Concentration-Guided Visual Detection of Multiphase Aliphatic Biogenic Amines through Amine–Phenol Recognition Using a Dual-State Emitter

Abstract

Intermolecular amine−phenol interactions are largely recognized as unique models with diverse supramolecular interactions. However, fluorescence (FL) variations originating from such interactions are rare. Herein, FL changes are well realized from amine−phenol interactions to identify an important biomarker, biogenic amines (BAs). A simple, inexpensive, and thermally stable anthracenylphosphonate is linked with 2,2′biphenol to design a functional dual-state emitter. Among the various amines tested, this emitter displays superior sensitivity with the lowest possible limit of detection as 5.8−9.7 ppb with aliphatic polyamines such as 1,3-, 1,4-, 1,5-, and 1,6-diamines and spermidine in the solution phase. Fast, on-spot detection of the BA vapors was visually conducted through a notable high-contrast change from blue to yellow emission in the solid state. FT-IR, 1 H/ 31 P NMR, and mass spectroscopic studies identify the groundstate amine−phenol interactions. The failure in BA detection with the 2,2′-dimethoxy-biphenyl-linked analog verifies the role of amine−phenol interactions. Mechanistic studies determine amine−phenol interactions in the ground and excited states. The molecular structure and packing of the doubly twisted probe are documented with a substantial void space facilitating close contact of the BAs with the strong amine−phenol interactions desired for efficient detection. Finally, this probe governs the freshness of a piece of Catla catla fish and prawn. Further, a remarkable concentration-controlled diverse emission with a red shift difference of 141 nm is detected with 1,3-diaminopropane (1,3-DAP) vapor (from 29 to 319 mg/L) for the first time. Thus, a cost-effective device is developed to detect 1,3-DAP at a precise concentration, visible through the naked eye.

Design of Highly Efficient Electronic Energy Transfer in Functionalized Quantum Dots Driven Specifically by Ethylenediamine

“…Furthermore, the successful synthesis of the QDs-Chromone is verified by the appearance of H in the aromatic ring within δ 7.5–9. Moreover, the signals of H in the aromatic ring shift to the upper field (from around δ 8 to around δ 7), and the appearance of H in the amidogen around δ 3 indicates the ring cleavage and the formation of the hydrogen bonds (N–H···O and O–H···O) which resulted in the expansion of the conjugate plane structure . Subsequently, the tiny emission band change of QDs before and after modification of MPA and chromone, together with the appearance of fluorescence intensity in the low wavelength region of QDs-Chromone verify the successful modification from another aspect, which also brings out the change of fluorescence from bright red to dark red and purple (Figure S6).…”

Concentration-tuned diverse response to selective biogenic amines using a reusable fluorophore: monitoring protein-rich food spoilage

“…17,18 Therefore, developing a handy and portable sensor for rapid on-site BA detection is essential. In response to these challenges, various cost-effective optical-based sensors have emerged as sensitive protocols; 19–22 however, the pitfalls of these probes include (i) non-reusability and poor color-contrast, (ii) scarcity of dyes for concentration-tuned detection of BAs (an urgent need to avoid food wastage) (iii) multistep synthesis of the probe using a high energy-consumption protocol (iv) restriction to solution state emission only (v) lack of sensitivity and selectivity (vi) most importantly, lack of vapor-responsive dyes, and (vii) practical applicability for effective and quick testing of chicken or fish. 23–25 Moreover, a typical fluorophore shows its response only by fluorescence quenching mechanism via a chemical reaction of an amine with an electrophilic center (emission quenching is not preferred due to misguided promises).…”

Isomeric Benzenediol-Linked Organophosphonates as a Handy Reusable Emitting Platform: Diversity in Polyamine Vapor Detection

“…In the context of the previous result, the following queries arise: Is the 1,1′-biphenyl-2,2′-diol system required to make a solid-state emitter? Will only 1,2-dihydroxybenzene (catechol) serve the purpose?…”

“…Does the phosphonate group play any role? Hydroxybenzene (phenol)-linked anthrylphosphonate was not responsive to the PAs vapor, but what about if it is connected to more acidic 1,3-dihydroxybenzene (resorcinol)? Herein, we design and conveniently afford a comparatively smaller analog without compromising the solid-state emission features.…”

“…Instead, we preferred designing only phosphonate-based emitters to detect PAs. In this context, a recent design on amine–hydroxy interactions using a 1,1′-biphenyl-2,2′-diol-linked emitter D for PA detection appeared promising, but it requires column purification and lacks selectivity . While dealing with D , it was realized that only a phenol-linked analog is insufficient to detect PAs .…”