Luminescent Detection of Colchicine by a Unique Indium–Organic

Article Cite This: Anal. Chem. XXXX, XXX, XXX−XXX

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Luminescent Detection of Colchicine by a Unique Indium−Organic Framework in Water with High Sensitivity Xiao-Lei Jiang, Sheng-Li Hou, Zhuo-Hao Jiao, and Bin Zhao* Department of Chemistry, Key Laboratory of Advanced Energy Material Chemistry, MOE, Nankai University, Tianjin 300071, China

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S Supporting Information *

ABSTRACT: Colchicine is highly toxic to creatures, and sensitively detecting colchicines is of profound significance in the pharmaceutical, clinical, food, and breeding industries. We herein designed and constructed a unique luminescent indium−organic framework {[(CH3)2NH2][In(L)]·9DMF}n (V105) via an in situ ligandmediated method, which possesses a 2-fold interpenetrated 3D anionic framework. Due to the large channels that exist in the framework with the size of 12 Å × 14 Å, V105 can rapidly remove harmful cationic dyes from water in a few minutes. Importantly, luminescent experiments demonstrate that V105 can selectively detect colchicine with high sensitivity in water, and the limit of detection can reach 1.0 × 10−7 M. To our knowledge, this is the first example of a metal−organic framework-based luminescent sensor for detecting colchicine.

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work, we rationally introduced a large external regulator ligand 4′,4′′-(1,4-Phenylene)bis(4,2′:6′,4′′-terpyridine) to modulate the interpenetrating structure, and a unique 2-fold interpenetrated three-dimensional anionic In-MOF, {[(CH3)2NH2][In(L)]·9DMF}n (V105) (H4L = 4,4′,4′′,4′′′(1,4-phenylene-bis(pyridine-4,2,6-triyl))tetrabenzoic acid) with mmt topology has been synthesized through in situ ligand-mediated methods. Because the large channels existed in the framework with a size of 12 Å × 14 Å, V105 can adsorb harmful cationic dyes, such as methylene blue (MB), malachite green (MAG), rhodamine B (RhB) and crystal violet (CV), in several minutes. More importantly, it can also serve as a sensitive and recyclable luminescent probe to detect colchicine in water, and the LOD can reach as low as 1.0 × 10−7 M. Furthermore, the framework can keep stable even after six cycles, and the detection limit has almost no change throughout the experiments. V105 represents the first example of a MOF-based luminescent probe to detect colchicine.

olchicine as a kind of proto-alkaloid is one of the oldest medicines used by humans.1 It has been used to treat many diseases, such as spontaneous inflammation, acute gout, cancer, and liver cirrhosis.2−4 On the other hand, colchicine is highly toxic, and even a small amount of colchicine may cause emesis, diarrhea, kidney failure, multiorgan failure, and bone marrow suppression.5 Hence, it has been banned in many countries. However, colchicine is still found in some medicines and feed industries. Considering these mentioned facts, the rapid and sensitive detection of colchicine from a variety of samples is of profound significance in the pharmaceutical, clinical, food, and breeding industries. To date, there have been many analytical methods developed for the detection of colchicine, like thin layer chromatography−densitometer, HPLC using UV or MS detection, liquid chromatography− tandem mass spectrometry, and electrochemical analysis,2,6−10 but these methods are generally time-consuming, expensive, and cumbersome. Therefore, it is necessary and urgent to find a highly efficient and sensitive method to detect colchicine. Luminescent metal−organic frameworks (MOFs) as newly emerged sensors have been extensively explored in recent years due to their high sensitivity, high selectivity, simple operation, and quick detection.11−13 They have been widely used to detect metal ions,14−19 explosives,20−24 organic small molecules,25−32 antibiotics,33,34 tumor markers,35,36 and so on.37−40 Based on these insights, a luminescent MOF may serve as a promising candidate to detect colchicine, but it has never been reported so far. Four-interpenetrated framework V103 has been reported in our previous work,41 but the small available space and pore sizes caused the low luminescent detection sensitivity. In this © XXXX American Chemical Society

