Copper Ion Fluorescent Probe Based on Zr-MOFs Composite Material

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Copper ion fluorescent probe based on Zr-MOFs composite material Jing Chen, Haiyong Chen, Tiansheng Wang, Jinfang Li, Jing Wang, and Xiaoquan Lu Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b03924 • Publication Date (Web): 11 Mar 2019 Downloaded from http://pubs.acs.org on March 11, 2019

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Analytical Chemistry

Copper ion fluorescent probe based on Zr-MOFs composite material Jing Chen†,1, Haiyong Chen†,1, Tiansheng Wang†, Jinfang Li†, Jing Wang†, Xiaoquan Lu*, †, ‡

†

Key Lab of Bioelectrochemistry & Environmental Analysis of Gansu Province,

College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou 730070, P. R. China. ‡

Tianjin Key Laboratory of Molecular Optoelectronic, Department of Chemistry,

Tianjin University, Tianjin, 300072, P. R. China.

*Corresponding author: Xiaoquan Lu E-mail: [email protected]; [email protected] Tel: +86 931 7971276/Fax: +86 931 797 1276

1These

authors contributed equally to this work.

1 ACS Paragon Plus Environment

Analytical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Abstract

In this work, a novel and effective ratio fluorescent porphyrin metal-organic framework (MOF) probe by encapsulating UiO-66(OH)2 into the porphyrin MOF (PCN-224) was prepared, showing the excellent fluorescence performance in detecting Cu2+. In this probe, the signal from the green-emission UiO-66(OH)2 encapsulated in PCN-224 was deemed as an effective reference, thus affording an effective built-in correction in complex environmental effects. The red-emission PCN-224 contained the active site for detecting Cu2+. At the same time, Cu2+ can selectively quench the fluorescence intensity of PCN-224. The ratiometric probe therefore gave an effective and reliable Cu2+ determination platform with a LOD value as low as 0.068 nM. This LOD result was better than the Cu2+ concentration limitation in drinking water regulated by World Health Organization (WHO) and reported by some other methods. This provides a simple new sensor for rapidly detecting copper ions, which can be further expanded in various environmental and biological analysis tasks.

Keyword: Metal-organic frameworks; Probe; Ratio fluorescent; Cu2+


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Introduction

At present, copper has wide range of applications in many fields, such as renewable energy, building, electrical equipment and industrial machinery1,2. In addition, copper is a quite important basic element in all creatures including humankind, which maintains the normal function of organs and life metabolic processes. However, it is harmful for physical health to ingest excessive copper, which leads to diarrhea, vomiting, some stomach upset and even severe damage in liver and kidney3,4. Taking into account the important role of copper in various fields, there must be excessive amounts of copper coming from industrial waste and domestic sewage in the environment, which could have bad influence on the surrounding ecosystem and even threaten human health. Copper concentration in the limitation of World Health Organization (WHO) and also Environmental Protection Agency (EPA) in United States cannot exceed 2 ppm and 1.3 ppm in drinking water5,6, respectively. Therefore, it is very important to provide a simple, rapid, highly sensitive and specific method for detecting Cu(II) ions. There were various ways to detect copper ion in aqueous solutions, such as some electrochemical methods9, inductively coupled plasma-atomic emission spectrometry (ICP-AES)7 or inductively coupled plasma-mass spectrometry (ICP-MS)8. However, their applications are restricted because these methods are often time-consuming, or requiring expensive equipment or relatively complex sample preparation. Recently,



