Elsevier

Journal of Hazardous Materials

Volume 418, 15 September 2021, 126271
Journal of Hazardous Materials

Research Paper
Designed multifunctional ratiometric fluorescent probe for directly detecting fluoride ion/ dichromate and indirectly monitoring urea

https://doi.org/10.1016/j.jhazmat.2021.126271Get rights and content

Highlights

  • A multifunctional probe for detecting F- /Cr2O72- and urea was designed.

  • The probe was utilized for labeling F-/Cr2O72- in sweat latent fingerprint.

  • It was applied to evaluate the degrees of F-/Cr2O72- in cells and urea in serum.

  • The portable test strips of probe for F- and Cr2O72- was designed.

Abstract

UiO-66-NH2@eosin Y composite was obtained by confining eosin Y (EY) into the cavities of Zr-MOF and could emit two fluorescence peaks at 453 and 543 nm at an excitation wavelength of 355 nm. This multi-responsive and multifunctional ratiometric fluorescent nanoprobe not only enable directly distinct detection of F-/Cr2O72- with ultra-high selectivity and sensitivity, but also could indirectly monitor the concentration of urea based on unique enzymatic hydrolysis reaction. The multifunctional probe was utilized for fluorescence labeling F-/Cr2O72- in sweat latent fingerprint through an environmentally friendly powder strategy and exhibited obvious luminescence visualization changes. Notably, the corresponding portable on-line test strips of probe for detection of F- and Cr2O72- were made for monitoring the levels of F- and Cr2O72-. Furthermore, the probe was applied to evaluate the degrees of F-/Cr2O72- in HepG-2 cell and urea in serum with superior results,which indicate the potential application of the as-synthesized UiO-66-NH2@EY as multifunctional probe for the detection of F-, Cr2O72- and urea in biological samples. Finally, in order to extend the device-based applications of probe, an AND-OR-coupled molecular logic gate was put on agenda.

Introduction

Fluoride as a convenient commercial additive is frequently used in medical product, fluoridated toothpaste, and even drinking water owing to its important roles in normal human physiological activities (Singh and Singh, 2020, Jia et al., 2010). However, excessive ingestion of fluoride may result in dental fluorosis, nephrotoxicity/gastric disorders, and urolithiasis in humans, which pose a major threat to human health (Li et al., 2014, Liu et al., 2020a, Liu et al., 2020b, Liu et al., 2020c). As for Cr (VI), it is a kind of common sensitizer with strong irritation and corrosiveness showing much more toxic than Cr (III) (Lin et al., 2017a, Lin et al., 2017). Repeated or long-term exposure to chromium compounds can lead to chronic upper respiratory tract inflammation, chromium nose disease, contact dermatitis and so on. When the organism accumulates to a certain extent, it may even cause mutations in human genes (Wen et al., 2021, Wang et al., 2016). Similarly, urea, as the end product of protein metabolism from body, when the concentration of it in serum is much higher than that of normal value, the adults will suffer from glomerulonephritis, kidney disease, chronic pyelonephritis, in severe cases, it can develop a deadly form of uremia (Xu et al., 2016, He et al., 2018a, He et al., 2018b). Thus, it is great significance to detect fluoride ion, dichromate and urea rapidly and sensitively in environmental and biological systems (Guo et al., 2019, Liu et al., 2021).

In the past few decades, conventional analytical methods have been developed for the detection of F-, Cr2O72- or urea, including electrochemistry, inductively coupled plasma mass spectrometry, atomic absorption spectrometry, and solvent extraction (Maikap et al., 2018, Zhu et al., 2019a, Zhu et al., 2019b, Luo and Do, 2004). However, these analysis methods usually need expensive and sophisticated instrumentation (Chen and Yan, 2009).

Additionally, the complex sample preparation steps are also required (Yan et al., 2009). In order to optimize above problems, fluorescent sensors with outstanding properties, such as simple operation, low cost, short response time, and highly sensitivity, emerge (Zhang et al., 2015, Pu et al., 2010). Very recently, luminescent metal–organic frameworks (MOFs) are of bright promise as a new class of microporous sensing materials because of their ultrahigh surface areas, functionalized pore walls, excellent luminous properties, and diversified host-guest interactions (Mostakim et al., 2018, Wang et al., 2017). Upon to now, a variety of luminescent MOFs-based sensors have been extensively used for discrimination of F-, Cr2O72- or urea, but they were usually single-responsive, such as NH2-MIL-101(Al)-FITC (Hinterholzinger et al., 2013), Tb3+@Zr-MOF (Zheng et al., 2018), Enhanced-Zr-MOF (Zhu et al., 2019a, Zhu et al., 2019b) and SION-105 (Ebrahim et al., 2019), all of them were only sensitive to F-, whereas Dyes⊂MOF-801(Yoo et al., 2019), JLU-MOF50 (Sun et al., 2018), BUT-28 (Xu et al., 2018a, Xu et al., 2018) were utilized for specific detection of Cr2O72-. Meanwhile, Tran et al. (2017) has developed a Ni-MOF for determination of urea in urine samples with a detection limit of 3 µM, while an enzyme-capsulated Zn-MOF composites for sensing of urea through in situ growth approach on coreless fibers was fabricated by Zhu et al. (2020). However, when faced with the requirements of multiple analytes detection, the above single-responsive probes would suffer from some drawbacks, for instance, time-consuming, cumbersome, cost of multiple probe synthesis and single emission signal subject to interference (Mukherjee et al., 2020, Sun et al., 2019). In order to solve this situation, the multisensory system appeared in our vision, while most of them were single-functional and only could detect targeted analytes in solution, requiring trained personnel to gather results from professional instrument (Wu et al., 2017a, Wu et al., 2017b; Xv et al., 2018). The detection process was not portable, and hence cannot be used for in situ monitoring at demanding places (Wang and Chen, 2020; Wang et al., 2020; Liu et al., 2014; Zhang et al., 2018). Meanwhile, most of the reports are based on non-ratio fluorescence changes to realize detection, which are easily disturbed by environmental factors (interference of probe concentration, light source, test equipment and measurement conditions), in addition, the biological studies of them were rarely unexplored (Li et al., 2020, Ma et al., 2014). Furthermore, in recent decades, lots of fluorescence-based sensing system are applied to Boolean logic operation. Based on it, the complex identification signals for analytes can be expressed through simple numbers “0” and “1”, which is more intuitive (Zhang et al., 2016, Xu et al., 2017). Notably, until now, no multi-responsive probe has been designed that can parallelly recognize inorganic fluoride ions, dichromate and small organic molecule urea. Alternatively, the probe with a broad range of applications (biology and environment) is more effective, which could integrate multiple probes into one that greatly reduce the consumption of synthesis for single probe.

