Luminescent lanthanide metal-organic framework test strip for immediate detection of tetracycline antibiotics in water

https://doi.org/10.1016/j.jhazmat.2019.121498Get rights and content

Highlights

  • A highly sensitive and selective sensor for tetracycline antibiotics of OTC and TC in water is developed.

  • LOD for sensing OTC and TC is as lower as 1.95 and 2.77 nM, respectively

  • Low-cost and easy to use test strip is produced for in situ detecting OTC and TC in real water samples

Abstract

Tetracycline antibiotics (TCs) are a kind of commonly used antibiotics for treating infections, however, the overuse of TCs has adversely affected human health and the ecosystem. Thus, detection of TCs in water is important but challenging. In this work, a luminescent lanthanide metal-organic framework (LnMOF) sensor (1) for immediate detection of oxytetracycline (OTC) and tetracycline (TC) is developed. The sensor has high acid-base and water stability. Investigation reveals that among the 27 species of antibiotics, anions and cations under investigation, 1 shows highly selective sensing towards OTC and TC, and the detection is not disturbed by the presence of other species. The limit of detection (LOD) for OTC and TC are ultra-sensitive value of 1.95 and 2.77 nM, respectively. Investigation reveals the sensing mechanism is due to the inner filter effect. Further studies reveal that the sensor can be used in real sample monitoring. More importantly, test strips based on 1 are manufactured. They are an easy-to-use, low-cost, highly selective and sensitive sensing device for detecting OTC and TC. The sensing can be distinguished immediately and easily by the naked eyes, making it an excellent candidate to monitor OTC and TC in real use.

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).

References (90)

  • Y. Feng et al.

    Carbon dots derived from rose flowers for tetracycline sensing

    Talanta

    (2015)
  • L. He et al.

    A novel magnetic MIL-101(Fe)/TiO2 composite for photo degradation of tetracycline under solar light

    J. Hazard. Mater.

    (2019)
  • L. Hong et al.

    Inkjet printing lanthanide doped nanorods test paper for visual assays of nitroaromatic explosives

    Anal. Chim. Acta

    (2013)
  • M.S. Hosseini et al.

    Fabrication of capacitive sensor based on Cu-BTC (MOF-199) nanoporous film for detection of ethanol and methanol vapors

    Sens. Actuators B Chem.

    (2016)
  • S. Jabbari et al.

    A novel enzyme based SPR-biosensor to detect bromocriptine as an ergoline derivative drug

    Sens. Actuators B Chem.

    (2017)
  • Y. Kang et al.

    A microscale multi-functional metal-organic framework as a fluorescence chemosensor for Fe(III), Al(III) and 2-hydroxy-1-naphthaldehyde

    J. Colloid Interf. Sci.

    (2016)
  • M. Kurzawa et al.

    Electrochemical determination of oxytetracycline in veterinary drugs

    J. Pharm. Biomed. Anal.

    (2004)
  • L. Lan et al.

    Recent advances in nanomaterial-based biosensors for antibiotics detection

    Biosens. Bioelectron.

    (2017)
  • S. Li et al.

    Photolytic and photocatalytic degradation of tetracycline: effect of humic acid on degradation kinetics and mechanisms

    J. Hazard. Mater.

    (2016)
  • N. Li et al.

    Simultaneous removal of tetracycline and oxytetracycline antibiotics from wastewater using a ZIF-8 metal organic-framework

    J. Hazard. Mater.

    (2019)
  • K. Lun et al.

    Electricity-magnetism and color-tunable trifunction simultaneously assembled into one strip of flexible microbelt via electrospinning

    Chem. Eng. J.

    (2015)
  • A. Motorina et al.

    Hybrid silica-polyelectrolyte films as optical sensing materials for tetracycline antibiotics

    Sens. Actuators B Chem.

    (2014)
  • E. Pousaneh et al.

    Tetranuclear yttrium and gadolinium 2-acetylcyclopentanoate clusters: synthesis and their use as spin-coating precursors for metal oxide film formation for field-effect transistor fabrication

    J Rare Earth

    (2018)
  • S. Santaeufemia et al.