novel fluorescence detection methods devoted to construct and design high effective fluorescence sensors have attracted widespread attention due to its advantages such as simplicity, fast response, high selectivity and high sensitivity10,11. In order to meet the design requirements of chemical sensors, novel metal organic frameworks (MOFs) hybrid material attracted widespread concern12,13. MOFs have applications in fields such as gas storage and separation14,15, chemical sensing16-19, catalysis20, and biomedicine21 because of their unique structure. In particular, the rational design of MOFs is very helpful for selectively detecting some small molecules or different ion species through the functionalization of the pore channel surface and the fine tuning of the chemical environment. Although some research groups have utilized luminescent MOFs to detect Cu(II), it is also challenging to study how to increase the sensitivity of the MOFs sensor for detecting Cu(II)22-24. In addition, porphyrin and the related macrocyclic compounds as rigid molecules can be used as bridging ligands in the assembly of MOFs due to their adjustable peripheral substituents, large physical size, and additional metallization sites within the ring25,26. Considering that porphyrin are intrinsic components of these MOFs, the introduction of porphyrin can be avoided. Furthermore, self-aggregation of porphyrin can be effectively reduced due to its good separation, which makes its fluorescence respond to the analyzed substance to be possible. Comparing with the porous materials containing porphyrin in their pores, porphyrin serves as an organic ligand for MOFs that are beneficial to stabilize the framework and to afford accessible, abundant recognition sites27. Recent research projects have also confirmed that the porphyrin MOFs are one of the most


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potential materials in the field of sensors28,29. In this work, a chemical sensor of the porphyrin MOFs composite material based on the Cu(II) ion ratio-based fluorescence shutdown was developed (Scheme 1). This material was prepared by adding a prepared UiO-66(OH)2 (University of Oslo) to the precursor solution of PCN-224 to prepare composite probe utilizing solvothermal reacting. In the framework of MOFs, the light emitted by the organic ligands of UiO66(OH)2 serves as a reference signal. At the same time, the macrocycle containing four N-TCPP units possesses good active sites and can amplify detection signal. By reacting with Cu(II) ions, some effect generates on the porphyrin plane and especially in its electronic structure, resulting in a change in the luminescent properties of the probe, but the luminescence properties of the 2,5-dihydroxyterephthalic acid are not affected. This composite material exhibits high selectivity and convenient sensing properties for many other metal ions on Cu(II) ions. In addition, low detection limits (LODs) are exhibited by comparing with other MOFs sensors. Therefore, the proposed fluorescence sensor based on UiO-66(OH)2@PCN can be used as a highly effective Cu(II) ions sensor.

Experimental Section Materials and Reagents. Zirconium Oxychloride Octahydrate (ZrOCl2·8H2O), 2,5-dihydroxyterephthalic acid and Benzoic Acid were both from Aladdin. Pyrrole and methyl p-formylbenzoate were obtained from Sigma-Aldrich. Minor modifications from the literature were made to obtain Meso-tetra-(4-carbomethoxyphenyl) porphyrin



(TCPP-OMe) and also meso-Tetra (4-carboxyphenyl) porphyrin (TCPP). Synthesis of UiO-66(OH)2@PCN (probe). Dissolving 120 mg ZrOCl2·8H2O, 40 mg TCPP and 1.6 g benzoic acid in 8 mL DMF, and then the mixed solution was sonicated for 10 min. After adding 0.8 mg UiO-66(OH)2 into the solution and sonicating this mixed solution for 20 min, the obtained solution was heated in a muffle furnace at 120 °C for 24 h and then cooled to room temperature. Furthermore, after centrifuging the resulting precipitate with 5000 rpm for 3 min, DMF was used to wash it for three times. Then, the solution was centrifuged and finally dried in a vacuum oven.

Results and Discussion Characterization of Probe. Figure 1a and b are scanning electron microscopy (SEM) of UiO-66(OH)2 and probe, respectively. Their respective morphologies are shown. UiO-66(OH)2 has a very homogeneous morphology and a characteristic cubic close-packed special structure having the average particle size of 120 nm, which is consistent with the reported results. Figure 1b shows PCN-224 encapsulated UiO66(OH)230. Obviously, the introduction of UiO-66(OH)2 does not change the PCN morphology. It still maintains a uniform cubic structure with the 1 μm averages particle size. In order to further observe the morphological and structural characteristics of the material, and to prove UiO-66(OH)2 is really wrapped in PCN, the properties of composite materials were characterized by transmission electron microscopy (TEM) (Figure 1c). In Figure 1c, the particles with an uniform size are distributed within the cube, indicating that UiO-66(OH)2 was successfully wrapped inside PCN-224. At the


