (c) an overlay image of parts a and b.

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