Research PaperFacile fabrication of Tb3+-functionalized COF mixed-matrix membrane as a highly sensitive platform for the sequential detection of oxolinic acid and nitrobenzene
Graphical Abstract
Introduction
Oxolinic acid (OA) is a quinolone antibacterial drug, which has been extensively utilized to prevent and cure bacterial infections caused by Gram-negative bacteria of poultry and aquatic animals (Tu et al., 2006). Excessive OA in organism and aquatic environment systems will result in toxic impacts on aquatic organisms and human health (Tu et al., 2006, Pereira et al., 2013). As a simple nitroaromatic compound, nitrobenzene (NB) is highly toxic, acute carcinogenic, and difficult to degrade, which can lead to serious health and environmental problems (Li et al., 2019, Singh and Nagaraja, 2014, Vellingiri et al., 2017). Therefore, it is very valuable to manufacture an effective and selective sensor to monitor OA and NB in various actual environments. Currently, a variety of technologies, such as high-performance liquid chromatography (HPLC), spectrophotometric, spectrofluorometric, capillary electrophoresis (CE) and cyclic voltammetry (CV) have been applied for the determination of OA and NB (Pereira et al., 2013, Li et al., 2019). Nevertheless, these analysis technologies are commonly laborious, expensive, and time-consuming. Fluorescence analysis has drawn remarkable attentions due to its nondestructive emitting signals, rapid response, high sensitivity and low cost (Lian et al., 2017, Qu and Yan, 2019, Lian and Yan, 2019), thus it is appropriate and challenging to fabricate a fluorescent sensor for monitoring OA and NB in specific environments.
Covalent organic frameworks (COFs), as a new-type class of porous crystalline material, perform several advantages such as well-defined structure, tunable pore size and ordered pore structure, which can facilitate the controllable and precise structural synthesis of COFs (Zhao et al., 2019, Cote, 2005, Lohse and Bein, 2018). Furthermore, the high porosity, low density, ultra-high pore volume ratio, high chemical and thermal stability of COFs have led to a series of excellent applications involving sensing, adsorption, optoelectronics, drug delivery, separation and so forth (Li et al., 2017, Wang et al., 2021, Ren et al., 2021, Liu et al., 2022, Yu and Li, 2022, Haug et al., 2020). Therein, polyimide covalent organic frameworks (PI-COFs) have been synthesized through combining tetrahedral and linear building units based on imidization reaction, which perform outstanding chemical resistance and high thermal stability (Han et al., 2018, Chu et al., 2012). The considerable chemical stability and facile synthesis can provide PI-COFs as excellent matrix bodes for grafting lanthanide complexes or lanthanide ions to obtain luminescent Ln-COF materials by post-synthetic modification (PSM) (Zhong et al., 2020). For instance, Anna et al. created a TpBpy-COF grafted with Eu/Tb and Dy acetylacetone complexes, which has been successfully prepared as a luminescent thermometer (Kaczmrek et al., 2020). Chidharth’s group has decorated lanthanides on a two-dimensional imine COF (TTA-DFP-COF) and regulated the ratio of Eu3+/Tb3+ to acquire white-light emission (Krishnaraj et al., 2019). What’s more, Ln-COF materials can combine the good thermal and mechanical stability of COFs with the narrow emission bands, high luminescence intensity and color purity of lanthanide complex (Lian et al., 2017, Qu and Yan, 2019, Lian and Yan, 2019, Lian and Yan, 2018). Therefore, developing Ln-COFs based fluorescence sensor to determine chemicals will exhibit great prospects in the future.
Except the above-mentioned advantages of COFs, the problems such as insolubility and recycling difficulty have limited their sensing performances in actual environments (Gole et al., 2018, Sick et al., 2018). In order to effectively solve these problems, it is very necessary and feasible to employ membranes to replace powder samples during actual sensing because membranes are very convenient to be separated and can be reused in the cyclic experiment (Hou et al., 2011). Recently, the preparing methods of various pure COF membranes have made significant progress (Hao et al., 2021, Medina et al., 2015, Dey et al., 2017). However, due to the poor processability of COF materials, fabricating robust COF membranes will be a great challenge and it is meaningful to improve the stability and processability of COF membranes for practical sensing applications (Colson et al., 2011).