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same time, the morphology of PCN-224 did not change. It is clear that the material was successfully prepared. The elemental analysis of probe in Figure 1d demonstrates presence of Zr elemental. In order to prove the successful preparation of the material and whether the crystal structure of the MOFs was damaged or changed, the PXRD characterization was performed (Figure 2). For the hydrothermally synthesized UiO-66(OH)2, the high crystalline and the topologically identical with UiO-66 showed the successful preparation of UiO-66(OH)230. And all main diffraction peaks of PCN-224 at 4.5°, 6.4°, 7.9°, 9.1°, 11.2° and 13.7° can be observed in the characterization diagram (Figure 2). These peaks are almost the same as the previously reported simulated PXRD diagram of PCN-224 crystals. Based on this, the characteristic diffraction peak sites of all the composites have no change by comparing with their standard PXRD. It proves that the UiO-66(OH)2 structure is not changed after being encapsulated, and the characteristic peaks of PCN-224 still exist after encapsulating the particles. Fourier Transform Infrared Spectroscopy (FT-IR) was used here to further characterize the material. By comparing Figure S-2a with c, UiO-66(OH)2 was successfully prepared. The broad and scattered absorption peak at 3100-3400 cm-1 is the stretching vibration generating from the associative hydroxyl group. The C=O bond and also C-O bond of the ligand have been coordinated with the metal ion to form a complex, which can be indicated by the C=O stretching vibration peak of the ligand at 1654 cm-1, the C-O peak at 1491 cm-1 and the shift of the δO=H peak at 1293 cm-1. In Figure S-2d, all characteristic peaks of the probe are present, which proves the existence



of UiO-66-(OH)2 and PCN-224. Spectral Characterization of Probe. The ultraviolet absorption spectra of the organic ligands 2,5-dihydroxyterephthalic acid and TCPP, UiO-66(OH)2 and probe are studied (Figure 3). Through comparative observation, it is found that after the materials composite, the characteristic peaks of UiO-66(OH)2 are blue-shifted, and the characteristic peaks of PCN are red-shifted. However, the composite materials have their both characteristic peaks at the same time, indicating the materials contain UiO66(OH)2 and PCN. In addition, the UV-vis spectrum of probe match well with the spectrum of TCPP. The porphyrin units in MOFs exist in the form of free-base TCPP, which can be proved by observing whether the four Q bands in the UV-vis spectra are present. Fluorescent Probe. Figure 4 shows the fluorescence quenching response of probe at the changed Cu2+concentrations at 25 °C. The probe was dispersed in an ethanol and water (v: v=1:1) mixed solution. And the excitation wavelength was 415 nm. Using the emission peak of 2,5-dihydroxyterephthalic acid at 531 nm as a reference signal, and the characteristic emission fluorescence of the bulk TCPP as a detection signal, the added Cu2+ responds to its fluorescence change. With the Cu2+ concentration in the solution gradually increases from 1 μM to 10 μM, the emission intensity of probe at the strongest TCPP emission peak at 645 nm gradually decreases, but the fluorescence signal of 2,5-dihydroxyterephthalic acid at 531 nm is almost unchanged. Therefore, the emission intensity ratio I531/I645 is analyzed as a ratio-type detection data. At 10 μM, Cu2+ exhibits a high percentage of fluorescence quenching for the probe, and quenches


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over 89% of original fluorescence signal intensity. Stern-Volmer equation shows this quenching efficiency. 𝐼 𝐼0

= 𝐾𝑠𝑣[𝑄] +1 (1)

