Strongly Chemiluminescent Acridinium Esters under Neutral Conditions

Synthesis, Properties, Determination, and Theoretical Study

Manabu Nakazono, Yuji Oshikawa, Mizuho Nakamura, Hidehiro Kubota, Shinkoh Nanbu

研究成果: ジャーナルへの寄稿記事

6 引用 (Scopus)

抄録

Various novel acridinium ester derivatives having phenyl and biphenyl moieties were synthesized, and their optimal chemiluminescence conditions were investigated. Several strongly chemiluminescent acridinium esters under neutral conditions were found, and then these derivatives were used to detect hydrogen peroxide and glucose. Acridinium esters having strong electron-withdrawing groups such as cyano, methoxycarbonyl, and nitro at the 4-position of the phenyl moiety in phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt showed strong chemiluminescence intensities. The chemiluminescence intensity of 3,4-dicyanophenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt was approximately 100 times stronger than that of phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt at pH 7. The linear calibration ranges of hydrogen peroxide and glucose were 0.05-10 mM and 10-2000 μM using 3,4-(dimethoxycarbonyl)phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt at pH 7 and pH 7.5, respectively. The proposed chemiluminescence reaction mechanism of acridinium ester via a dioxetanone structure was evaluated via quantum chemical calculation on density functional theory. The proposed mechanism was composed of the nucleophilic addition reaction of hydroperoxide anion, dioxetanone ring formation, and nonadiabatic transition due to spin-orbit coupling around the transition state (TS) to the triplet state (T1) following the decomposition pathway. The TS which appeared in the thermal decomposition would be a rate-determining step for all three processes.

元の言語英語
ページ(範囲)2450-2461
ページ数12
ジャーナルJournal of Organic Chemistry
82
発行部数5
DOI
出版物ステータス出版済み - 3 3 2017

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Acridines
Chemiluminescence
Esters
Salts
Hydrogen Peroxide
Derivatives
Glucose
Addition reactions
Density functional theory
Anions
Orbits
Pyrolysis
Calibration
Decomposition
trifluoromethanesulfonic acid
Electrons
dioxetanone

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

これを引用

Strongly Chemiluminescent Acridinium Esters under Neutral Conditions : Synthesis, Properties, Determination, and Theoretical Study. / Nakazono, Manabu; Oshikawa, Yuji; Nakamura, Mizuho; Kubota, Hidehiro; Nanbu, Shinkoh.

:: Journal of Organic Chemistry, 巻 82, 番号 5, 03.03.2017, p. 2450-2461.

研究成果: ジャーナルへの寄稿記事

Nakazono, Manabu ; Oshikawa, Yuji ; Nakamura, Mizuho ; Kubota, Hidehiro ; Nanbu, Shinkoh. / Strongly Chemiluminescent Acridinium Esters under Neutral Conditions : Synthesis, Properties, Determination, and Theoretical Study. :: Journal of Organic Chemistry. 2017 ; 巻 82, 番号 5. pp. 2450-2461.
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abstract = "Various novel acridinium ester derivatives having phenyl and biphenyl moieties were synthesized, and their optimal chemiluminescence conditions were investigated. Several strongly chemiluminescent acridinium esters under neutral conditions were found, and then these derivatives were used to detect hydrogen peroxide and glucose. Acridinium esters having strong electron-withdrawing groups such as cyano, methoxycarbonyl, and nitro at the 4-position of the phenyl moiety in phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt showed strong chemiluminescence intensities. The chemiluminescence intensity of 3,4-dicyanophenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt was approximately 100 times stronger than that of phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt at pH 7. The linear calibration ranges of hydrogen peroxide and glucose were 0.05-10 mM and 10-2000 μM using 3,4-(dimethoxycarbonyl)phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt at pH 7 and pH 7.5, respectively. The proposed chemiluminescence reaction mechanism of acridinium ester via a dioxetanone structure was evaluated via quantum chemical calculation on density functional theory. The proposed mechanism was composed of the nucleophilic addition reaction of hydroperoxide anion, dioxetanone ring formation, and nonadiabatic transition due to spin-orbit coupling around the transition state (TS) to the triplet state (T1) following the decomposition pathway. The TS which appeared in the thermal decomposition would be a rate-determining step for all three processes.",
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T2 - Synthesis, Properties, Determination, and Theoretical Study

AU - Nakazono, Manabu

AU - Oshikawa, Yuji

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AU - Nanbu, Shinkoh

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N2 - Various novel acridinium ester derivatives having phenyl and biphenyl moieties were synthesized, and their optimal chemiluminescence conditions were investigated. Several strongly chemiluminescent acridinium esters under neutral conditions were found, and then these derivatives were used to detect hydrogen peroxide and glucose. Acridinium esters having strong electron-withdrawing groups such as cyano, methoxycarbonyl, and nitro at the 4-position of the phenyl moiety in phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt showed strong chemiluminescence intensities. The chemiluminescence intensity of 3,4-dicyanophenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt was approximately 100 times stronger than that of phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt at pH 7. The linear calibration ranges of hydrogen peroxide and glucose were 0.05-10 mM and 10-2000 μM using 3,4-(dimethoxycarbonyl)phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt at pH 7 and pH 7.5, respectively. The proposed chemiluminescence reaction mechanism of acridinium ester via a dioxetanone structure was evaluated via quantum chemical calculation on density functional theory. The proposed mechanism was composed of the nucleophilic addition reaction of hydroperoxide anion, dioxetanone ring formation, and nonadiabatic transition due to spin-orbit coupling around the transition state (TS) to the triplet state (T1) following the decomposition pathway. The TS which appeared in the thermal decomposition would be a rate-determining step for all three processes.

AB - Various novel acridinium ester derivatives having phenyl and biphenyl moieties were synthesized, and their optimal chemiluminescence conditions were investigated. Several strongly chemiluminescent acridinium esters under neutral conditions were found, and then these derivatives were used to detect hydrogen peroxide and glucose. Acridinium esters having strong electron-withdrawing groups such as cyano, methoxycarbonyl, and nitro at the 4-position of the phenyl moiety in phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt showed strong chemiluminescence intensities. The chemiluminescence intensity of 3,4-dicyanophenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt was approximately 100 times stronger than that of phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt at pH 7. The linear calibration ranges of hydrogen peroxide and glucose were 0.05-10 mM and 10-2000 μM using 3,4-(dimethoxycarbonyl)phenyl 10-methyl-10λ4-acridine-9-carboxylate trifluoromethanesulfonate salt at pH 7 and pH 7.5, respectively. The proposed chemiluminescence reaction mechanism of acridinium ester via a dioxetanone structure was evaluated via quantum chemical calculation on density functional theory. The proposed mechanism was composed of the nucleophilic addition reaction of hydroperoxide anion, dioxetanone ring formation, and nonadiabatic transition due to spin-orbit coupling around the transition state (TS) to the triplet state (T1) following the decomposition pathway. The TS which appeared in the thermal decomposition would be a rate-determining step for all three processes.

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