A Turn-on Fluorescent Sensor for Pyrophosphate Based on the Disassembly of Cu²⁺-Mediated Perylene Diimide Aggregates

Abstract

A complex between an anionic perylene diimide derivative (PDI-GlyAsp) and cupric ion has been prepared and applied to be turn-on fluorescent probe for the detection of pyrophosphate (PPi) in 100% aqueous solution. The complex formation process and PPi detection have been studied by absorption and emission spectroscopy. It was confirmed that the introduction of cupric ion into PDI-GlyAsp solution resulted in the assembly of PDI-GlyAsp into PDI-GlyAsp/Cu(2+) aggregates, leading to the fluorescence quenching of PDI-GlyAsp. Upon addition of PPi into the above solution led to the disassembly of the aggregates due to the competitive binding of PPi with Cu(2+) in the PDI-GlyAsp/Cu(2+) complex, and a recovery of PDI-GlyAsp emission was observed. Therefore, the PDI-GlyAsp/Cu(2+) complex can be applied as a turn-on fluorescent probe for detecting PPi with high selectivity and sensitivity.

A Viologen–Perylenediimide Conjugate as an Efficient Base Sensor with Solvatochromic Property

“…In this regard, perylenediimides (PDIs) are aw ell-studied class of fluorophores with excellent electronic, optical, and redox properties. [21][22][23] The presence of ap lanar p-conjugated core leads to the formation of both J-and H-type aggregates, depending on the functionalization at the imide positions and the medium (solvent). [21][22][23] In addition, the PDI chromophores have an added advantage in the designo fs ensors because of their inclination towardss elf-assembly through p-p stacking, electrostatic, and solvationi nteractions.…”

“…[21][22][23] In addition, the PDI chromophores have an added advantage in the designo fs ensors because of their inclination towardss elf-assembly through p-p stacking, electrostatic, and solvationi nteractions. [21][22][23][24][25][26][27] The aggregation of PDIs and consequently the changes in their photophysical properties are highly influenced by the medium, and thus PDIs with appropriate conjugation can be solubilized in solvents with aw ide range of polarity and used as solvatochromic agents. [24][25][26][27] Aggregationo fP DIs is associated withd rastic effects on their photophysical properties.…”

Recent Developments in G-Quadruplex Probes

“…Perylene Dyes. Perylene dyes have attracted interest in a range of sensing applications, such as pH (Zhang et al, 2009), organic amine vapors (Jiang et al, 2010), and pyrophosphate ions (Feng et al, 2012). Perlyene diimide dyes are known to possess high photochemical stabilities and fluorescence quantum yields.…”

Assembly Modulation of PDI Derivative as a Supramolecular Fluorescence Switching Probe for Detection of Cationic Surfactant and Metal Ions in Aqueous Media

“…[1][2][3][4][5][6][7] With such advantageous properties, PDI derivatives have been considered as optimal fluorescent dyes and utilized in a wide variety of applications such as laser dyes, photovoltaic cells, fluorescence switches, molecular wires, molecular transistors and sensors. [8][9][10][11][12][13][14][15][16][17] However, PDI structure and planar π-electron deficient aromatic nature are known to promote strongly the formation of aggregates through stacking interactions between the π-conjugated core 1 and this strong aggregation tendency in aqueous media results in fluorescence quenching. [18][19] Inspite of aggregation and resultant low fluorescence, PDI derivatives have been considered to be excellent fluorophore in sensor design because of excellent electron accepting ability and high fluorescence in the disassembled state.…”