Next Article in Journal
Improving the Robustness of Time Difference of Arrival Estimation Based on the Energy Center of Gravity Rearrangement
Previous Article in Journal
Assessing Gait & Balance in Adults with Mild Balance Impairment: G&B App Reliability and Validity
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Sensors
Volume 23
Issue 24
10.3390/s23249719
sensors-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

A Soluble Porous Coordination Polymer for Fluorescence Sensing of Explosives and Toxic Anions under Homogeneous Environment

by
Jiang Jiang
1,†,
Zi-Wei Li
2,†,
Zhao-Feng Wu
2,* and
Xiao-Ying Huang
2
1
College of Life Sciences, Fujian Agriculture and Forestry University, Fuzhou 350002, China
2
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou 350002, China
*
Author to whom correspondence should be addressed.
†
These authors contributed equally to this work.
Sensors 2023, 23(24), 9719; https://doi.org/10.3390/s23249719
Submission received: 16 November 2023 / Revised: 5 December 2023 / Accepted: 6 December 2023 / Published: 9 December 2023
(This article belongs to the Section Chemical Sensors)
Browse Figures
Versions Notes

Abstract

:
In the past decades, porous coordination polymers (PCPs) based fluorescent (FL) sensors have received intense attention due to their promising applications. In this work, a soluble Zn-PCP is presented as a sensitive probe towards explosive molecules, chromate, and dichromate ions. In former reports, PCP sensors were usually ground into fine powders and then dispersed in solvents to form FL emulsion for sensing applications. However, their insoluble characters would cause the sensing accuracy which is prone to interference from environmental effects. While in this work, the as-made PCP could be directly soluble in organic solvents to form a clear solution with bright blue emission, representing the first soluble PCP based fluorescence sensor to probe explosive molecules under a homogeneous environment. Moreover, the FL PCP solution also shows sensitive detection behaviors towards the toxic anions of CrO42− and Cr2O72−, which exhibit a good linear relationship between the fluorescence intensity of Zn-PCP and the concentrations of both analytes. This work provides a reference for designing task-specific PCP sensors utilized under a homogeneous environment.

1. Introduction

The past two decades have witnessed the great progress made in fluorescent porous coordination polymers (FL-PCPs) and their applications in lighting, sensing, imaging, and so forth [1,2,3,4,5]. Thus far, most of the reported fluorescence PCPs are constructed from rare-earth metal ions due to the bright emission and abundant emission colors [6,7,8,9]. However, the rare-earth metal resource is limited and has been widely utilized in other strategic industries; thus, it is desirable to develop FL PCPs on basis of other abundant metals. On the other hand, the fluorescence detecting processes are prone to interference from environmental effects, e.g., the concentration of FL materials, excitation intensity, temperature, instrumental parameters, and so forth [10,11,12,13]. Therefore, it is still challenging to design novel types of FL PCP probes with high accuracy and sensitivity.
In the general detection procedure, the as-made PCPs have to be ground into fine powder and dispersed in a specific solvent to form a comparatively stable fluorescence emulsion. Then, the fluorescence detection is carried out by adding the analytes into the fluorescence emulsion and then the change of the FL intensity is recorded by a FL spectrophotometer [14,15]. As we know, most PCPs are insoluble in common solvents, which unavoidably results in the inadequate dispersion for the subsequent sensing experiments. As a result, under such an inhomogeneous system, the non-uniformity of the particle size, the unavoidable PCP particle movements, etc., are inevitable interferences which would affect the accuracy of the fluorescence detection. Therefore, it would be much more desirable to develop soluble FL PCPs that could work under a homogeneous circumstance.
On the other hand, chemical sensors designed for molecules involved in safety and health issues with high sensitivity and selectivity are of great importance in the field of materials science. Carbon disulfide (CS2) is an important chemical in the preparation of viscose rayon fibers, but as a volatile organic solvent, it also can become a neurotoxin. It could trigger atherosclerosis and coronary artery disease by exposure at an extended concentration level [16,17,18]. In addition, the nitroaromatic compounds have been widely utilized in varied areas. For example, nitrobenzene is a chemical specifically used in medicine while those bearing di- or tri-nitro groups are well known as high explosives. However, they can also be notorious environmental pollutants causing serious health and safety problems [19,20]. Thus far, the most regular way to detect CS2 and nitroaromatic molecules is based on sophisticated analytical instruments and well-trained canines with professional skills [21,22], which might hinder its wide applications, especially in undeveloped areas. Therefore, developing sensitive and selective fluorescence sensors towards these analytes would be a significant but a challenging task.
Bearing these in mind, a Zn-PCP is presented in this work which could be soluble in organic solvents, e.g., N,N′-dimethyl formamide (DMF), dichloromethane (CH2Cl2), and 1,4-dioxane [23,24]. Interestingly, Zn-PCP exhibits an aggregation induced quenching fluorescence after dissolving in solvents. The clear solution emits a bright blue light after being diluted to a low concentration. The emissive solution shows a sensitive fluorescence quenching effect towards nitro-bearing molecules, including but not limited to nitrobenzene, nitroaniline, and nitrophenol. Moreover, it also shows a sensitive fluorescence quenching performance towards dichromate and dichromate ions, demonstrating its detecting ability for toxic metal ion species, Figure 1. As far as we are aware, the fluorescence detection in a homogeneous system using a soluble FL PCP has never been reported up to date.

2. Experimental Details

2.1. Materials and Methods

All reagents and chemicals were purchased from commercial sources and used without further purification. The UV-Vis absorption spectra were measured at room temperature using a Perkin-Elmer Lambda 900 spectrometer. Powder X-ray diffraction (PXRD) patterns were collected in the angular range of 2θ = 3–60° on a Miniflex II diffractometer using CuKα radiation. Fluorescence spectra of the compounds in the solid state and FL sensing experiments were recorded on a PerkinElmer LS55 FL spectrometer at 298 K. Fourier transform infrared (FTIR) spectra were recorded on a Vertex70 IR spectrometer at 298 K. Energy dispersive spectroscopy (EDS) and the scanning electron microscope (SEM) were conducted using a JEOL JSM-6700F scanning electron microscope.