In addition, EY, a good-photostability and low-toxicity organic dye, is often acted as fluorescent inlaid molecule (Li et al., 2019). In order to construct a dual-emitting probe, EY was embedded into the large-cavity of the UiO-type MOF, which possess 3D network structure and can restrict the releasing of loaded dyes. Here, the amino-functionalized UiO-66-NH2 with blue emission was more preferred that often used as postmodified precursor framework (Du et al., 2017, Yu et al., 2019).

In this study, a multi-responsive multifunctional ratiometric fluorescent (RF) probe(UiO-66-NH2 @EY)was constructed by encapsulating EY molecules into the cavity of Zr-MOF(Scheme 1), which could parallelly and directly identify of F- and Cr2O72-, then, after introduction of urease, the pH-sensitive probe would also be used to realize the biorecognition of urea based on unique enzymatic hydrolysis reaction.

The detection process of F- was achieved by hydrogen bond effect and the recognition of Cr2O72- is based on energy competition transfer mechanism, finally, through catalyzing the hydrolysis of urea with a special urease, the pH value of the probe system changes, thus, the sensing of urea could realize indirectly by monitoring the fluorescence change caused by pH value. Notably, to our delight, the multi-applications of probe have been fully investigated. The relevant portable on-line fluorescent test strips and solid powder of probe for rapid detecting F- /Cr2O72- have been conducted, which may be utilized to label F-/ Cr2O72- in polluted environment through colorimetric visual changes. Further, the bioimaging phenomenon shows that the UiO-66-NH2 @EY possesses excellent biocompatibility that is suitable for monitoring the levels of F- and Cr2O72- in HepG-2 cells, meanwhile, the results of evaluating urea concentration in diluted serum samples are also superior. Finally, the ions-triggered luminescence switching of toxic F-/Cr2O72- is further explored by the AND-OR-coupled molecular logic gate, which could exhibit as an indispensable molecular device to support complex logic operation. In view of the above facts, an effectively portable multifunctional fluorescence technique was fabricated, which could quickly identify the targeted analytes in environment and cells/serum by chromogenic/fluorescent changes.

Section snippets

Chemicals and instruments

ZrCl4, 2-amino-1,4-benzene dicarboxylate (BDC-NH2), EY molecule (a classic xanthene dye) and glacial acetic acid was purchased from Shenyang Laibo Electronics Co. All the reagents and solvents were commercially available and used as received without purification. The X-ray powder diffraction patterns of UiO-66-NH2 andUiO-66-NH2@EY were performed by Bruker D8 diffractometers using Cu Kα radiation. S-4800 scanning electron microscope (SEM) (Hitachi, Japan) was used for conducting the morphology

Characterization and photoluminescence studies of UiO-66-NH2@EY

In Fig. 1A, it can be seen that the UiO-66-NH2 presents representative Fm3m symmetric space group matches well with the reported literature (Wu et al., 2017a, Wu et al., 2017b), indicating the successful synthesis of the UiO-66-NH2. After packaging EY, the diffraction peaks of the UiO-66-NH2@EY are almost unchanged compared to UiO-66-NH2, which demonstrate that the introduction of EY did not affect its crystal structure.

The SEM pattern of Fig. 1B shows the octahedral structure of UiO-66-NH2

Conclusions

In summary, a multi-responsive and multifunctional RF probe UiO-66-NH2@EY was developed, which can selectively and parallelly recognize F-, Cr2O72- and small organic molecule urea by unique detection characteristics and mechanisms. The application of probe was diversified that can not only be applied to biological and ecological environment for related analytes detection but also used for design of molecular logic gates. Here, the UiO-66-NH2@EY exhibits superior detection performance that

CRediT authorship contribution statement

I have made substantial contributions to the conception or design of the work; or the acquisition, analysis, or interpretation of data for the work; I have drafted the work and revised. All persons who have made substantial contributions to the work reported in the manuscript, professor Lei Zhang provided editing and writing assistance. All authors approved the final version to be published; Author signature: Yaqiong Zhang, Lei zhang.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This project was supported by National Nature Science Foundation of China (NSFC 51672116) and (NSFC21707061), Liaoning Province Science and Technology Planning Project (No. 20180551203).

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