TY - JOUR
T1 - Ratiometric turn-on fluorophore displacement ensembles for nitroaromatic explosives detection
AU - Lee, Ji Yoon
AU - Root, Harrison D.
AU - Ali, Rashid
AU - An, Won
AU - Lynch, Vincent M.
AU - Bähring, Steffen
AU - Kim, In Su
AU - Sessler, Jonathan L.
AU - Park, Jung Su
PY - 2020/11/18
Y1 - 2020/11/18
N2 - There is a recognized need in the area of explosives detection for fluorescence-based sensing systems that are capable of not only producing a turn-on response but also generating a distinctive spectral signature for a given analyte. Here, we report several supramolecular ensembles displaying efficient fluorophore displacement that give rise to an increase in fluorescence intensity upon exposure to various nitroaromatic compounds. The synthetic supramolecular constructs in question consist of a tetrathiafulvalene (TTF)-based pyrrolic macrocycle, benzo-TTF-calix[4]pyrrole (Bz-TTF-C4P), and fluorescent dyes, monomeric or dimeric naphthalenediimide (NDI) and perylenediimide (PDI) derivatives, as well as chloride or hexafluorophosphate (PF6-) salts of rhodamine 6G (Rh-6G). In chloroform solution, these assemblies exist in the form of discrete supramolecular complexes or oligomeric aggregates depending on the specific dye combinations in question. Each ensemble was tested as a potential explosive-responsive fluorescence indicator displacement assay (FIDA) by challenging it with a series of di- and trinitroaromatic compounds and examining the change in fluorescence spectral characteristics. Upon addition of nitroaromatic compounds (NACs), either a "turn-on"or a "turn-off"fluorescent response was observed depending on the nature of the constituent fluorophore and, where applicable, the counteranion. The FIDAs based on the PDI derivatives were found to display not only a ratiometric fluorescence enhancement but also analyte-dependent spectral changes when treated with NACs. The NAC-induced fluorescence spectral response of each ensemble was rationalized on the basis of various solution-phase spectroscopic studies, as well as single-crystal X-ray diffraction analyses.
AB - There is a recognized need in the area of explosives detection for fluorescence-based sensing systems that are capable of not only producing a turn-on response but also generating a distinctive spectral signature for a given analyte. Here, we report several supramolecular ensembles displaying efficient fluorophore displacement that give rise to an increase in fluorescence intensity upon exposure to various nitroaromatic compounds. The synthetic supramolecular constructs in question consist of a tetrathiafulvalene (TTF)-based pyrrolic macrocycle, benzo-TTF-calix[4]pyrrole (Bz-TTF-C4P), and fluorescent dyes, monomeric or dimeric naphthalenediimide (NDI) and perylenediimide (PDI) derivatives, as well as chloride or hexafluorophosphate (PF6-) salts of rhodamine 6G (Rh-6G). In chloroform solution, these assemblies exist in the form of discrete supramolecular complexes or oligomeric aggregates depending on the specific dye combinations in question. Each ensemble was tested as a potential explosive-responsive fluorescence indicator displacement assay (FIDA) by challenging it with a series of di- and trinitroaromatic compounds and examining the change in fluorescence spectral characteristics. Upon addition of nitroaromatic compounds (NACs), either a "turn-on"or a "turn-off"fluorescent response was observed depending on the nature of the constituent fluorophore and, where applicable, the counteranion. The FIDAs based on the PDI derivatives were found to display not only a ratiometric fluorescence enhancement but also analyte-dependent spectral changes when treated with NACs. The NAC-induced fluorescence spectral response of each ensemble was rationalized on the basis of various solution-phase spectroscopic studies, as well as single-crystal X-ray diffraction analyses.
U2 - 10.1021/jacs.0c08106
DO - 10.1021/jacs.0c08106
M3 - Journal article
C2 - 33063999
SN - 0002-7863
VL - 142
SP - 19579
EP - 19587
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 46
ER -