Pyrene-Based AIEE Active Nanoprobe for Zn²⁺ and Tyrosine Detection Demonstrated by DFT, Bioimaging, and Organic Thin-Film Transistor

Abstract

The development of aggregation-induced emission enhancement (AIEE) active nanoprobes without any synthetic complication for solution-state and organic thin-film transistor (OTFT)-based sensory applications is still a challenging task. In this study, the novel pyrene-incorporated Schiff base (5-phenyl-4-((pyren-1-ylmethylene)amino)-4H-1,2,4-triazole-3-thiol; PT2) with an AIEE property was synthesized via a one-pot reaction and was reported for detecting Zn 2+ and tyrosine in the solution state and OTFT. In the AIEE studies of PT2 (in CH 3 CN) at various water fractions (f w : 0− 97.5%), the existence of J-aggregation, crystalline changes, and nanofibers formation was confirmed by ultraviolet absorption/photoluminescence (UV/PL) spectroscopy, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and dynamiclight scattering (DLS) techniques. Similarly, PT2-based Zn 2+ detection and sensory reversibility with tyrosine were demonstrated by UV/PL studies with evidence related to crystalline/nanolevel changes in PXRD, SEM, TEM, AFM, and DLS data. Distinct decay profiles associated with the AIEE and sensory responses of PT2 were observed in time-resolved photoluminescence spectra. From the standard deviation and linear fittings of PL titrations, detection limits (LODs) of the Zn 2+ with PT2 and the tyrosine with PT2-Zn 2+ were estimated as 0.79 and 45 nM, respectively. High-resolution mass and 1 H NMR results confirmed 2:1 and 1:1 stoichiometry and binding sites of PT2-Zn 2+ -PT2* and tyrosine-Zn 2+ complexes. Moreover, the values of association constants determined by linear fittings were 4.205 × 10 −7 and 1.73 × 10 −8 M −2 , correspondingly. Optimization via the density functional theory disclosed the binding sites and suppression of twisted intramolecular charge transfer/photoinduced electron transfer (TICT/ PET) as well as the involvement of restricted intramolecular rotation in the AIEE and PET "ON-OFF-ON" mechanisms in the Zn 2+ and tyrosine sensors. Results from the B16−F10 cellular and zebrafish imaging of AIEE, Zn 2+ , and tyrosine sensors further attested the applicability of PT2 in biological samples. Finally, the PT2 and pentacene-incorporated OTFT devices were fabricated. The devices displayed more than 90% change in drain-source current when reacted with Zn 2+ with an LOD of 5.46 μM but showed no response to tyrosine, thereby confirming the reversibility. Moreover, the OTFT devices also demonstrated Zn 2+ ion detection in tap water and lake water samples.

Pyrene-Based AIE Active Materials for Bioimaging and Theranostics Applications

“…The one-pot synthesized pyrene-based Schiff base derivatives C29 – C32 (see Figure 16 c–e; FBP , PCS1 , PCS2 and PT2 are the individual representations in their original reports) were reported in metal ions sensing and AIE-based cellular imaging studies [ 98 , 99 , 100 ]. Among them, the C29 (detect Fe 3+ , Al 3+ and Cr 3+ ions) displayed a blue emissive cell lines in the absence of metal ions due to the AIE effect [ 98 ].…”

“…Recently, a pyrene-conjugate Schiff base C32 (see Figure 16 e) was reported for Zn 2+ and tyrosine detection in a solution state and an organic thin film transistor (OTFT) [ 100 ]. The probe C32 is low toxicity and displays the bioimaging ability to the Zn 2+ and tyrosine.…”

Idiosyncatic recognition of Zn2+ and CN− using pyrazolyl-hydroxy-coumarin scaffold and live cell imaging: depiction of luminescent Zn(ii)-metallocryptand

“…Polypodal Schiff bases may synthesize multinuclear metallo–macrocycle complexes, 1,2 which may act as potential magnetic materials, 3,4 homogeneous catalysts, 5 optical and electronic materials, 6,7 sensing devices, 8 etc . Schiff bases with fluorogenic components such as carbazole, 9,10 quinoline, 11,12 rhodamine, 13,14 naphthyl, 15,16 pyrenyl, 17,18 fluorenyl, 19,20 and diformyl 21,22 influence the emission energy, intensity, pattern, and the molecules might serve as sensitive detectors of ions/molecules. Fluorogenic units of Coumarin derivatives 23–25 are beneficial for their diverse pharmacological properties, low toxicity, and interesting photophysical responses to analytes.…”

Diamond-Based Electrodes for Detection of Metal Ions and Anions

“…Detection and quantification of hazardous pollutants, biomolecules, drugs, herbicides, metal ions, and anions are essential to maintaining environmental sustainability [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 ]. A number of methods involving organic nanoprobes, covalent–organic frameworks (COFs), metal–organic frameworks (MOFs), metal nanoparticles, hybrid nanomaterials, small molecules, and polymers were engaged in the quantitation of specific analytes [ 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 ].…”

“…Detection and quantification of hazardous pollutants, biomolecules, drugs, herbicides, metal ions, and anions are essential to maintaining environmental sustainability [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 ]. A number of methods involving organic nanoprobes, covalent–organic frameworks (COFs), metal–organic frameworks (MOFs), metal nanoparticles, hybrid nanomaterials, small molecules, and polymers were engaged in the quantitation of specific analytes [ 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 ]. On the other end of the spectrum, instrumental tactics, such as inductively coupled plasma mass spectrometry, high-performance liquid chromatography, gas chromatography, atomic absorption spectrometry, electrochemical studies, and immunoassays have been pronounced as the conventional cost-effective approaches [ 14 , 15 , 16 , 17 , 18 , 19 , 20 ].…”