2.2. Syntheses of Zn-PCP

The synthesis was carried out according to the procedures in the former article with a slight modification [23,24]. In a typical synthesis, 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobisindane (TTSBI) (0.375 mmol), tetrafluoroterephthalonitrile (0.4 mmol), Zn(OAc)2 salt (0.125 mmol), and K2CO3 (300 mg) were mixed and ground in a mortar over 30 min, and the resulting mixture was washed throughout with deionized H2O and methanol (Figure 1). The final powder of Zn-PCP was dried at 333 K for 12 h. The as-made sample could be soluble in CH2Cl2, DMF, or 1,4-dioxane to afford clear green solution.

2.3. Fluorescence Sensing Measurements

The Zn-PCP dissolved in different solvents was prepared by adding 1 mL DMF solution of Zn-PCP (1 mg/mL) into 1 mL organic solvents; for fluorescence sensing, 2 mg Zn-PCP was dissolved in 2 mL DMF and the solution was placed in a quartz cell of 1 cm width, and then a pipette was used to add 10−2 M nitrobenzene, nitro-molecule ethanol solution, o-nitrophenol, o-nitroaniline, 10−3 M 2,4-dinitroaniline, and TNP or 10−2 M Cr-bearing anion solutions into the Zn-PCP solution to record the fluorescence signal. For all the detection measurements, the fluorescence solutions of Zn-PCP were excited at 425 nm while monitoring the corresponding emission wavelengths from 450 nm to 650 nm.