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EXPERIMENTAL SECTION Materials and Methods. Indium(III) nitrate hydrate (In(NO3)3·5H2O) was bought at Sinopharm chemical reagent Co. Ltd.. Organic ligand 4,4′,4′′,4′′′′-(1,4-phenylene-bis(pyridine-4,2,6-triyl))tetrabenzoic acid (H4L) and regulator ligand 4′,4′′-(1,4-phenylene)bis(4, 2′:6′,4′′-terpyridine) were bought at Hengshan chemical corporation. N,N-DimethylforReceived: March 18, 2019 Accepted: June 28, 2019 Published: June 28, 2019 A

DOI: 10.1021/acs.analchem.9b01379 Anal. Chem. XXXX, XXX, XXX−XXX

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Analytical Chemistry mamide (DMF), acetonitrile, and other solvents were purchased from Fuchen chemical corporation. Bovine serum was bought at Tianjin Solomon Biotechnology Co. Ltd. All the raw materials for synthesis were commercially available and directly used without further purification. Powder X-ray diffraction (PXRD) was performed on Ultima IV (Rigaku) using Cu Kα radiation (40 kV, 40 mA). The thermogravimetric analysis (TGA) data were measured from NETZSCH TG 209 under a N2 atmosphere, with the heating rate of 10 °C/min. Fourier transform infrared spectra was measured by Bruker Tensor 27 spectrophotometer in the range of 400− 4000 cm−1. X-ray photoelectron spectrometer (XPS) analyses were measured on an Axis Ultra DLD (Kratos Analytical Ltd.) spectrometer, and the Al Kα radiation was used as an X-ray source with monochromatized X-ray radiation. The UV−vis absorption spectra were measured by a UV-3600 (SHIMADZU) UV−vis-NIR spectrophotometer. ICP-AES was measured by Thermo IRIS Advantage, in NanKai University, the detection limit is 0.035 ppm. Synthesis of {[(CH3)2NH2][In(L)]·9DMF}n (V105). A total of 100 μL of acetic acid was added to a mixture of 15 mg of In(NO3)3, 7 mg of 4′,4′′-(1,4-phenylene)bis(4,2′:6′,4′′terpyridine), and 15 mg of H4L in 1 mL of DMF and 2 mL of acetonitrile. Then the mixture was sealed in a 7 mL glass bottle and heated to 100 °C to react for 72 h and then slowly cooled to room temperature subsequently. The crystal of the pale yellow hexagon is finally obtained with the yield of 52% (based on H4L). IR (cm−1; Figure S2): 1595 (vs), 1542 (s), 1509 (m), 1378 (vs), 1103 (w), 1063 (m), 1016 (m), 865 (w), 822 (s), 786 (vs), 742 (m), 703 (m), 667 (s), 664 (s). X-ray Structure Determination and Structure Refinement. The crystallographic diffraction data was measured by a Bruker D8 Venture Single Crystal Diffractometer equipped with a graphite-monochromatic Mo Kα radiation (λ = 0.71073 Å). Solved through direct methods then refined to convergence by least-squares method on F2 using the SHELXTL (olex 2) programs,42,43 All the atoms except the hydrogen atoms were refined with anisotropic parameters. Due to the existence of severely disordered solvent molecules in the crystal channels, some attempts to locate and refine were unsuccessful. To remove the highly disordered solvent molecules, we used PLATON/SQUEEZE programe.44 Detailed crystal data and structure refinements for V105 are listed in Table S1.

