Sensitive assays by nucleophile-induced rearrangement of photoactivated diarylethenes

Sebastian Fredrich, Aurelio Bonasera, Virginia Valderrey, Stefan Hecht

Research output: Contribution to journalArticleAcademicpeer-review

9 Citations (Scopus)
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Abstract

Upon light-induced isomerization, diarylethenes (DAEs) equipped with reactive aldehyde moieties rearrange selectively in the presence of amines, accompanied by decoloration. In a comprehensive study, the probe structure was optimized with regard to its inherent reactivity in the nucleophile-triggered rearrangement reaction. Detailed structure−reactivity relationships could be derived, in particular with regard to the type of integrated (het)aryl moieties as well as the location of the formyl residue, and the probes’ intrinsic reactivity with primary and secondary amines was optimized. Utilizing an ancillary base, the initially formed rearrangement product can engage in a subsequent catalytic cycle, leading to an amplified decoloration process. This additional catalytic pathway allows us to enhance the sensitivity of our method and successfully discriminate between amines and thiols. Moreover, probes that exhibit strong analyte-induced fluorescence modulation have been designed to further decrease the detection limit by using a more sensitive read-out. The optimized DAE probes are promising molecular components for future programmable sensing materials and devices.
Original languageEnglish
Pages (from-to)6432-6440
Number of pages9
JournalJournal of the American Chemical Society
Volume140
Issue number20
DOIs
Publication statusPublished - 14 May 2018

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Nucleophiles
Amines
Assays
Molecular Probes
Isomerization
Sulfhydryl Compounds
Aldehydes
Limit of Detection
Modulation
Light
Equipment and Supplies

Bibliographical note

PMID: 29756777

Cite this

Fredrich, Sebastian ; Bonasera, Aurelio ; Valderrey, Virginia ; Hecht, Stefan. / Sensitive assays by nucleophile-induced rearrangement of photoactivated diarylethenes. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 20. pp. 6432-6440.
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Sensitive assays by nucleophile-induced rearrangement of photoactivated diarylethenes. / Fredrich, Sebastian; Bonasera, Aurelio; Valderrey, Virginia; Hecht, Stefan.

In: Journal of the American Chemical Society, Vol. 140, No. 20, 14.05.2018, p. 6432-6440.

Research output: Contribution to journalArticleAcademicpeer-review

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AB - Upon light-induced isomerization, diarylethenes (DAEs) equipped with reactive aldehyde moieties rearrange selectively in the presence of amines, accompanied by decoloration. In a comprehensive study, the probe structure was optimized with regard to its inherent reactivity in the nucleophile-triggered rearrangement reaction. Detailed structure−reactivity relationships could be derived, in particular with regard to the type of integrated (het)aryl moieties as well as the location of the formyl residue, and the probes’ intrinsic reactivity with primary and secondary amines was optimized. Utilizing an ancillary base, the initially formed rearrangement product can engage in a subsequent catalytic cycle, leading to an amplified decoloration process. This additional catalytic pathway allows us to enhance the sensitivity of our method and successfully discriminate between amines and thiols. Moreover, probes that exhibit strong analyte-induced fluorescence modulation have been designed to further decrease the detection limit by using a more sensitive read-out. The optimized DAE probes are promising molecular components for future programmable sensing materials and devices.

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