3. Results and Discussions

The Zn-PCP was prepared through the solid-state interaction of TTSBI ligand bearing -OH groups, tetrafluoroterephthalonitrile and Zn2+ ion in a solid state under a base condition (Figure 1) [23,24]. To certify the successfully synthesis of the Zn-PCP, many measurements including but not limited to X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), the scanning electron microscope (SEM), and Fourier transform infrared (FTIR) spectra have been conducted. As shown in Figure 2a, the SEM measurement demonstrated the as-made Zn-PCP sample was made up of interconnected and aggregated particles with μm sizes. No K and F elements were detected by EDS measurement for the as-made sample, indicating F was removed through coordination reaction while the residual K2CO3 was clearly removed by washing the samples, Figure S1. The Zn, C, N, O components were further identified by elemental mapping images, revealing specifically Zn element was distributed uniformly in the as-made Zn-PCP particle (Figure 2a and Figure S2). The XPS was applied to analyze the surface chemistry of the as-made Zn-PCP (Figure 2b and Figure S3). As depicted in Figure 2b, there are two energy bands maximized at 1022.8 and 1045.9 eV, which are typical values ascribed to the Zn 2p 3/2 and 2p 1/2 electrons of Zn2+ ions. The successful coordination between the ligands and Zn2+ ions could be identified by the sharp decrease of -OH vibrational peak around 3300 cm- in FTIR spectra for the as-made Zn-PCP sample (Figure S4) [23]. However, PXRD of the as-made sample indicates Zn-PCP exhibits the amorphous character, which is in accordance with the former research (Figure S5) [23]. The unique folding conformation of TTSBI was transferred to the as-made Zn-PCP through coordination polymerization, resulting in the porous structure by stacking of the zigzag polymer chains (Figure 3a) [23]. The as-made Zn-PCP is soluble in solvents such as DMF, CH2Cl2, and 1,4-dioxane, which is in accordance with the former research (inset in Figure 3b) [24]. Zn-PCP exhibits no fluorescence at the solid state, but it could emit a bright blue emission maximized at 475 nm after dissolving into DMF. The FL intensity shows some extent of increase by diluting the concentration from 1 to 0.05 mg/mL, and then the FL intensity begins to decrease, exhibiting an aggregation-induced quenching fluorescence (Figure 3b). The chromaticity coordinate for the sample of 0.05 mg/mL is (0.15, 0.21) when monitored at 425 nm excitation wavelength (Figures S6 and S7). The fluorescence of the TTSBI and tetrafluoroterephthalonitrile are also measured to investigate the origin of the luminescence for Zn-PCP. As seen in Figures S8 and S9, the TTSBI exhibits fluorescence with a monochromatic band maximized at 430 nm excited by 360 nm light, while the tetrafluoroterephthalonitrile shows a green emission with two bands maximized at 470 and 540 nm excited with 420 nm light, respectively. Therefore, the origin of the fluorescence would arise from the organic ligands centered (LC) luminescence. The single emission band of the as-made Zn-PCP shows some extent of blue and red-shift compared with that of the TTSBI and the etrafluoroterephthalonitrile ligands. The emission shift might be caused by the energy transfer between the metal ions and linkers after being assembled into the framework materials [1,2,3].
Then, we investigated the potential fluorescence sensing applications of the Zn-PCP solution. As shown in Figure 4a, the common lab solvents have almost no influence on the fluorescence of Zn-PCP solution except for some extent of changes in their fluorescence intensity. Impressively, it shows an obvious quenching response by adding CS2 into the fluorescence solution, demonstrating a selective sensing performance of Zn-PCP towards CS2. As we know, although CS2 has been widely used in industrial applications, the bad smell and potential leaking risk also could cause environmental and health issues [25,26]. Therefore, compared with the conventional physicochemical detecting methods usually suffering from expensive instruments, professional technicians, and hard popularization in undeveloped areas [27,28,29], it is desirable to explore a more convenient and economic fluorescence sensing way based on FL materials. The detection sensitivity for CS2 is further investigated in detail. As depicted in Figure 4b, more than 60% fluorescence intensity is quenched after only 10 μL CS2 is being added into the emulsion with only a volume ratio of 0.5 vol% (the volume percentage of CS2 in 2 mL Zn-PCP solution, inset of Figure 4b). The sensing sensitivity is comparable to that of Mg5(OH)2(BTEC)2(H2O)4·11H2O (H4BTEC = 1,2,4,5-benzenetetracarboxylic acid) which could quench 66% of its fluorescence by adding 10 uL CS2 into the FL emulsion [30], but it is much more sensitive than that of other PCP sensors such as Zr6(µ3-O)4(OH)8(tcbpe)2(H2O)4 (H4tcbpe = 4′,4‴,4′′′′′,4′′′′′′′-(ethene-1,1,2,2-tetrayl) tetrakis(([1,10-biphenyl]-4-carboxylic acid)) and [Mg2Zn2(OH)2(1,4-NDC)3(H2O)2]·6H2O (1,4-H2NDC = 1,4-naphthalene dicarboxylic acid) which can quench more than 60% FL intensity of the emulsions at a concentration of 1.0 vol% and 1.5 vol% CS2, respectively [31,32]. According to the former research involving both experimental measurements and DFT calculation results, the interactions occurring between the CS2 and the organic linkers in Zn-PCP with the C-H bonds might cause the electron transfer process and quench the fluorescence [32].
To our knowledge, nitro-bearing compounds are of great importance to industries and militaries. However, their distinct characters, especially the explosive and toxic characters, also pose a threat to life safety and national security [33,34]. Impressively, the fluorescence solution of Zn-PCP exhibits very sensitive fluorescence quenching behaviour to nitro-bearing compounds. As seen in Figure 5a, as with the sensing of CS2, the fluorescence intensity of the Zn-PCP is reduced gradually by adding a 10−2 M ethanol solution of the nitrobenzene. To quantitatively analyse the quenching effect, the SV equation of I0/I = 1 + Ksv[M] (I0 and I are the luminescence intensity of the fluorescence solution without and with addition of quenching molecule, and [M] is the molarity of quencher and Ksv is the quenching constant) is analysed. As shown in Figure 5b, the SV plot displays a very good linear behaviour with R2 = 0.99756, and the Ksv value is calculated to be 0.54 × 103 M−. The detection limit value is 1.60 × 10−1 M calculated from 3δ/slope. On basis of the same fluorescence detecting procedure, the sensing experiments of Zn-PCP towards o-nitrophenol and o-nitroaniline are also performed. As seen in Figure 5c,d, the Zn-PCP also exhibits sensitive fluorescence quenching performances after addition of the 10−2 M o-nitrophenol and o-nitroaniline into the FL Zn-PCP solution. The SV plots also display a good linear behaviour with high R2 values. Accordingly, the Ksv values are calculated to be 0.106 × 104 and 0.685 × 104 M−, respectively (Figures S10 and S11). The detection limit values are 8.17 × 10−2 and 1.26 × 10−2 M, respectively. The comparative and sensitive quenching results demonstrate the universal sensing performances of Zn-PCP towards nitro-molecules. The sensing performance towards 2,4-dinitroaniline exhibits much more sensitivity than that for the nitro-quenchers with a mono-nitro group. As depicted in Figure 5e, the fluorescence could be quenched more than 60% when only 10 μM 2,4-dinitroaniline is added into the fluorescence solution, and the SV plots show a good linear relationship with R2 of 0.99475 and the Ksv is calculated to be 0.15 × 105 M− (Figure S12). The detection limit value is 5.78 × 10−3 M. Based on the Ksv value for comparative study, the sensing performance towards 2,4-dinitroaniline is comparable to that of the porous Mg5(OH)2(BTEC)2(H2O)4·11H2O with Ksv value of 2.35 × 104 M− [30], demonstrating the potential applications in selective fluorescence detecting for nitro-bearing explosives.
As we know, the trinitrophenol (TNP) is a classic representative of explosive molecules. Here, the fluorescence sensing experiment to TNP is also performed using the same experimental procedures. As shown in Figure 5f, the fluorescence Zn-PCP solution exhibits the most obviously quenching behavior towards TNP, and the fluorescence intensity could be quenched more than 50% when only 7.5 μM TNP is added into the fluorescence solution. The R2 = 0.9915 indicates the accuracy and sensitive sensing performance. The Ksv value of 0.16 × 106 M− is two magnitudes of enhanced sensing sensitivity than that of o-nitrophenol and o-nitroaniline (Figure S13). The detection limit value is 5.42 × 10−4 M. The reported PCPs for sensing of TNP are listed in Table 1 for a comprehensive study. As shown in Table 1, using Ksv value as a reference, the TNP detection sensitivity of Zn-PCP is comparable and even better than those of other fluorescence PCP sensors. These PCPs are regularly constructed based on transition or rare earth metal ions, which have to be ground into powder and dispersed in solvents for conducting fluorescence sensing measurements [35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50].
The Zn-PCP not only exhibits a sensitive detecting response to explosive molecules but also shows a fluorescence quenching performance to toxic metal ion species. As we know, the excess Cr3+, especially Cr6+ ions, can lead to deformity, and Cr-containing wastes have become a serious environmental issue [51,52]. Therefore, finding a sensitive chemical sensor towards Cr-bearing pollutants is of great significance to probe the environment and health problems. As depicted in Figure 6a,c, the fluorescence intensity of Zn-PCP solution could be significantly decreased gradually by adding 10−2 M solutions with CrO42− and Cr2O72− anions that acted as fluorescence quenchers. With the addition of CrO42− into the FL Zn-PCP solution in an incremental way, the fluorescence intensity quenches obviously, and the quenching percentage exhibits a good linear relationship with the concentration of quencher, Figure 6a. The linear SV plot displays a high R2 value of 0.998, and the Ksv value is 0.14 × 104 M−, Figure 6b. While for sensing of Cr2O72− anions, the fluorescence intensity of Zn-PCP could be quenched more than 50% when adding only 50 μL quencher, indicating a sensitive sensing performance to Cr2O72−, Figure 6c. As shown in Figure 6d, the SV plot also exhibits an excellent probing accuracy with an R2 value of 0.99475 and the Ksv value is calculated to be 0.15 × 105 M−. The detection limit values for CrO42− and Cr2O72− are 6.19 × 10−2 and 5.78 × 10−3 M, respectively. The probing sensitivity could be comparable to the porous transition or rare earth metal-based CP sensors [53,54,55]. Both the sensitive behaviors and the sensing accuracy demonstrate the advantages of using soluble PCP as a fluorescence sensor in probing dangerous and toxic species under a homogeneous environment.
As we are aware, due to the presence of low-lying unoccupied π* molecular orbitals, the nitroaromatic molecules are generally accepted to be efficient acceptors for electrons from fluorophores in their excited state, resulting in the fluorescence quenching response [56,57,58,59]. The sensing sensitivity in detecting nitro-bearing molecules follows the orders of Ksv values of mono- (o-nitrophenol, o-nitroaniline with 104 M− magnitude) < dual- (2,4-dinitroaniline with 105 M− magnitude) < tri- (TNP with 106 M− magnitude), experimentally demonstrating the nitro group with strong electron withdrawing stability is an efficient acceptor causing the fluorescence quenching. In addition, taking TNP for an instance, the absorption of 10−3 M TNP exhibits some extent of overlap with the fluorescence spectra of the Zn-PCP solution. This measurement indicates the energy transfer happens between TNP and Zn-PCP, which further contributes to quenching of the fluorescence with more sensitive detecting performance to TNP than that of other explosives (Figure S14). As the Cr6+ metal ion owns unfulfilled d configuration, both CrO42− and Cr2O72− anions have strong electron-withdrawing ability as that happening in sensing explosive molecules [60,61,62,63]. The electrons of Zn-PCP excited by photons could be transferred to the anions resulting in a decrease of fluorescence intensity.

