Preparation and Characterization of Thermochemiluminescent Acridine-Containing 1,2-Dioxetanes as Promising Ultrasensitive Labels in Bioanalysis

详细信息    查看全文

• 作者：Massimo Di Fusco ; Arianna Quintavalla ; Claudio Trombini ; Marco Lombardo ; Aldo Roda ; Massimo Guardigli ; Mara Mirasoli
• 刊名：Journal of Organic Chemistry
• 出版年：2013
• 出版时间：November 15, 2013
• 年：2013
• 卷：78
• 期：22
• 页码：11238-11246
• 全文大小：335K
• 年卷期：v.78,no.22(November 15, 2013)
• ISSN：1520-6904

文摘

Thermochemiluminescence is the luminescence process in which a thermodynamically unstable molecule decomposes with light emission when heated above a threshold temperature. We recently reported the thermochemiluminescence properties of an acridine-containing 1,2-dioxetane, which emits at relatively low temperatures (i.e., below 100 掳C). Herein, we explored the effect of the introduction of methyl substituents in the acridine system. The methyl group did not determine an excessive destabilization of 1,2-dioxetane ring nor significantly affect the general physical properties of the molecule. Monosubstituted methyl derivatives and a series of derivatives bearing several combinations of two, three, and four methyl groups were prepared. The rate of formation of 1,2-dioxetane derivatives 1b鈥?b>k strongly depended on the methyl substitution pattern. All members of this library of mono-, di-, tri-, and tetramethyl-substituted derivatives were characterized in terms of photophysical and thermochemiluminescence properties. The introduction of methyl groups into the acridine ring caused a marked decrease in the activation energy of the thermochemiluminescent reaction. Tri- and tetramethyl-substituted acridones had the highest fluorescence quantum yields, in the range 0.48鈥?.52, and the corresponding 1,2-dioxetanes 1h and 1j showed in thermochemiluminescence imaging experiments limit of detection values more than ten times lower with respect to the unsubstituted derivative.