where I0 means the fluorescence signal intensity obtained by the probe before adding the detection target. I means the intensity obtained after adding the detection target. [Q] is actual molar concentration in the detection target solution. Ksv is a quenching constant. In Figure 4b, a good linear correlation with R2 = 0.9947 is shown in 0-10 μM Cu2+. Ksv is significant for describing the efficiency of fluorescence quenching. For Cu2+, this constant is 4.03×105 M-1. As shown in Figure 5b, with the constant increase of Cu2+ concentration, I531/I645 decreases continuously, and the linearity is good in the range of 0 to 1 nM Cu2+: the linear relationship at I531/I645 is y = 1.478 + 1.004x, R2 = 0.9996. The fluorescence intensity of the blank probe solution is used to calculate the standard deviation σ before Cu2+ is added (Figure 5a). Finally, the detection limit of probe for Cu2+ can reach 0.068 nM, which is far below the concentration specified by the WHO and the US EPA in drinking water. This value is also lower than the detection limit of most previously reported MOFs-based Cu(II) ion sensors, as shown in Table 1. It also shows the high sensitivity of the probe for detecting Cu2+ in the aqueous solution. Selectivity and Sensitivity Test of Probe. To investigate the potential of the fluorescent probe for detecting Cu(II) ions, the fluorescence intensity change of the probe with various cations (Ca2+, Fe3+, Fe2+, Na+, Zn2+, Ag+, Ba2+, Mn2+, Cd2+, K+, and Mg2+) was tested, and the data were analyzed based on the change of I531/I645. In 9 ACS Paragon Plus Environment


Figure 6, the red bars indicate the effects of various metal ions (20 μM) on the probe, respectively. It is found that only Cu2+ can cause changes in the ratio of fluorescence intensity, while other ions have less influence on the probe. This difference is mainly because that Cu2+ possesses the stronger affinity to the porphyrin core active site in the probe44. Then, we further explored the competition experiments between each ion and Cu2+. After the ions reacted respectively with the probe, Cu2+ was added. As shown in Figure 7, the I531/I645 value in each ion solution keep increase with the addition of Cu2+. Therefore, the probe can be quenched just by Cu2+. This result indicates that the coexistent ions do not interfere with the Cu2+ detection by probe. Therefore, the probe can detect Cu2+ with high selectivity regardless of existing other ions or not. Application of the Fluorescent Probes in Real Water Samples. For further evaluating the anti-interference ability and the feasibility of using this dual-emissionratio fluorescent probe for rapidly and ultrasensitively detecting Cu2+ in practical applications, the real-time water samples (Yellow River water, tap water) was tested by fluorescence spectroscopy. By adding the different volumes of standard copper solution into 2 mL prepared solutions, the detection results are shown in Table 2. In Table 2, it is obvious that the proposed method has strong ability to analyze the real samples. Coexisting ions and organic pollutants cannot generate effective interference in the detection, which proves that the probe has excellent selectivity. At the same time, it demonstrates the accuracy and reliability of the probe in detecting Cu2+ in the environmental samples.

Conclusion In summary, the luminescence MOFs of porphyrins have been successfully applied


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to rapidly and specifically detecting Cu(II) ions. As a novel "turn-off" sensor, fluorescent probe exhibits the excellent fluorescence performance for tracing Cu2+ based on the fluorescence quenching ability of Cu2+ to the probe. This work fully explains that the sensor has sufficient potential to detect Cu2+ of water samples in complex environments, even could provide hope for helpfully preventing the copperrelated diseases. As discussed, a new simple sensor for rapidly detecting copper ions was successfully developed and can be further expanded in the application of various environmental and biological analysis tasks.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.anal-chem.xxxxxxx. Additional information as noted in text; detailed information about experimental section: materials and reagents, apparatus, synthesis of TCPP-OMe, synthesis of TCPP, synthesis of UiO-66(OH)2 and fluorescence sensing experiment; Supplemental figures and table: the 1H-NMR spectrum of TCPP ligand and FT-IR images of UiO-66(OH)2, TCPP, H2DHT and probe (PDF)

AUTHOR INFORMATION Corresponding Authors



* Tel: +86-931-7971276. Fax: +86-931-7971276. E-mail: [email protected]. * Tel: +86-22-83613361. Fax: +86-22-83613361. E-mail: [email protected] Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS The work is supported by Natural Science Foundation of China (No. 21565022, 21575115, 21705117); Chang Jiang Scholars and Innovative Research Team Program from Ministry of Education in China (IRT-16R61) and Gansu Provincial Higher Education Research Project (2017-D-01), Gansu Provincial Science and Technology Project (18YF1GA050).