4. Conclusions

In summary, a Zn-PCP assembled by mechanical grinding of Zn2+, TTSBI, and the etrafluoroterephthalonitrile ligands is presented. Different from the former reported PCP materials, the as-made Zn-PCP could be soluble in regularly used lab solvents of DMF, CH2Cl2, and 1,4-dioxane to form a clear solution which showed an interesting aggregation-induced quenching fluorescence. Importantly, the Zn-PCP could be adopted as a fluorescence sensor to detect nitro-bearing molecules and toxic anions under a homogeneous environment, exhibiting sensitive sensing performances with great accuracy and selectivity. The sensing performances of Zn-PCP were comparatively studied and the potential probing mechanism has also been discussed. This work can not only enrich the sensing members in the family of PCP sensors but also provide a good example for designing novel fluorescence PCP sensors which could be applied under a homogeneous environment.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/s23249719/s1, Figure S1: The EDX measurement for the as-made Zn-PCP; Figure S2: SEM image and C, N, O elemental maps of the as-made Zn-PCP; Figure S3: The XPS of C1s, N1s, and O1s in Zn-PCP sample; Figure S4: The IR spectrum of the as-made Zn-PCP; Figure S5: The PXRD pattern of the as-made Zn-PCP; Figure S6: The excitation spectra of Zn-PCP solution; Figure S7: The CIE chromaticity diagram for Zn-PCP solution with concentration of 0.05 mg/mL; Figure S8: The excitation and emission spectra of the TTSBI solution; Figure S9: The excitation and emission spectra of the tetrafluoroterephthalonitrile solution; Figure S10–S13: The SV equation curve for o-nitrophenol, o-nitroaniline, 2,4-dinitroaniline, and TNP with Ksv and R2 values; Figure S14: UV absorption for 10−3 M TNP and the FL spectrum of Zn-PCP solution.