Figure 1. (a) Coordination environment of In3+ and H4 L. (b) Single layer network of V105 along the a-axis. (c) The 2-fold interpenetrated 3D framework and the 1D channel from the c-axis of V105. (d) The mmt topology of V105.

along the c-axis (Figure 1c), and the total available space can reach a high value of 71.7%, calculated by the PLATON program. Powder X-ray Diffraction (PXRD) Analyses and Thermogravimetric Analyses (TGA). The PXRD patterns (Figure S5a) exhibits that the experimental peaks are in accordance with the simulated one, which demonstrated that V105 has high phase purity. The thermogravimetric analysis (TGA) was performed in a N2 atmosphere from 40 to 800 °C with the heating rate of 10 °C min−1, the sharp weight loss of 43.21% from 40 to 400 °C is ascribed to the loss of nine DMF molecules in the channel (calcd, 43.07%; Figure S5a), further indicating the high porosity of V105. After changing the inner solvents by acetonitrile and air-drying, the lost solvents are extremely decreased, but the corresponding weight loss temperature is consistent with the original TGA. The framework begins to decompose at 400 °C, indicating that the framework possesses good thermal stability. Dyes Adsorption Properties. Considering V105 is an anionic framework and has a large pore size, the explorations on the adsorption of harmful cationic dyes in water were investigated. Four common toxic cationic dyes (MB, MAG, RhB, and CV) with different sizes were chosen as diagnostic agents. In a typical experiment, the same amount of activated V105 (10 mg) was immersed into MB (20 mg L−1, 3 mL), MAG (30 mg L−1, 3 mL), RhB (10 mg L−1, 3 mL), and CV (10 mg L−1, 3 mL) solutions at room temperature,

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RESULTS AND DISCUSSION Structure Analysis. Single crystal X-ray diffraction analysis reveals that V105 crystallizes in the orthorhombic system with the space group P bcn (Table S1). The asymmetric unit includes one tetradentate ligand L4− and one In ion. Each In ion is coordinated with four L4− ligands, and each L4− connected with four In ions, forming a (4, 4)-connected mmt-type topology framework (Figure 1 and Figure S1). The In−O bond lengths range from 2.104 to 2.157 Å, which matched well with the previous research.45,46 The oxidation state of indium ion was confirmed by XPS spectra, and the bonding energy of 450.3 eV (3d3/2) and 442.7 eV (3d5/2) is according with the representative In3+ (Figure S3). The assynthesized V105 is an anionic framework, and the [(CH3)2NH2]+ generated by N,N-dimethylformamide in situ decomposition serve as the counterions to balance the charge. Although V105 is a 2-fold interpenetrated framework, it still has a large one-dimensional channel with a size of 12 Å × 14 Å B

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ligands. The coordination of anion ligand L4− makes the ligand emission peak slightly blue shift. In addition, the luminescent intensity of V105 changed negligibly, even after suspending in water for 72 h (Figure S13), revealing the luminescent property of V105 has good water stability. Considering the good stability and luminescent performances in aqueous solution, we try to investigate whether V105 can detect colchicine in water among various interferents including L-proline, NaHCO3, NaCl, KCl, glucose, Na2HPO4, NaH2PO4, MgCl2, and CaCl2 (which simulated the plasma environment). In a classic experiment, 3 mg of V105 was mashed and suspended into 2.9 mL of deionized water by ultrasonication at room temperature. Then, 100 μL of colchicine (5 mg mL−1) or other interferents (5 mg mL−1) were added into the above-mentioned solutions, respectively. As shown in Figures 4a and S14, the luminescent emission had

respectively. Then, the adsorption process was monitored by UV−visible spectroscopy. As shown in Figure 2, the

Figure 2. Removal ratio of MB, MAG, RhB, and CV by V105.

concentration of these dyes reduced significantly in several minutes. At the same time, the pale yellow crystals gradually turned blue, green, pink, and purple, respectively (Figures S6− S9). Finally, V105 can completely adsorb MB, MAG, and RhB in 10, 20, and 30 min, respectively. Even the large molecular CV, it also can be fully adsorbed in 4 h. Under the microscope it was found that after adsorbing these dyes, the color of the crystal changed both inside and outside, which proved that the dyes were adsorbed in the pore instead of the surface (Figure 3). These results demonstrate that V105 has a large pore and can rapidly and effectively adsorb harmful cationic dyes in water.