    Bioremediation of oxytetracycline in seawater by living and dead biomass of the microalga Phaeodactylum tricornutum

    J. Hazard. Mater.

    (2016)
  • L. Shen et al.

    Rapid colorimetric sensing of tetracycline antibiotics with in situ growth of gold nanoparticles

    Anal. Chim. Acta

    (2014)
  • M. Tabrizchi et al.

    Detection of explosives by positive corona discharge ion mobility spectrometry

    J. Hazard. Mater.

    (2010)
  • P. Vinas et al.

    Liquid chromatography with ultraviolet absorbance detection for the analysis of tetracycline residues in honey

    J. Chromatogr. A

    (2004)
  • G.H. Wan et al.

    Determination of tetracyclines residues in honey using high-performance liquid chromatography with potassium permanganate-sodium sulfite-beta-cyclodextrin chemiluminescence detection

    J. Chromatogr. B

    (2005)
  • X.-S. Wang et al.

    Fast, highly selective and sensitive anionic metal-organic framework with nitrogen-rich sites fluorescent chemosensor for nitro explosives detection

    J. Hazard. Mater.

    (2018)
  • P. Wang et al.

    Novel silver nanoparticle-enhanced fluorometric determination of trace tetracyclines in aqueous solutions

    Talanta

    (2016)
  • J. Xu et al.

    A novel visual ratiometric fluorescent sensing platform for highly-sensitive visual detection of tetracyclines by a lanthanide-functionalized palygorskite nanomaterial

    J. Hazard. Mater.

    (2018)
  • Z.-Q. Yan et al.

    Basophilic method for lanthanide MOFs with a drug ligand: crystal structure and luminescence

    Inorg. Chim. Acta Rev.

    (2015)
  • M.-Q. Yang et al.

    Highly sensitive and selective sensing of CH3Hg+ via oscillation effect in Eu-cluster

    Sens. Actuators B Chem.

    (2017)
  • K. Yang et al.

    Dual-channel probe of carbon dots cooperating with gold nanoclusters employed for assaying multiple targets

    Biosens. Bioelectron.

    (2017)
  • E.T. Yun et al.

    Oxidation of organic pollutants by peroxymonosulfate activated with low-temperature-modified nanodiamonds: understanding the reaction kinetics and mechanism

    Appl. Catal. B-Environ.

    (2018)
  • C.-H. Zeng et al.

    A polymorphic lanthanide complex as selective Co2+ sensor and luminescent timer

    Sens. Actuators B Chem.

    (2015)
  • F. Zhang et al.

    Mixed matrix membranes incorporated with Ln-MOF for selective and sensitive detection of nitrofuran antibiotics based on inner filter effect

    Talanta

    (2017)
  • X. Zhang et al.

    A stable lanthanide-functionalized nanoscale metal-organic framework as a fluorescent probe for pH

    Sens. Actuators B Chem.

    (2018)
  • K. Zheng et al.

    Highly luminescent Ln-MOFs based on 1,3-adamantanediacetic acid as bifunctional sensor

    Sens. Actuators B Chem.

    (2018)
  • D.S. Aga et al.

    Application of ELISA in determining the fate of tetracyclines in land-applied livestock wastes

    Analyst

    (2003)
  • G. Bao et al.

    A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

    Light-Sci. Appl.

    (2018)
  • V. Chernikova et al.

    Liquid phase epitaxial growth of heterostructured hierarchical MOF thin films

    Chem. Commun.

    (2017)
  • Z. Cui et al.

    Anionic lanthanide metal-organic frameworks: selective separation of cationic dyes, solvatochromic behavior, and luminescent sensing of Co(II) ion

    Inorg. Chem.

    (2018)
  • G. Fu et al.

    An efficient and weak efficiency-roll-off near-infrared (NIR) polymer light-emitting diode (PLED) based on a PVK-supported Zn2+–Yb3+-containing metallopolymer

    J. Mater. Chem. C Mater. Opt. Electron. Devices

    (2018)
  • W.-H. Huang et al.

    Water-stable metal-organic frameworks with selective sensing on Fe3+ and nitroaromatic explosives, and stimuli-responsive luminescence on lanthanide encapsulation

    Inorg. Chem.

    (2019)
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