Author Contributions

Parts of experimental measurements, Z.-W.L. and Z.-F.W.; writing—review and editing, Z.-F.W.; supervision, J.J. and X.-Y.H. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Natural Science Foundation of Fujian Province (2021J01513) and National Natural Science Foundation of China (No. 22175178).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data are contained within the article and supplementary materials.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Luminescent Functional Metal–Organic Frameworks. Chem. Rev. 2012, 112, 1126–1162. [Google Scholar] [CrossRef] [PubMed]
  2. Kreno, L.E.; Leong, K.; Farha, O.K.; Allendorf, M.; Van Duyne, R.P.; Hupp, J.T. Metal–Organic Framework Materials as Chemical Sensors. Chem. Rev. 2012, 112, 1105–1125. [Google Scholar] [CrossRef] [PubMed]
  3. Lustig, W.P.; Mukherjee, S.; Rudd, N.D.; Desai, A.V.; Li, J.; Ghosh, S.K. Metal–organic frameworks: Functional luminescent and photonic materials for sensing applications. Chem. Soc. Rev. 2017, 46, 3242–3285. [Google Scholar] [CrossRef] [PubMed]
  4. Cui, Y.; Zhang, J.; He, H.; Qian, G. Photonic functional metal–organic frameworks. Chem. Soc. Rev. 2018, 47, 5740–5785. [Google Scholar] [CrossRef] [PubMed]
  5. Pan, M.; Liao, W.-M.; Yin, S.-Y.; Sun, S.-S.; Su, C.-Y. Single-Phase White-Light-Emitting and Photoluminescent Color-Tuning Coordination Assemblies. Chem. Rev. 2018, 118, 8889–8935. [Google Scholar] [CrossRef] [PubMed]
  6. Rocha, J.; Carlos, L.D.; Paz, F.A.A.; Ananias, D. Luminescent multifunctional lanthanides-based metal–organic frameworks. Chem. Soc. Rev. 2010, 40, 926–940. [Google Scholar] [CrossRef] [PubMed]
  7. Mahata, P.; Mondal, S.K.; Singha, D.K.; Majee, P. Luminescent rare-earth-based MOFs as optical sensors. Dalton Trans. 2016, 46, 301–328. [Google Scholar] [CrossRef]
  8. Saraci, F.; Quezada-Novoa, V.; Donnarumma, P.R.; Howarth, A.J. Rare-earth metal–organic frameworks: From structure to applications. Chem. Soc. Rev. 2020, 49, 7949–7977. [Google Scholar] [CrossRef]
  9. Zhao, Y.; Li, D. Lanthanide-functionalized metal–organic frameworks as ratiometric luminescent sensors. J. Mater. Chem. C 2020, 8, 12739–12754. [Google Scholar] [CrossRef]
  10. Bagheri, M.; Masoomi, M.Y.; Morsali, A. Highly sensitive and selective ratiometric fluorescent metal–organic framework sensor to nitroaniline in presence of nitroaromatic compounds and VOCs. Sens. Actuators B Chem. 2017, 243, 353–360. [Google Scholar] [CrossRef]
  11. Wu, Z.-F.; Tan, B.; Gong, L.-K.; Zhang, X.; Wang, H.; Fang, Y.; Hei, X.-Z.; Zhang, Z.-Z.; Zhang, G.-Y.; Huang, X.-Y.; et al. A CuI modified Mg-coordination polymer as a ratiometric fluorescent probe for toxic thiol molecules. J. Mater. Chem. C 2018, 6, 13367–13374. [Google Scholar] [CrossRef]
  12. Zhao, H.; Ni, J.; Zhang, J.-J.; Liu, S.-Q.; Sun, Y.-J.; Zhou, H.; Li, Y.-Q.; Duan, C.-Y. A trichromatic MOF composite for multidimensional ratiometric luminescent sensing. Chem. Sci. 2018, 9, 2918–2926. [Google Scholar] [CrossRef] [PubMed]
  13. Patel, N.; Shukla, P.; Lama, P.; Das, S.; Pal, T.K. Engineering of Metal–Organic Frameworks as Ratiometric Sensors. Cryst. Growth Des. 2022, 22, 3518–3564. [Google Scholar] [CrossRef]
  14. Hu, Z.; Lustig, W.P.; Zhang, J.; Zheng, C.; Wang, H.; Teat, S.J.; Gong, Q.; Rudd, N.D.; Li, J. Effective Detection of Mycotoxins by a Highly Luminescent Metal–Organic Framework. J. Am. Chem. Soc. 2015, 137, 16209–16215. [Google Scholar] [CrossRef] [PubMed]
  15. Li, J.; Yuan, S.; Qin, J.; Pang, J.; Zhang, P.; Zhang, Y.; Huang, Y.; Drake, H.F.; Liu, W.R.; Zhou, H. Stepwise Assembly of Turn-on Fluorescence Sensors in Multicomponent Metal–Organic Frameworks for in Vitro Cyanide Detection. Angew. Chem. Int. Ed. 2020, 59, 9319–9323. [Google Scholar] [CrossRef] [PubMed]
  16. Gargurevich, I.A. Hydrogen Sulfide Combustion: Relevant Issues under Claus Furnace Conditions. Ind. Eng. Chem. Res. 2005, 44, 7706–7729. [Google Scholar] [CrossRef]
  17. Meng, X.; de Jong, W.; Pal, R.; Verkooijen, A.H. In bed and downstream hot gas desulphurization during solid fuel gasification: A review. Fuel Process. Technol. 2010, 91, 964–981. [Google Scholar] [CrossRef]
  18. Glarborg, P.; Halaburt, B.; Marshall, P.; Guillory, A.; Troe, J.; Thellefsen, M.; Christensen, K. Oxidation of Reduced Sulfur Species: Carbon Disulfide. J. Phys. Chem. A 2014, 118, 6798–6809. [Google Scholar] [CrossRef]
  19. Majumder, P.S.; Gupta, S. Hybrid reactor for priority pollutant nitrobenzene removal. Water Res. 2003, 37, 4331–4336. [Google Scholar] [CrossRef]
  20. Sun, X.; Wang, Y.; Lei, Y. Fluorescence based explosive detection: From mechanisms to sensory materials. Chem. Soc. Rev. 2015, 44, 8019–8061. [Google Scholar] [CrossRef]
  21. Ciaffoni, L.; Peverall, R.; Ritchie, G.A.D. Breath ammonia levels in a normal human population study as determined by photoacoustic laser spectroscopy. J. Breath Res. 2011, 5, 037101. [Google Scholar]
  22. Davies, A.G.; Burnett, A.D.; Fan, W.; Linfield, E.H.; Cunningham, J.E. Terahertz spectroscopy of explosives and drugs. Mater. Today 2008, 11, 18–26. [Google Scholar] [CrossRef]