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(40)Bhattacharyya, S.; Chakraborty, A.; Jayaramulu, K.; Hazra, A.; Maji, T. K. A bimodal anionic MOF: turn-off sensing of CuII and specific sensitization of EuIII. Chem. Commun. 2014, 50(88), 13567-13570. (41)Liu, B.; Wu, W. P.; Hou, L.; Wang, Y. Y. Four uncommon nanocage-based LnMOFs: highly selective luminescent sensing for Cu2+ ions and selective CO2 capture. Chem. Commun. 2014, 50(63), 8731-8734. (42)Pang, L. Y.; Yang, G. P.; Jin, J. C.; Kang, M.; Fu, A. Y.; Wang, Y. Y.; Shi, Q. Z. A Rare L1D + R1D → 3D Luminescent Dense Polymer as Multifunctional Sensor to Nitro Aromatic Compounds, Cu2+, and Bases. Cryst. Growth Des. 2014, 14(6), 2954-2961. (43)Hao, Z.; Song, X.; Zhu, M.; Meng, X.; Zhao, S.; Su, S.; Yang, W.; Song, S.; Zhang, H.

One-dimensional channel-structured Eu-MOF for sensing small organic

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Scheme 1. Process for encapsulating the UiO-66(OH)2 into the porphyrin metalorganic framework (PCN-224) and concept for sensing Cu2+.



Figure 1. SEM images of a) UiO-66(OH)2 and b) probe; c) TEM image of probe; d) EDS elemental analysis of probe.


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Figure 2. The PXRD patterns of different materials.



Figure 3. The UV-Vis spectra of different materials in DMF.


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Figure 4. a) The fluorescence emission spectra of probe (50 mg·L-1) with different Cu(II) ion concentrations from 0 to 10 (λex=415 nm); b) Corresponding Stern-Volmer plot of the quenching fluorescence intensity of probe.



Figure 5. a) The fluorescence spectra of blank probe (50 mg·L-1) at different measurements; b) The calibration curve of fluorescence intensity against Cu(II) ion concentration.


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Figure 6. Fluorescence response of various metal ions and Cu2+ to probe.



Figure 7. Fluorescence response of probe in the presence of interfered metal ions in the absence (the black pillar) and presence (the red pillar) of Cu2+.


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Table 1. Previously Reported Various MOF-based Sensors for Cu(II) Ion. MOF

LOD

Year

Probe

0.068 nM

This work

MOF-525

67 nM

201731

Cd-MOF-74

78.7 μM

201732

{[Nd2(NH2-BDC)3(DMF)4]}n

24.95 μM

201733

MIL-53-L

10 μM

201634

PCN-222-Pd(II)

50 nM

201635

[Cd2(PAM)2(dpe)2(H2O)2]·0.5(dpe)

1 mM

201523

[Eu(pdc)1.5(DMF)]·(DMF)·0.5(H2O)0.5

10 μM

201536

[Eu(HL)(L)(H2O)2]·2H2O

10 μM

201537

[ZnL2]n

1 μM

201538

[Cd(2-aip)(bpy)]·2DMF

10 mM

201539

{[Mg3(ndc)2.5(HCO2)2(H2O)][NH2Me2·2H2O·DMF}

10 μM

201440

[Eu3(hcoo)2(R-COO)8]

10 μM

201441

[Cd(H2ttac)bpp]n

0.63 mM

201442

Eu(FBPT)(H2O)(DMF)

10 μM

201343



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Table 2. Determination of Cu2+ in Real Samples.

sample

initial Cu2+ (nM)

spiked Cu2+ (nM)

proposed method Cu2+ (nM)

Recovery (%)

Yellow river water 1

5.64

6

12.19

109.1


5.64

8

13.87

102.8


5.64

10

15.71

100.7

Tap water 1

4.25

6

10.28

100.5

Tap water 2

4.25

8

11.94

96.1

Tap water 3

4.25

10

13.74

94.9


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For TOC only:


Copper Ion Fluorescent Probe Based on Zr-MOFs Composite Material

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