Luminescent lanthanide metal-organic framework test strip for immediate detection of tetracycline antibiotics in water
Introduction
Tetracycline antibiotics (TCs), such as oxytetracycline (OTC) and tetracycline (TC) (Scheme S1) are one of the most commonly used antibiotics in the treatment of infectious diseases in human beings (Tsai et al., 2010). However, misuse or overuse of TCs can lead to high levels of antibiotic residues in water, which can result in the accumulation of TCs in the food chain, which in turn may bring about harmful effect to human health such as hepatotoxicity and gastrointestinal disturbance (van Houten et al., 2019; Li and Hu, 2016). In recent years, TCs are heavily used in the agricultural industry; effluents containing TCs from pharmaceutical factories are also damaging to the ecosystem (Santaeufemia et al., 2016). As one kind of organic compounds, TCs are hard to degrade (Abazari et al., 2019; Chen et al., 2019a; Yun et al., 2018; Chen et al., 2019b; He et al., 2019) and remove (Chen et al., 2019c; Li et al., 2019), and their overuse often results in the presence of residue TCs in ground water, surface water and drinking water (Santaeufemia et al., 2016), especially in developing and less developed countries. Therefore, the design and fabrication of the sensor for the detection of TCs has attracted great attention (Sheng et al., 2018).
In the last decade, numerous analytical methods have been reported for the determination of TCs. Sophicated instrumental methods including high performance liquid chromatography (HPLC) (Vinas et al., 2004), liquid chromatograph with tandem mass spectrometry (LC–MS) (Aguilera-Luiz et al., 2008), capillary electrophoresis (CE) (Wu et al., 2016) and capillary electrophoresis-mass spectrometric (CE-MS) (Tong et al., 2009) have been used to detect TCs (Tabrizchi and Ilbeigi, 2010; Shen et al., 2014). These methods show high sensitivity and accuracy (Tabrizchi and Ilbeigi, 2010; Shen et al., 2014), but they require expensive and complicated equipment, cumbersome and time-consuming sample pretreatment procedures, thus limiting their application (Yamamoto et al., 2013). Other methods such as electrochemical method (Yan et al., 2015a), optical fiber (Liu et al., 1998), fluorescent sensor (Xu et al., 2018a; Motorina et al., 2014), thin-layer chromatography (TLC) (Weng et al., 2003), enzyme-linked immunosorbent assay (ELISA) (Aga et al., 2003), and some other methods (Kurzawa and Kowalczyk-Marzec, 2004) are also successfully developed for the sensing of TCs with highly accuracy and sensitivity, but still exist some defects such as requirement of highly trained technical personnel or complicate sample pretreatment process (Lan et al., 2017).
Luminescent sensors are much more convenient on-site detection technology with short response time, high sensitivity and excellent operability (Bagheri et al., 2018). Luminescent lanthanide complex-based sensor has attracted much attention because of its numerous advantages (Zhang et al., 2018a; Fu et al., 2018; Liao et al., 2018; Manfrinetti et al., 2018; Xu et al., 2018b), such as high stability,(Huang et al., 2019) low bio-toxicity, high optical purity, line-like emission peaks, long luminescence lifetimes, large Stokes shift value, excellent upconversion property, tunable luminescence and antiphotobleaching (Kang et al., 2016; Yan et al., 2017; Yeung et al., 2017; Yan, 2017; Bao et al., 2018). Lanthanide complex/lanthanide metal-organic frameworks (LnMOF) have been reported to sense various species of metal ions (Lu et al., 2018; Liu et al., 2018; Cui et al., 2018; Zhao et al., 2016), anions (Wu et al., 2017), aromatic explosives (Li et al., 2018), biomarkers (Wu et al., 2018), pH (Zhang et al., 2018b), temperature (Cui et al., 2014), and can be used as multi-functional probe (Sun et al., 2017; Li et al., 2016). These documented results confirm the lanthanide complex and LnMOF are powerful analytical tool to sense various species (Xu et al., 2016). As a result, the functional combination of luminescent LnMOF and TCs sensor has become a promising and hot research topic (van Rosmalen et al., 2018).