  23. Zhang, P.; Li, H.; Veith, G.M.; Dai, S. Soluble Porous Coordination Polymers by Mechanochemistry: From Metal-Containing Films/Membranes to Active Catalysts for Aerobic Oxidation. Adv. Mater. 2014, 27, 234–239. [Google Scholar] [CrossRef] [PubMed]
  24. Huang, Y.-B.; Wang, Q.; Liang, J.; Wang, X.; Cao, R. Soluble Metal-Nanoparticle-Decorated Porous Coordination Polymers for the Homogenization of Heterogeneous Catalysis. J. Am. Chem. Soc. 2016, 138, 10104–10107. [Google Scholar] [CrossRef] [PubMed]
  25. Phillips, M. Detection of carbon disulfide in breath and air: A possible new risk factor for coronary artery disease. Int. Arch. Occup. Environ. Health 1992, 64, 119–123. [Google Scholar] [CrossRef] [PubMed]
  26. DeMartino, A.W.; Zigler, D.F.; Fukuto, J.M.; Ford, P.C. Carbon disulfide. Just toxic or also bioregulatory and/or therapeutic? Chem. Soc. Rev. 2017, 46, 21–39. [Google Scholar] [CrossRef] [PubMed]
  27. Xie, H.; Moore, R.M. Carbon Disulfide Measurement in Marine Waters Using Oxygen-Doped Electron Capture Detection with Purge−Trap Preconcentration. Anal. Chem. 1997, 69, 1753–1755. [Google Scholar] [CrossRef] [PubMed]
  28. Han, B.; Li, Y.; Qian, B.; He, Y.; Peng, L.; Yu, H. A novel liquid chromatography detector based on a dielectric barrier discharge molecular emission spectrometer with online microwave-assisted hydrolysis for determination of dithiocarbamates. Analyst 2018, 143, 2790–2798. [Google Scholar] [CrossRef]
  29. Yan, L.; Zhang, Y.; Yan, H.; Fan, Y.; Liu, X.; Ma, C.; Shi, Q. Molecular Characterization of Lignite Extracts of Methanol and Carbon Disulfide/N-Methyl-2-pyrrolidone by High-Resolution Mass Spectrometry. ACS Omega 2020, 5, 31085–31091. [Google Scholar] [CrossRef]
  30. Wu, Z.-F.; Tan, B.; Feng, M.-L.; Lan, A.-J.; Huang, X.-Y. A magnesium MOF as a sensitive fluorescence sensor for CS2 and nitroaromatic compounds. J. Mater. Chem. A 2014, 2, 6426–6431. [Google Scholar] [CrossRef]
  31. Wu, Z.-F.; Huang, X.-Y. A series of Mg–Zn heterometallic coordination polymers: Synthesis, characterization, and fluorescence sensing for Fe3+, CS2, and nitroaromatic compounds. Dalton Trans. 2017, 46, 12597–12604. [Google Scholar] [CrossRef] [PubMed]
  32. Velasco, E.; Osumi, Y.; Teat, S.J.; Jensen, S.; Tan, K.; Thonhauser, T.; Li, J. Fluorescent Detection of Carbon Disulfide by a Highly Emissive and Robust Isoreticular Series of Zr-Based Luminescent Metal Organic Frameworks (LMOFs). Chemistry 2021, 3, 327–337. [Google Scholar] [CrossRef]
  33. Mahbub, P.; Nesterenko, P.N. Application of photo degradation for remediation of cyclic nitramine and nitroaromatic explosives. RSC Adv. 2016, 6, 77603–77621. [Google Scholar] [CrossRef]
  34. Chhatwal, M.; Mittal, R.; Gupta, R.D.; Awasthi, S.K. Sensing ensembles for nitroaromatics. J. Mater. Chem. C 2018, 6, 12142–12158. [Google Scholar] [CrossRef]
  35. Kaur, M.; Yusuf, M.; Malik, A.K. Synthesis of Copper Metal Organic Framework Based on Schiff Base Tricarboxylate Ligand for Highly Selective and Sensitive Detection of 2,4,6-Trinitrophenol in Aqueous Medium. J. Fluoresc. 2021, 31, 1959–1973. [Google Scholar] [CrossRef] [PubMed]
  36. Song, X.-Z.; Song, S.-Y.; Zhao, S.-N.; Hao, Z.-M.; Zhu, M.; Meng, X.; Wu, L.-L.; Zhang, H.-J. Single-Crystal-to-Single-Crystal Transformation of a Europium(III) Metal–Organic Framework Producing a Multi-responsive Luminescent Sensor. Adv. Funct. Mater. 2014, 24, 4034–4041. [Google Scholar] [CrossRef]
  37. Nagarkar, S.S.; Desai, A.V.; Ghosh, S.K. A fluorescent metal–organic framework for highly selective detection of nitro explosives in the aqueous phase. Chem. Commun. 2014, 50, 8915–8918. [Google Scholar] [CrossRef]
  38. Zhou, E.-L.; Huang, P.; Qin, C.; Shao, K.-Z.; Su, Z.-M. A stable luminescent anionic porous metal–organic framework for moderate adsorption of CO2 and selective detection of nitro explosives. J. Mater. Chem. A 2015, 3, 7224–7228. [Google Scholar] [CrossRef]
  39. Nagarkar, S.S.; Joarder, B.; Chaudhari, A.K.; Mukherjee, S.; Ghosh, S.K. Highly Selective Detection of Nitro Explosives by a Luminescent Metal–Organic Framework. Angew. Chem. Int. Ed. 2013, 52, 2881–2885. [Google Scholar] [CrossRef]
  40. Song, B.-Q.; Qin, C.; Zhang, Y.-T.; Wu, X.-S.; Yang, L.; Shao, K.-Z.; Su, Z.-M. Spontaneous chiral resolution of a rare 3D self-penetration coordination polymer for sensitive aqueous-phase detection of picric acid. Dalton Trans. 2015, 44, 18386–18394. [Google Scholar] [CrossRef]
  41. Joarder, B.; Desai, A.V.; Samanta, P.; Mukherjee, S.; Ghosh, S.K. Selective and Sensitive Aqueous-Phase Detection of 2,4,6-Trinitrophenol (TNP) by an Amine-Functionalized Metal–Organic Framework. Chem. Eur. J. 2015, 21, 965–969. [Google Scholar] [CrossRef] [PubMed]
  42. Dhankhar, S.S.; Sharma, N.; Nagaraja, C.M. Construction of bifunctional 2-fold interpenetrated Zn(ii) MOFs exhibiting selective CO2 adsorption and aqueous-phase sensing of 2,4,6-trinitrophenol. Inorg. Chem. Front. 2019, 6, 1058–1067. [Google Scholar] [CrossRef]
