Aggregation Induced Emission Switching Based Ultrasensitive Ratiometric Detection of Biogenic Diamines Using a Perylenediimide-Based Smart Fluoroprobe

Abstract

In recent years, the widely explored phenomenon “aggregation-induced emission (AIE)” has played a crucial role in the development of luminescent materials for light-emitting applications. In the same direction, the contribution of its sister concept “AIE switching” has been impressive. In comparison, the application of this concept in the field of biosensing or bioimaging is still in its infancy. Therefore, to shed light into the sensing of bioanalytes, we have developed a new perylenediimide (PDI)-based small fluorescent probe, benzoannulated PDI (Bp­(Im)2MA), that selectively detects diamines and biogenic amines (BAs) in solution via an “AIE-switching” phenomenon. The synthesized probe containing the bay-annulated anhydride moiety exhibits strong cyan emission in solution. In the mechanism, we have shown that the terminal free amine group of BAs readily reacts with a highly reactive anhydride moiety, which opens the cyclic anhydride moiety. In the open conformation, the free amine group along with a carboxylate group modulates the polarity of the system strikingly. Because of this induced polarity, the monomer of Bp­(Im)2MA-BAs conjugate aggregated in solution, thereby exhibiting a significant change in emission property in solution. This method may also be called a very simple and straightforward “naked eye” detection of BAs in solution, with a nanomolar detection limit. A detailed spectroscopic and microscopic investigation demonstrated the existence of the aggregated state. As the reporter dye also emits strongly in the solid state (yellowish orange), it therefore instantly made vapor-phase detection of BAs feasible. Finally, this vapor-phase detection of BAs by the probe was applied very effectively in the determination of spoilage of raw fish.

A Fluorescent Metal–Organic Framework for Food Real‐Time Visual Monitoring

“…The value of chromatism (Δ E * ab ) was quantified to represent the visual performance of probes. As shown in Figure 2d and Figure S13, Supporting Information, the Δ E * ab was much higher than those of many top‐performing ratiometric probes, such as MR@EuMOF, [ 16a ] CDs/CdTe QDs, [ 27 ] PFTBTCOOH/CS‐graft‐OA, [ 28 ] Bp(Im) 2 MA, [ 29 ] PAHO S , [ 30 ] and comparable with that of CA‐PpIX/CA‐FITC. [ 31 ] Additionally, unlike other ratiometric probes (green area: visualization methods), the linear range of our probe is highly overlapped with the BA index range (≈5–50 mg L −1 , the concentration range between fresh and spoiled food), implying its potential for visual monitoring of effective BAs concentration for the degree of food spoilage.…”

AIEgens: An emerging fluorescent sensing tool to aid food safety and quality control

“…One of the isomers (HMBA-4), whose nanoarchitecture showed best sensitivity to amines, was applied as indicators for monitoring meat spoilage. Ratiometric fluorescence assay can eliminate the interference of external factors, thus ensuring more accurate evaluation for trace analytes (Roy, Sajeev, Sharma, & Koner, 2019). Recently, Hu et al (2019) synthesized a battery of AIE active polyheterocycles with reversible ratiometric fluorescence response to protonation and deprotonation (Figure 4e).…”

Solid-Supported Amplification of Aggregation Emission: A Tetraphenylethylene–Cucurbit[6]uril@Hydroxyapatite-Based Supramolecular Sensing Assembly for the Detection of Spermine and Spermidine in Human Urine and Blood

“…In recent years, the focus has been on a novel class of fluorophores that fluoresce upon aggregation (i.e., AIEgens) − as they could largely address the fundamental issue of aggregation-caused quenching (ACQ) of conventional fluorophores. , Tetraphenylethylene (TPE) has emerged as the highest manifested aggregation-induced emission (AIE) moiety, − and a notable development within the field is the design of TPE-derived water-soluble amphiphiles as “light-up” probes for the detection of bioanalytes. − Coming back to biogenic polyamine sensing, a few reaction-based AIEgens are available for the sensing of SP and SPD. − Although some of them are sensitive methods, by design, they interact with a variety of biogenic polyamines in a nonspecific manner utilizing the amine functionality and thus, they are not selective to individual polyamines, which hampers efforts to identify specific polyamine profiles associated with certain diseases. This implies the role of host–guest recognition in imparting high selectivity.…”