A multifunctional selective “turn-on” fluorescent chemosensor for detection of Group IIIA ions Al3+, Ga3+ and In3+

Abstract

A versatile chemosensor 1 (E)-2-(((8-hydroxy-2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)amino)-1H-benzo[de]isoquinoline-1,3(2H)-dione, based on naphthalimide and julolidine moieties, was developed for highly distinguishable and selective recognition of Group IIIA metal ions (Al3+, Ga3+ and In3+). Sensor 1 exhibited significant 'off-on' fluorescence responses at 488 nm in the presence of Al3+ and at 570 nm in the presence of Ga3+ and In3+. The same emission of Ga3+ and In3+ could be distinguished through different color changes (from colorless to yellow for Ga3+ and no color change for In3+). Binding constants of 1 for Ga3+ and In3+ are the highest reported to date for an organic chemosensor. A 2 : 1 binding mode between 1 with Al3+, Ga3+ and In3+ is proposed based on electrospray ionization mass spectrometry, Job plot analysis, and theoretical calculations.

Novel 2‐hydroxynaphthalene‐based fluorescent turn‐on sensor for highly sensitive and selective detection of Al3+ and its application in imaging in vitro and in vivo

“…Deprotonation of the hydrogen bond donor (−OH groups) and inhibition of the ESIPT process in most ESIPT sensors by chelation with Al 3+ ions can result in a single wavelength of the keto (K*) emission. [17,33,39,40] However, supported by 1 H NMR data in DMSO-d 6 , the arising of the dual emission spectra of the bis-NAPPD-Al 3+ complex system could be explained by the coexistence of both the excited state enol (E*) form and the excited state keto (K*) form, which implies that chelation with Al 3+ ions might induce the formation of long-lived enol (E*) and keto (K*) photoproducts. [17] Interestingly, bis-NAPPD showed a linear relationship (R 2 = 0.99093) between the emission intensity and the concentration ratio of [Al 3+ ]/[bis-NAPPD] in the range of 0-10 μM.…”

Mechanistic Insight into Selective Sensing of Hazardous Hg2+ and Explosive Picric Acid by Using a Pyrene‐Azine‐Hydroxyquinoline Framework in Differential Media

“…The binding mode of interaction between PHQ and Hg 2 + has been established by 1 upon addition of Hg 2 + ions to bare ligand ( Figure S9). Upon interaction with Hg 2 + , the broad band at 3440 cm À 1 attributed to phenolic -OH is perturbed significantly with a reduced and shifted absorption band to 3040 cm À 1 .…”

“…In recent times, a paradigm drift towards the development of simple molecule based multifunctional chemosensors, potentially capable to selectively target both metal ions as well as small molecules of environmental and biological significance, is witnessed in the field of analytical research. [1,2] These multiple target sensors have many advantages over single ion recognition based traditional chemosensors such as easy synthetic protocols, cost effectiveness, superb efficiency towards multiple targets of interest, easy sample preparation, real time responses, operational simplicity and recoverability. [3][4][5][6][7] Azine based Schiff base molecular systems, which are recognized with easy synthetic protocols, provide ample opportunities to develop push-pull architectures with D-π-A type conjugation through azine linkages in conjunction with excellent chromophoric units.…”

Synthesis and Derivatization of Julolidine: A Powerful Heterocyclic Structure

“…Reactions employing 8‐hydroxy‐9‐formyljulolidine ( 134 ) and 4‐(hydrazinylmethyl)‐7‐nitrobenzo[c][1,2,5]oxadiazole (Table , Entry 10) or 2‐amino‐1 H ‐benzo[de]isoquinoline‐1,3(2 H )‐dione (Table , Entry 11) resulted in low yield of the desired products , . However, the reactions of 134 with N 1 ‐(5‐nitropyridin‐2‐yl) ethane‐1,2‐diamine and 2,3‐diaminomaleonitrile diamine resulted in good yields (Table , Entries 12–14) , , .…”

“…In addition, paper test strips containing 377 were developed and used successfully for colorimetric analysis of such ions. Julolidine 378 acted as probe for multiple cation detection, with detection limits for Al 3+ and In 3+ of 4.79 and 7.92 µM, respectively …”