As insoluble micro-sized coordination polymers (CPs) and metal-organic frameworks (MOFs) materials are usually not homogeneous in solutions, there are a growing number of investigations on how to prepare nanoparticles (Tian et al., 2018), coatings (Pousaneh et al., 2018), films (Zhu et al., 2013) and test strips (Lun et al., 2015). Until recently, there are several ways to make CPs or MOFs films, such as spin coating method (Yin et al., 2018), electrochemical approach (Linnemann et al., 2017), vapor phase synthesis (Tanaka et al., 2018), Langmuir-Schaefer technique over cross-linked asymmetric polyimide supports (Navarro et al., 2018), spin coating technique on a quartz crystal microbalance (QCM) (Chappanda et al., 2018), templated growth method on copper supports (Yoon et al., 2017); and sequential deposition of layers from two different MOFs (Chernikova et al., 2017). Most of these CP/MOF films made using these methods are based on transition metal complexes which cannot satisfy all the sensing applications (Hosseini et al., 2016). Moreover, lanthanide complex film is rarely reported (Kesama et al., 2016). Another portable device of the test strip that based on lanthanide complex is even less investigated than the lanthanide complex film (Hong et al., 2013). Thus, more effort should be devoted to invent a facile method for making mechanically robust test strips that based on lanthanide complex for satisfying more sensing applications.
Bearing in mind the above considerations, and based on the results of our previous works on luminescent lanthanide complex-based sensor (Wong et al., 2006; Zeng et al., 2015; Yang et al., 2017a; Zheng et al., 2018, 2015) and sensing device fabrication (Zhu et al., 2013), we herein developed a sensor to detect OTC and TC in water. The sensor has a formula of [Tb(HL)L(H2O)]n (1, H2L = salicylic acid), which is constructed by a drug of salicylic acid (Yan et al., 2015b). 1 has the following advantages as a specific probe for OTC and TC: (1) phenolic hydroxyl and carboxyl groups on the ligand can effectively coordinate with Tb3+, then sensitize the photo’s energy and transfer it to Tb3+ through the “antenna” effect; (2) the overlap between the UV-absorption spectra of OTC/TC and the excitation spectrum of 1 prevents the “antenna effect” in LnMOF due to the inner filter effect (Zhang et al., 2017), thereby causing luminescence quenching. The LOD for sensing OTC and TC are 1.95 and 2.77 nM, respectively. Furthermore, luminescent test strip based on 1 was produced with a facile method. The test strip is sensitive to detect OTC/TC, and the sensing results can be discriminated immediately and easily by the naked eyes.
Section snippets
Materials
Tb(NO3)3·6H2O was obtained in our lab by dissolving Tb4O7 (99.9%) with 64–68% HNO3, with the addition of plenty H2O2, and then evaporated at 100 °C until a crystal film was formed. In order to characterise the Tb(NO3)3·6H2O synthesized in our lab, X-ray photoelectron spectroscopy (XPS) experiment was conducted, and the result revealed there was only Tb3+, O and N in the product, implying the high purity of Tb(NO3)3·6H2O (Fig. S1) (Sienkiewicz-Gromiuk et al., 2016). Salicylic acid (H2L, 99%) was
Structure analyses
Fig. 1 shows that the PXRD pattern of the as-synthesized 1 matches well with the simulated peaks of single-crystal data (CCDC 1032281) (Yan et al., 2015b), indicating high phase purity of bulk sample 1. The second building unit of [Tb(HL)L(H2O)] consists of two Tb3+, two phenol hydroxyl and carboxyl deprotonated L, two carboxyl deprotonated HL, as well as two coordination H2O (Fig. S2a) to form an electroneutral unit. Tb3+ is coordinated by eight O atoms, which come from one coordination H2O,
Conclusion
In summary, an acid-base and water stable LnMOF sensor exhibits highly sensitive and selective sensing towards OTC and TC was developed. The selective detection is mainly based on the sensitive luminescence quenching of 1 by OTC and TC, and the quenching mechanism can be attributed to the inner filter effect. The LOD for OTC and TC are ultra sensitive values of 1.95 and 2.77 nM, respectively, which is comparable to the sophisticated method of HPLC. The high selectivity and immediate response
Declaration of Competing Interest
There are no conflicts to declare.
Acknowledgement
This work was supported financially by the National Natural Science Foundation of China (51962008 and 51472275).
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