Figure 4. (a) Intensities of V105 suspensions with various serum components and colchicine (monitored at 472 nm). (b) Luminescence responses of V105 toward colchicine in the presence of background of other various serum components (monitored at 472 nm).

almost no change after adding the other interferents, while the luminescent intensity decreased dramatically when colchicine was added, indicating that V105 can serve as a promising luminescent probe to detect colchicine. To our knowledge, V105 represents the first example of a MOF-based sensor to selective detect colchicine. In order to investigate whether the detection sensitivity will be affected by other coexistent substrates, 100 μL of colchicine (5 mg mL−1) and 100 μL of another interference (5 mg mL−1) were mixed in 2.8 mL of suspended solutions, which contain 3 mg of V105. Then, the luminescent intensity was detected and the results were recorded in Figure 4b. After introducing other interferents, the quenching effect caused by colchicine was not affected, demonstrating V105 can selectively detect colchicine in the presence of various interferents.

Figure 3. Crystal of V105 before (a) and after adsorbing MB (b), RhB (c), MAG (d) and CV (e); V105 after adsorbing MB (b-p), RhB (c-p), MAG (d-p), and CV (e-p) and cutting into broken crystals.

Luminescence Behaviors for Detecting Colchicine. The liquid photoluminescence spectra of H4L and V105 were obtained at room temperature under 300 nm excitation. As shown in Figure S12, V105 exhibited a characteristic emission peak at 472 nm, which is close to one of the emission peaks of ligand H4L (375 and 478 nm), meaning the luminescence of V105 is mainly attributed to the emission of the organic C

DOI: 10.1021/acs.analchem.9b01379 Anal. Chem. XXXX, XXX, XXX−XXX

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In a typical experiment, V105 was suspended in a series of different concentrations of colchicine in 100× diluted bovine serum (0.1−43 μM), and the corresponding luminescent spectra were recorded in Figure S16. It was consistent with the result of no bovine serum added in colchicine solution, and with the increase of colchicine concentration, the luminescent intensity of V105 gradually decreased. As Figure S17 shows, the quenching effect can be fitted as I0/I = 1.059 + 0.167[C] (I0 and I are the luminescence intensity of V105 before and after adding colchicine, respectively; and [C] is the molar concentration of colchicine) with a correlation coefficient (R2) of 0.994 in the low concentration range, which is very close to the linear Stern−Volmer equation: I0/I = 1 + KSV[C]. The calculated KSV is equal to 1.67 × 105 L mol−1, and the LOD was calculated to be 6.25 × 10−7 M. Herein, V105 can act as a sensitivity luminescent sensor to detect colchicine in biological samples. As a luminescent probe, the recyclability is also critical in practical application. Herein, the regenerated experiments of V105 as a luminescent sensor were further explored. After detecting of colchicine, the suspending V105 was isolated by centrifugation and further washed with water five times. Then, subsequent recycling experiments were operated as the initial run. The results in Figure 6 exhibit that, even after six cycles,

To explore the sensitivity of V105 for detecting colchicine, V105 was suspended in a series of different concentrations of colchicine (0.19−58.61 μM), and the corresponding luminescent spectra were recorded in Figures 5a and S15. With the

Figure 5. (a) Emission spectra of V105 dispersed in different concentrations of colchicine solution. (b) The S−V plot of colchicine (monitored at 472 nm).

increase of colchicine concentration, the luminescent intensity of V105 gradually decreased. To further investigate the quenching effect of colchicine on the emission intensity, the relationship between the colchicine concentration [C] and the quenching efficiency was studied. As Figure 5b shows, the quenching effect can be fitted as I0/I = 1.029 + 0.145 [C] (I0 and I are the luminescence intensity of V105 before and after adding colchicine, respectively; and [C] is the molar concentration of colchicine) with a correlation coefficient (R2) of 0.998 in the low concentration range of 0.19−6.55 μM, which is very close to the linear Stern−Volmer equation: I0/I = 1 + KSV[C]. The calculated KSV is equal to 1.45 × 105 L mol−1. Markedly, the decreased luminescence intensity can be still clearly distinguished when the colchicine concentration reduces to 1.9 × 10−7 M. Based on 3σ/k (the relative standard deviation (RSD) of 10 blank measurements is expressed as σ; k represents the slope of linear fitting in the linear range of concentration vs relative luminescence intensity), LOD was calculated to be 1.0 × 10−7 M. Moreover, the LOD of other colchicine detection methods were listed in Table S2. These results reveal that V105 has excellent sensitivity to detect colchicine in water. Analysis of Real Samples. To explore the feasibility of V105 for detecting colchicine in complex biological samples, V105 was used to detect colchicine in bovine serum.

