Hybrid Copper Iodide Cluster-Based Pellet Sensor for Highly Selective Optical Detection of o-Nitrophenol and Tetracycline Hydrochloride in Aqueous Solution

Abstract

o-Nitrophenol (o-NP) and tetracycline hydrochloride (TCH) residues in various aquatic environments are two environmental contaminants, which are seriously dangerous to both social safety and the environment. Detection of such species in a water system with one optical sensor is coveted for outdoor operation but has not been reported. Herein, we report the function synergistic strategy for the construction of a stable and luminescent hybrid copper­(I) iodine cluster-based sensor [Cu4I4(ETBT)4] (UJN-Cu2, ETBT = 2-ethylbenzo­[d]­thiazole). A custom-designed detecting cell for a solid sensor is used to detect the two types of contaminations. The pressed pellet of UJN-Cu2 is capable of photoluminescence distinguishing o-NP from its two isomers p-NP and m-NP, as well as TCH from commonly used antibiotics in aqueous solutions. Importantly, UJN-Cu2 represents the first bifunctional luminescence sensor for highly selective and sensitive detection of o-NP and TCH with a limit of detection (LOD) of 2.30 and 4.15 μM, respectively. Theoretical calculations and experimental results indicate that the charge transfer between Cu and ETBT is responsible for the excitation spectrum centered at 394 nm, which has a superior overlap with the absorptions of o-NP and TCH. The UJN-Cu2 pellet optical sensor has obvious advantages including being extremely easy to carry and use, dual-detection ability, and excellent recyclability and sensitivity, which make it is suitable for a long-time in-field outdoor detection application. The present work not only develops the first dual-detection optical sensor for nitroaromatics and antibiotics but also unveils the feasibility of the hybrid copper­(I) iodine cluster as a solid sensor in hunting environmental pollutants.

Innovative Dual-Emitting Ratiometric Fluorescence Sensor for Tetracyclines Detection Based on Boron Nitride Quantum Dots and Europium Ions

“…Tetracyclines (TCs), including tetracycline (TET), oxytetracycline (OXY), and doxycycline (DOX), have been extensively employed for the prevention and control of microorganic infections because of the broad-spectrum antibacterial effect, availability, and low cost. However, the overdose or long-term low dose use of TCs can lead to residues in animal products, which would cause direct toxicity, liver damage, allergic action, and bacterial resistance . In order to ensure food security and protect consumer health, several countries have defined the maximum residue limits (MRLs) for TCs residues in animal-based foods.…”

Polytorsional-amide/carboxylates-directed Cd(ii) coordination polymers exhibiting multi-functional sensing behaviors

“…It is found that the fluorescence lifetime of the complexes has almost no change before and after quenching, which indicates that the fluorescence quenching phenomenon is mainly caused by the static quenching effect mechanism. 78 …”

State of the art methods and challenges of luminescent metal–organic frameworks for antibiotic detection

“…6a). 85 The lifetime of NJU-Cu2 centred at the emission peak of 578 nm was ∼6.21 μs. This strong emission is ascribed to the charge transfer triplet excited state between Cu and the ligand, which is consistent with previous relevant mechanism studies of the copper iodine cluster.…”

“…83 Recently, two Cu x I y -based LMOFs have been reported as luminescence sensors for monitoring antibiotics. 84,85 In 2018, G. Liu et al synthesized a novel chair-like [Cu 4 I 4 ] cluster-based LMOF, [Cu 4 I 4 (EBT) 5 ] (UJN-Cu, EBT = 3-ethyl-1,3benzothiazole-2-thione) (Fig. 5a).…”