| 著者 |
Chen X, Sugiyama H, Nishimura T, Ueno M, Asakawa H, Yamashita M, Tuo DH, Imamura R, Masuo Y, Maeda K, Komatsu R, Miyazawa K, Takao S, Kobayashi M, Tadokoro Y, Arakawa H, Fukuma T, Arai S, Pu YJ, Maeda K, Ogoshi T, Hirao A.
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| Abstract |
A rapid method for quantifying the niacin metabolite 1-methylnicotinamide (1-MNA) in human blood is required to address the limitations of existing low-throughput techniques such as mass spectrometry. In previous studies, we demonstrated that supramolecular pillar[6]arenes (P6As) bearing either carboxylate groups (P6AC) or sulfonate groups (P6AS) functioned as "turn-off" fluorescent sensors for 1-MNA detection in urine by photoinduced electron transfer (PET). However, because the concentration of 1-MNA in blood is very low, PET-based detection in aqueous solutions was insufficient for reliable quantification on its own. Here, we report that phosphonate-functionalized P6A (P6AP) in 90% acetonitrile formed aggregates with columnar morphology, which was associated with markedly enhanced detection sensitivity for 1-MNA. Under these conditions, aggregation-induced emission (AIE) resulted in increases in the fluorescence intensity, photoluminescence quantum yield, and photoluminescence lifetime. The addition of 1-MNA suppressed the formation of columnar aggregates of P6AP, and this was accompanied by decreases in the fluorescence intensity, photoluminescence quantum yield, and photoluminescence lifetime. This solvation-dependent fluorescence response substantially improved the detection sensitivity for 1-MNA, enabling its detection in human blood. By contrast, in 80% acetonitrile, P6AP showed AIE but did not exhibit similar columnar aggregates or increase the sensitivity. Overall, the aggregation-state-associated enhancement of the fluorescence response provides a functional framework that enhances fluorescence-based detection and represents a promising platform for extension to a broad range of biologically relevant analytes.
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