Figure 6. Luminescent intensity of V105 for detection colchicine during recycle.

the luminescence intensity and quenching efficiency are almost consistent with the original results. Subsequently, the stabilities of V105 after six cycles were further explored by the TGA (Figure S5b) and PXRD (Figure S4b), and the results were consistent with the original results, respectively. Meanwhile, the In leaching in the eluate was analyzed by ICP-AES, and no In ion was detected in the example (below the detecting limit). These results mentioned above revealed the framework can remain stable after luminescent detection. More importantly, the recycle investigations on detecting colchicine in bovine serum have also been carried out, and even after six cycles, the luminescence intensity and quenching efficiency are almost consistent with the original results (Figure S18). These results show that V105 can be used as a recyclable probe to detect colchicine by a simple and quick method. Based on what is mentioned above, the possible quenching mechanism is proposed. First, PXRD patterns (Figure S4b), ICP analysis, and TGA results (Figure S5b) suggested that the framework of V105 was still intact after luminescent detection D

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of colchicine, which indicated that the luminescent quenching was not due to the collapse of the framework. Second, the overlap between the excitation bands of V105 and the absorption bands of colchicine (Figure 7) suggested the

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.analchem.9b01379. IR, TGA, XPS, UV−vis and PXRD results (PDF) X-ray crystallographic data in CIF format (CIF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Fax: 022-23502458. ORCID

Sheng-Li Hou: 0000-0002-5331-3911 Bin Zhao: 0000-0001-9003-9731 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by NSFC (21625103, 21571107, 21421001) and the 111 project from the Ministry of Education of China (B12015).

Figure 7. Absorption spectra of colchicine and the excitation spectrum of H4L and V105 in water.

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DEDICATION Dedicated to the 100th anniversary of Nankai University.

existence of competitive absorption, which was the main reason for the luminescent quenching. Third, the emission bands of H4L and V105 have an overlap with the absorption band of colchicine (Figure S19), implying the energy can be transferred from V105 to the analyte, reducing the luminescent intensity. The similar results were also reported by previous research.22,47 Besides, the Stern−Volmer equation between the luminescent quenching rate and the colchicine quantitative concentration was also explored.48,49 As shown in Figure 5b, at high concentration, the Stern−Volmer plot deviated from linearity and curved upward, which suggested that dynamic static quenching processes exist simultaneously.50−52 Since the luminescence of V105 is mainly attributed to the emission of H4L, direct ligand luminescent detection of colchicine has also been explored (Figure S20). And the LOD is calculated to be 1.4 × 10−6 M (Figure S21), while the LOD of V105 can reach to 1.0 × 10−7 M. The result indicated that the framework of V105 could improve the sensitivity of luminescence detection, which mainly originates from reducing energy dissipation of the rigid framework and effectively enriching the analyte in the channel of V105 (Figure S22).

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CONCLUSIONS

In summary, a novel 2-fold interpenetrated 3D anionic InMOF V105 was successfully synthesized by an in situ ligandmediated method. Owing to a large 1D channel with a size of 12 Å × 14 Å along c-aix, it can quickly adsorb harmful cationic dyes from water in a few minutes. Importantly, it also can serve as a sensitive luminescent probe to detect colchicine in water and biological samples, and the detection limit can reach 1.0 × 10−7 M. Furthermore, the framework can keep stable even after six cycles, indicating V105 can be used as a recyclable sensor in practical applications. It is worth noting that this is the first example of a MOF-based luminescence probe being used in colchicine detection. E

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DOI: 10.1021/acs.analchem.9b01379 Anal. Chem. XXXX, XXX, XXX−XXX