  43. Liu, Y.; Wang, Y.; Zhang, Y.; Karmaker, P.G.; Zhang, L.; Huo, F.; Yang, X.; Zhao, B. Mechanistic insights into the luminescent sensing of nitrophenol compounds by a cationic Zn-based metal-organic framework. Dye. Pigment. 2022, 199, 110099. [Google Scholar] [CrossRef]
  44. Nagarkar, S.S.; Desai, A.V.; Samanta, P.; Ghosh, S.K. Aqueous phase selective detection of 2,4,6-trinitrophenol using a fluorescent metal–organic framework with a pendant recognition site. Dalton Trans. 2015, 44, 15175–15180. [Google Scholar] [CrossRef] [PubMed]
  45. Ghosh, P.; Saha, S.K.; Roychowdhury, A.; Banerjee, P. Recognition of an Explosive and Mutagenic Water Pollutant, 2,4,6-Trinitrophenol, by Cost-Effective Luminescent MOFs. Eur. J. Inorg. Chem. 2015, 2015, 2851–2857. [Google Scholar] [CrossRef]
  46. Ge, S.-S.; Zhang, Y.-H.; Yang, X.-Q.; Mu, X.-G. Three metal organic frameworks based on mixed ligands: Synthesis, crystal structures and luminescent sensing of nitro explosives. Transit. Met. Chem. 2023, 48, 37–45. [Google Scholar] [CrossRef]
  47. Cao, L.-H.; Shi, F.; Zhang, W.-M.; Zang, S.-Q.; Mak, T.C.W. Selective Sensing of Fe3+ and Al3+ Ions and Detection of 2,4,6-Trinitrophenol by a Water-Stable Terbium-Based Metal–Organic Framework. Chem. Eur. J. 2015, 21, 15705–15712. [Google Scholar] [CrossRef]
  48. Chen, H.; Zhang, Z.; Hu, T.; Zhang, X. An NH2-modified {EuIII2}–organic framework for the efficient chemical fixation of CO2 and highly selective sensing of 2,4,6-trinitrophenol. Inorg. Chem. Front. 2021, 8, 4376–4385. [Google Scholar] [CrossRef]
  49. Mukherjee, S.; Desai, A.V.; Manna, B.; Inamdar, A.I.; Ghosh, S.K. Exploitation of Guest Accessible Aliphatic Amine Functionality of a Metal–Organic Framework for Selective Detection of 2,4,6-Trinitrophenol (TNP) in Water. Cryst. Growth. Des. 2015, 15, 4627–4634. [Google Scholar] [CrossRef]
  50. Zou, Y.; Huang, K.; Zhang, X.; Qin, D.; Zhao, B. Tetraphenylpyrazine-Based Manganese Metal–Organic Framework as a Multifunctional Sensor for Cu2+, Cr3+, MnO4–, and 2,4,6-Trinitrophenol and the Construction of a Molecular Logical Gate. Inorg. Chem. 2021, 60, 11222–11230. [Google Scholar] [CrossRef]
  51. Rai, V.; Vajpayee, P.; Singh, S.N.; Mehrotra, S. Effect of chromium accumulation on photosynthetic pigments, oxidative stress defense system, nitrate reduction, proline level and eugenol content of Ocimum tenuiflorum L. Plant Sci. 2004, 167, 1159–1169. [Google Scholar] [CrossRef]
  52. Wang, Y.-S.; Pan, Z.-Y.; Lang, J.-M.; Xu, J.-M.; Zheng, Y.-G. Bioleaching of chromium from tannery sludge by indigenous Acidithiobacillus thiooxidans. J. Hazard. Mater. 2007, 147, 319–324. [Google Scholar] [CrossRef]
  53. Lv, R.; Wang, J.; Zhang, Y.; Li, H.; Yang, L.; Liao, S.; Gu, W.; Liu, X. An amino-decorated dual-functional metal–organic framework for highly selective sensing of Cr(iii) and Cr(vi) ions and detection of nitroaromatic explosives. J. Mater. Chem. A 2016, 4, 15494–15500. [Google Scholar] [CrossRef]
  54. Jia, X.-X.; Yao, R.-X.; Zhang, F.-Q.; Zhang, X.-M. A Fluorescent Anionic MOF with Zn4(trz)2 Chain for Highly Selective Visual Sensing of Contaminants: Cr(III) Ion and TNP. Inorg. Chem. 2017, 56, 2690–2696. [Google Scholar] [CrossRef] [PubMed]
  55. Zhan, Z.; Liang, X.; Zhang, X.; Jia, Y.; Hu, M. A water-stable europium-MOF as a multifunctional luminescent sensor for some trivalent metal ions (Fe3+, Cr3+, Al3+), PO43− ions, and nitroaromatic explosives. Dalton Trans. 2019, 48, 1786–1794. [Google Scholar] [CrossRef] [PubMed]
  56. Hu, Z.; Deibert, B.J.; Li, J. Luminescent metal–organic frameworks for chemical sensing and explosive detection. Chem. Soc. Rev. 2014, 43, 5815–5840. [Google Scholar] [CrossRef] [PubMed]
  57. Zhou, H.; Chua, M.H.; Tang, B.Z.; Xu, J. Aggregation-induced emission (AIE)-active polymers for explosive detection. Polym. Chem. 2019, 10, 3822–3840. [Google Scholar] [CrossRef]
  58. Dutta, A.; Singh, A.; Wang, X.; Kumar, A.; Liu, J. Luminescent sensing of nitroaromatics by crystalline porous materials. CrystEngComm 2020, 22, 7736–7781. [Google Scholar] [CrossRef]
  59. Li, H.-Y.; Zhao, S.-N.; Zang, S.-Q.; Li, J. Functional metal–organic frameworks as effective sensors of gases and volatile compounds. Chem. Soc. Rev. 2020, 49, 6364–6401. [Google Scholar] [CrossRef]
  60. Zhao, D.; Cui, Y.; Yang, Y.; Qian, G. Sensing-functional luminescent metal–organic frameworks. CrystEngComm 2016, 18, 3746–3759. [Google Scholar] [CrossRef]
  61. Yang, G.; Jiang, X.; Xu, H.; Zhao, B. Applications of MOFs as Luminescent Sensors for Environmental Pollutants. Small 2021, 17, 2005327. [Google Scholar] [CrossRef]
  62. Alzaimoor, E.F.H.; Khan, E. Metal–Organic Frameworks (MOFs)-Based Sensors for the Detection of Heavy Metals: A Review. Crit. Rev. Anal. Chem. 2023, 1–22. [Google Scholar] [CrossRef]
  63. Sohrabi, H.; Ghasemzadeh, S.; Shakib, S.; Majidi, M.R.; Razmjou, A.; Yoon, Y.; Khataee, A. Metal–Organic Framework-Based Biosensing Platforms for the Sensitive Determination of Trace Elements and Heavy Metals: A Comprehensive Review. Ind. Eng. Chem. Res. 2022, 62, 4611–4627. [Google Scholar] [CrossRef]
