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.

Fredrich S., Bonasera A., Valderrey V., Hecht S. (2018). Sensitive Assays by Nucleophile-Induced Rearrangement of Photoactivated Diarylethenes. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140(20), 6432-6440 [10.1021/jacs.8b02982].

Sensitive Assays by Nucleophile-Induced Rearrangement of Photoactivated Diarylethenes

Bonasera A.;
2018-01-01

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.
2018
Fredrich S., Bonasera A., Valderrey V., Hecht S. (2018). Sensitive Assays by Nucleophile-Induced Rearrangement of Photoactivated Diarylethenes. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140(20), 6432-6440 [10.1021/jacs.8b02982].
File in questo prodotto:
File Dimensione Formato  
B4_ja8b02982.pdf

Solo gestori archvio

Descrizione: Ahead of print
Tipologia: Versione Editoriale
Dimensione 3.71 MB
Formato Adobe PDF
3.71 MB Adobe PDF   Visualizza/Apri   Richiedi una copia
jacs.8b02982.pdf

Solo gestori archvio

Descrizione: Articolo
Tipologia: Versione Editoriale
Dimensione 3.66 MB
Formato Adobe PDF
3.66 MB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10447/369201
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 40
  • ???jsp.display-item.citation.isi??? 42
social impact