Incorporating micron or nano-sized crystals into polymer matrix to fabricate mixed-matrix membrane (MMM) has been fully treated as a feasible synthetic strategy (Kitao et al., 2017, Dechnik et al., 2017). As one of the most promising porous polymer membranes, polyvinylidene fluoride (PVDF) has been widely adopted to prepare MMM for chemical sensing because of its high thermal stability, mechanical strength and chemical inertness (Lee et al., 2016, Zhu et al., 2017). Based on encapsulating coordination polymers (CPs) into PVDF membranes, metal organic frameworks (MOFs) have been proven to be available in chemical sensing (Zhai et al., 2018, Zhang et al., 2018). For example, Li and coworkers prepared a luminescent CPs-doped PVDF MMM with resistance to moisture, being environmentally friendly, low cost and high response rate for detecting NB; Zhang and colleagues has synthesized an Al-MIL-53-NO2 MMM with outstanding flexibility and processability, which exhibited the highly selective and sensitive sensing ability for H2S detection. Owing to the organic framework, COFs exhibits excellent chemical compatibility with the organic polymer phase (Yang et al., 2018, Kang et al., 2016, Lu et al., 2015). COF-based PVDF MMMs combine the sensing properties of COFs with the excellent porous, flexibility and processability properties of PVDF to produce hybrid membranes with resistant to acid-alkali, environmental-friendly, low cost, facile preparation, flexibility and high detection sensitivity (Duan et al., 2019). In addition, this flexible MMM can not only detect analytes in aqueous solution, but also monitor gas pollutant. However, the researches on chemical sensing realized by flexible COF-based PVDF MMM has not been reported so far, which can be a challenge in future.
Herein, a Tb3+-functionalized PI-COF material (Tb3+@PI-COF) was prepared firstly by PSM, then a Tb3+@PI-COF MMM (M) was fabricated by incorporating the highly stable Tb3+@PI-COF as fillers and PVDF solution as membrane phase. In this work, M exhibited highly selectivity and sensitivity during the sensing detection for oxolinic acid (OA) and nitrobenzene (NB). Based on a “turn-on” response mode, M can be utilized for the selective detection of OA with a low detection limit (0.0686 µM) in the concentration range of 10−7–10−2 M. In the process of detecting OA, a green luminescent complex (M-15/OA) has been formed. During the detection of M-15/OA toward NB, M-15/OA exhibited a distinctive emission quenching with the low detection limit of 1.22 ppm and a fast “on-off” fluorescence switching process. This work offers a promising method for the combination of lanthanides with selective quinolones (OA) to prepare a novel luminescent sensor. Therefore, combining great sensing properties of the Tb3+@COF composite with the processability of the polymer makes this MMM sensor become a good candidate for practical sensing applications, as confirmed by employing M to quantitatively detect OA and NB under different conditions.
Section snippets
Synthesis of PI-COF
In the experiment, pyromellitic dianhydride (PMDA, 10 mmol, 2.18 g) and melamine (MA, 10 mmol, 1.26 g) with equal molar ratios were mixed to form a mixture. The mixture was ground for 30 min, then transferred to a crucible with a cover and heated to 325 °C with the heating rate of 5 °C min−1 under argon atmosphere for 4 h (Chu et al., 2012). The obtained pale-yellow products were collected, and washed with deionized water. The target products were dried at 80 °C overnight to obtain PI-COF. This
Characterization of PI-COF, Tb3+@PI-COF and M
The powder X-ray diffraction (PXRD) patterns of the PI-COF, Tb3+@PI-COF and M were shown in Fig. 2a. For PI-COF, the character diffraction is the same as previously reported (Han et al., 2018). The PXRD pattern of Tb3+@PI-COF can be matched well with PI-COF, for instance, the relatively strong diffraction peak at 2θ = 29.6° is in good agreement with the literature, implying the loading of Tb3+ doesn’t destroy the integrity and crystallinity of COFs (Han et al., 2018). In addition, the
Conclusions
In summary, Tb3+@COF nanoparticles are incorporated into PVDF polymer matrix, thereby obtaining a new type of Tb3+@COF MMM (M) for the first time. The flexible M-15 has successfully realized the detection of OA and NB, and the results proved that it has remarkable selectivity and sensitivity (0.0686 µM for OA and 1.22 ppm for NB, respectively). The anti-disturbance, as well as chemical stability in a wide pH range (3–12) make M-15 become the effective luminescent sensor toward OA in serum and
CRediT authorship contribution statement
Xuepin Quan: Conceptualization, Formal analysis, Writing – original draft. Xin Xu: Conceptualization, Formal analysis. Bing Yan: Funding acquisition, Supervision, Writing – review & editing.
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.
Acknowledgment
This work was supported by the National Natural Science Foundation of China (21971194) and Developing Science Funds of Tongji University.
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