Sensors 23 09719 g001
Figure 1. Schematic illustration of synthesis of the soluble Zn-PCP with fluorescence sensing performances towards explosives and toxic anions.
Figure 1. Schematic illustration of synthesis of the soluble Zn-PCP with fluorescence sensing performances towards explosives and toxic anions.
Sensors 23 09719 g001
Sensors 23 09719 g002
Figure 2. (a) SEM image and elemental maps of the as-made Zn-PCP, scale bar is 70 μm. (b) XPS measurement for Zn2p in Zn-PCP.
Figure 2. (a) SEM image and elemental maps of the as-made Zn-PCP, scale bar is 70 μm. (b) XPS measurement for Zn2p in Zn-PCP.
Sensors 23 09719 g002
Sensors 23 09719 g003
Figure 3. (a) The schematic structure for the Zn-PCP. Color scheme: red ball, O; blue ball, N; gray ball, C; light gray ball, H [23,24]. (b) The fluorescence spectra of Zn-PCP in DMF solution with different concentrations. Insert is the fluorescence photograph of the Zn-PCP solution under 420 nm light.
Figure 3. (a) The schematic structure for the Zn-PCP. Color scheme: red ball, O; blue ball, N; gray ball, C; light gray ball, H [23,24]. (b) The fluorescence spectra of Zn-PCP in DMF solution with different concentrations. Insert is the fluorescence photograph of the Zn-PCP solution under 420 nm light.
Sensors 23 09719 g003
Sensors 23 09719 g004
Figure 4. (a) The fluorescence of the Zn-PCP dissolved in different solvents. (b) The fluorescence spectra of Zn-PCP in DMF solution upon addition of various amounts of CS2. Insert is the photograph of fluorescence solutions before and after adding CS2.
Figure 4. (a) The fluorescence of the Zn-PCP dissolved in different solvents. (b) The fluorescence spectra of Zn-PCP in DMF solution upon addition of various amounts of CS2. Insert is the photograph of fluorescence solutions before and after adding CS2.
Sensors 23 09719 g004
Sensors 23 09719 g005
Figure 5. (a) The fluorescence spectra of Zn-PCP solution upon addition of various amounts of 10−2 M nitrobenzene. (b) The corresponding SV equation curve with Ksv and R2 values. (c–f) are the fluorescence spectra of Zn-PCP solution upon addition of various amounts of 10−2 M o-nitrophenol, o-nitroaniline, and 10−3 M 2,4-dinitroaniline and TNP.
Figure 5. (a) The fluorescence spectra of Zn-PCP solution upon addition of various amounts of 10−2 M nitrobenzene. (b) The corresponding SV equation curve with Ksv and R2 values. (c–f) are the fluorescence spectra of Zn-PCP solution upon addition of various amounts of 10−2 M o-nitrophenol, o-nitroaniline, and 10−3 M 2,4-dinitroaniline and TNP.
Sensors 23 09719 g005
Sensors 23 09719 g006
Figure 6. (a,c) are the fluorescence spectra of Zn-PCP in DMF solution upon addition of various amounts of 10−2 M CrO42− and Cr2O72− solutions, respectively. (b,d) are the corresponding SV equation curve with Ksv and R2 values.
Figure 6. (a,c) are the fluorescence spectra of Zn-PCP in DMF solution upon addition of various amounts of 10−2 M CrO42− and Cr2O72− solutions, respectively. (b,d) are the corresponding SV equation curve with Ksv and R2 values.
Sensors 23 09719 g006
Table 1. The selected CP based fluorescence sensors for TNP.
Table 1. The selected CP based fluorescence sensors for TNP.
PCPsKsv/M−1Reference
Zn-PCP0.16 × 106This work
Cu-CIP1.07 × 104[36]
[Eu3(L)3(HCOO)(μ3-OH)2(H2O)]∙x(solv)2.1 × 104[37]
Zr6O4(OH)6(L)62.9 × 104[38]
[(CH3)2NH2]3[Zn4Na(BPTC)3]∙4CH3OH∙2DMF3.2 × 104[39]
[Cd(NDC)0.5(PCA)]3.5 × 104[40]
[Cd(NDC)L]2∙H2O3.7 × 104[41]
[Zn8(ad)4(BPDC)6O∙2Me2NH2]4.6 × 104[42]
[Zn(BINDI)0.5(bpa)0.5(H2O)]∙4H2O4.9 × 104[43]
[Zn(BINDI)0.5(bpe)]∙3H2O1.29 × 104
[Zn3(TIAB)2(IMDC)2]·(NO3)2·(DMF)2·(H2O)25.68 × 104[44]
Zr6O4(OH)6(L)65.8 × 104[45]
Zn(NDC)(H2O)6.0 × 104[46]
Cd(NDC)(H2O)2.38 × 104
Zn(bipa)(suc)6.48 × 104[47]
[Tb(L)1.5(H2O)]∙3H2O7.47 × 104[48]
(Me2NH2)4[Eu4(DDAC)3(HCO2)(OH2)2]·8DMF·9H2O8.6 × 104[49]
[Zn4(DMF)(Ur)2(NDC)4]1.08 × 105[50]
{Mn(Tipp)(A)2}n·2H2O1.18 × 105[51]
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Jiang, J.; Li, Z.-W.; Wu, Z.-F.; Huang, X.-Y. A Soluble Porous Coordination Polymer for Fluorescence Sensing of Explosives and Toxic Anions under Homogeneous Environment. Sensors 2023, 23, 9719. https://doi.org/10.3390/s23249719

AMA Style

Jiang J, Li Z-W, Wu Z-F, Huang X-Y. A Soluble Porous Coordination Polymer for Fluorescence Sensing of Explosives and Toxic Anions under Homogeneous Environment. Sensors. 2023; 23(24):9719. https://doi.org/10.3390/s23249719

Chicago/Turabian Style

Jiang, Jiang, Zi-Wei Li, Zhao-Feng Wu, and Xiao-Ying Huang. 2023. "A Soluble Porous Coordination Polymer for Fluorescence Sensing of Explosives and Toxic Anions under Homogeneous Environment" Sensors 23, no. 24: 9719. https://doi.org/10.3390/s23249719

APA Style

Jiang, J., Li, Z. -W., Wu, Z. -F., & Huang, X. -Y. (2023). A Soluble Porous Coordination Polymer for Fluorescence Sensing of Explosives and Toxic Anions under Homogeneous Environment. Sensors, 23(24), 9719. https://doi.org/10.3390/s23249719

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop