Detection of Purine Metabolite Uric Acid with Picolinic Acid

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Functional Nanostructured Materials (including low-D carbon)

Detection of Purine Metabolite Uric Acid with Picolinic Acid Functionalized Metal Organic Framework Shumei Qu, Zheng Li, and Qiong Jia ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b07442 • Publication Date (Web): 28 Aug 2019 Downloaded from pubs.acs.org on August 28, 2019

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ACS Applied Materials & Interfaces

Detection of Purine Metabolite Uric Acid with Picolinic Acid Functionalized Metal Organic Framework

Shumei Qu, † Zheng Li,† and Qiong Jia *, †, ‡ † College ‡ Key

of Chemistry, Jilin University, Changchun 130012, China

Laboratory for Molecular Enzymology and Engineering of Ministry of Education, School

of Life Sciences, Jilin University, Changchun 130012, China

ABSTRACT

Uric acid (UA) is a purine metabolite closely related to the metabolic function of human. Fluorescence analysis is a very effective method because of high selectivity and sensitivity but still remains a great challenge for direct UA detection. In this work, a fluorescent sensor based on post-functionalized metal organic framework (UiO-PSM) was designed focusing on the direct detection of UA. UiO-PSM was synthesized from a zirconium-based MOF (UiO-66-NH2) and 2-picolinic acid (PA) through an amidation reaction. Because UA could quench the fluorescence of UiO-PSM through coordination, hydrogen bonding, and π-π interactions, the sensor could detect UA directly. UiO-PSM exhibited the advantages of short reaction time, high selectivity, high sensitivity, and wide linear range for UA detection. This work provided a novel method for UA detection and had potential application value in clinical diagnosis.

KEYWORDS: uric acid, metal-organic frameworks, fluorescent sensor, post synthetic modification, static quenching mechanism

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1. INTRODUCTION

Uric acid (2, 6, 8-trihydroxypurine, UA) is the final product of purine (e.g., adenine, guanine) metabolism, which can be excreted with urine.1 The normal range of UA levels in healthy adults are 0.13−0.46 mM in serum and 1.49−4.50 mM in urine.2 On the one hand, the UA level with abnormally high in serum (hyperuricemia) is closely associated with diseases, such as urathritis, arthrophlogosis, chronic nephropathy, Lesch-Nyhan syndrome, etc.3,4 On the other hand, extreme low level of UA in serum (hypouricemia) is associated with multiple sclerosis or oxidative stress.1,5 Therefore, there is a great importance of the quantitative detection of UA level in clinical diagnosis of related diseases. The most popular method for UA detection is enzyme based assay. UA is enzymatically hydrolyzed to produce allantoin and hydrogen peroxide, after which the detection of UA is indirectly achieved by determining the content of hydrogen peroxide.6 Although it is widely used, this method still has many limitations, e.g., the interference from other biological analytes (ascorbate, bilirubin), long incubation time (∼30 min), strict pH conditions, expensive enzyme, and low determination accuracy.7,8 So far, some methods have been reported to directly detect UA to avoid the shortcomings of enzyme based assay, such as high performance liquid chromatography

(HPLC),9

gas

chromatography-mass

spectrometry

(GC-MS),10

electrochemistry,11 and fluorescence.12 Among them, fluorescence analysis is a very effective method because of the advantages of rapidness, high selectivity and sensitivity, convenience, and low cost.13‒15 Until now, only a handful of fluorescent sensors for direct UA detection have been developed including carbon dots,16 quantum dots,17 polymers,18 and metal organic frameworks (MOFs).19 MOFs are crystalline materials with intramolecular pores formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds,20,21 and have been 2


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applied in many fields, e.g., separation,22,23 catalysis,24,25 gas storage,26,27 biomedical applications,28,29 drug delivery,30,31 and chemical sensing.32,33 The organic ligands of MOFs usually contain aromatic rings and can connect various functional groups. The highly conjugated framework structure and functionalized groups endow MOFs with fluorescent performances. Furthermore, the fluorescent properties of MOFs are highly sensitive to the changes of surrounding environment,34,35 therefore, MOF-based materials exhibit great potential to be designed as fluorescence sensors focusing on various targets. The introduction of appropriate recognition groups into MOFs can improve the sensitivity and specificity of MOFs.36,37 Post-synthetic modification (PSM) is an efficient strategy to introduce functional groups with appropriate recognition sites into MOFs to obtain highperformance fluorescent sensors,37,38 In Yan et al.’s work, a luminescent MOF Cu2+@MIL91(Al:Eu) was synthesized and utilized for direct detecting uric acid via an on-off-on pattern.12 Except the above study, a literature investigation shows that there are not other reports about post-synthesized modified MOFs-based fluorescent sensors for the detection of UA. In our previous work, we designed a MOFs-based sensor toward free bilirubin detection via a PSM procedure of UiO-66-NH2 with 2,3,4-trihydroxybenzaldehyde.36 UiO-66-NH2 (zirconiumbased MOF) was employed because of its excellent water and chemical stability, and unsaturated coordination metal active sites (Zr).39‒41 Furthermore, the amino groups on UiO66-NH2 make it facile to perform the PSM process.38 Therefore, it has attracted much attention when used for the development of MOFs-based sensors. Herein, we designed a fluorescent sensing material (UiO-PSM) based on covalent PSM of UiO-66-NH2 with 2-picolinic acid (PA) via an amidation reaction and applied to the direct UA determination (Scheme 1). PA was selected as the modifier because it could not only provide appropriate recognition sites for the interaction with UA but also increased the conjugation degree of MOF.18,42,43 The present work was the first attempt that PA modified MOF was used 3



as a fluorescent assay, which provided a rapid, highly specific and sensitive direct monitor method of UA. The developed UiO-PSM probe was successfully applied to the detection of UA in human serum and urine samples and exhibited great potential for exploring their further biosensing applications.

Scheme 1. The synthesis process of UiO-PSM.

2. EXPERIMENTAL SECTION

2.1. Preparation of UiO-PSM.

All reagents were obtained through supplier channels and listed in Supporting Information. PA (0.5 mmol, 62.2 mg) was dropped into 5 mL methanol, after which DMAP (1 mmol), EDC (1 mmol), and TEA (4 mL) were added and stirred for 1 h at room temperature. The prepared UiO-66-NH2 (50 mg) was suspended in 5 mL methanol and sonicated for 20 min. Then the PA solution was added dropwise into the UiO-66-NH2 solution with stirring at 0 °C. The mixture was kept at 0 °C for 1 h, after which the suspension was refluxed at 45 °C for 3 days under nitrogen atmosphere. The obtained yellow solid was washed with methanol and dried in a vacuum at 70 °C overnight. 4


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2.2. Fluorescence Detection of UA.

3 mg UiO-PSM was mixed with 3 mL phosphate buffered saline solution (1 mg mL−1). After sonicating for 30 min, UA solutions were added. The mixture was transferred to a 1 cm × 1 cm quartz cell, and fluorescence experiments were carried out. The fluorescence intensity change of UiO-PSM was monitored at 435 nm (λex = 377 nm). Detailed information was placed in Supporting Information.

3. RESULTS AND DISCUSSION

3.1. Characterization of UiO-PSM.

Scanning electron microscopic (SEM) images were shown in Figure S1. UiO-66-NH2 exhibited crystals morphology of octahedron (Figure S1A).40 After the PSM process, the morphology and diameter of UiO-PSM did not change compared with UiO-66-NH2 (Figure S1B). The crystal structures of UiO-66-NH2 and UiO-PSM were further investigated with powder X-ray diffraction (PXRD). The positions of the diffraction peaks were consistent with those of the single crystal simulated PXRD in previous literatures,44,45 and there were no superfluous miscellaneous peaks. In addition, the peaks at 7.45°, 8.48°, and 25.23° corresponded to the (1 1 1), (2 0 0), and (6 0 0) planes of the single crystals, respectively (Figure 1A).39,46 The results showed that the crystal structure and phase purity of the synthesized MOFs were good. Furthermore, the diffraction peaks changed little after introducing PA, indicating that the crystallinity of UiO-66-NH2 was not affected by the post-synthesis process.

5



BET surface areas of UiO-66-NH2 and UiO-PSM were obtained through the measurement of N2 adsorption-desorption isotherms (Figure 1B). BET surface area of UiO-PSM (851 m2 g−1) was less than that of UiO-66-NH2 (1044 m2 g−1) due to introducing PA. In addition, the curves belonged to type I isotherms, demonstrating that the synthesized UiO-66-NH2 and UiO-PSM were microporous materials.47 1H nuclear magnetic resonance (1H NMR) spectra were measured and employed to calculate the yield (Figure S2).48 The calculation results showed that the conversion yield was 42 ± 1%, illustrating the success of PSM of UiO-66-NH2.

Figure 1. (A) PXRD patterns, (B) N2 uptake isotherms, and (C) FT-IR spectra of (a) UiO-66NH2 and (b) UiO-PSM. (D) N 1s spectrum of UiO-PSM. Inset: N 1s spectrum of UiO-66-NH2.

Fourier-transform infrared (FT-IR) spectra of UiO-66-NH2 and UiO-PSM were displayed in Figure 1C. For UiO-66-NH2 spectrum (curve a), the peaks at 3469 cm−1 and 3362 cm−1 belonged to the symmetrical and asymmetrical stretching vibrations of primary amine 6


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functional groups. However, such peaks were replaced by a peak at 3324 cm−1 in UiO-PSM spectrum (curve b), which could be chalked up to the stretching vibration of secondary amine functional groups.49 Furthermore, the peaks of amide C=O at 1657 cm−1 and pyridine N at 1308 cm−1 appeared in UiO-PSM spectrum. The composition of UiO-66-NH2 and UiO-PSM were characterized by X-ray photoelectron spectroscopic (XPS) (Figure S3). Compared with UiO66-NH2, new peaks of amide N and pyridine N at 399.5 eV and 398.8 eV appeared in N 1s spectrum of UiO-PSM (Figure 1D).50 The thermal stabilities of UiO-66-NH2 and UiO-PSM were studied via thermogravimetricderivative thermogravimetric analysis (TG-DTG). For UiO-66-NH2 (Figure 2A), the decomposition of solvents in the framework resulted in weight loss before 255 °C. When the temperature rose to 676 °C, the weight loss was caused by the thermal dissociation of UiO-66NH2. For UiO-PSM (Figure 2B), the weight loss from 264 °C to 478 °C was because of the thermal dissociation of PA. The characterization results indicated that the thermal stability of UiO-PSM was high. Elemental analysis demonstrated that C, H, and N contents in UiO-PSM were 38.01%, 2.72%, and 6.93%, respectively (Table S1). Furthermore, elemental contents of UiO-PSM had an evident increase compared with UiO-66-NH2 because of the introduction of PA.

Figure 2. TG-DTG curves of (A) UiO-66-NH2 and (B) UiO-PSM.

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3.2. Fluorescence Properties of UiO-PSM.

As shown in Figure S4A, the fluorescence emission of UiO-66-NH2 appeared at 419 nm (λex = 373 nm), which was due to the ligand-to-metal charge transfer (LMCT).44 After modification, UiO-PSM had the fluorescence emission at 435 nm (λex = 377 nm) (Figure 3A). Moreover, UiO-PSM had a brighter blue fluorescence than UiO-66-NH2 (Figure S4B), and the maximum emission wavelength had a red shift, indicating that the conjugation degree and LMCT efficiency of MOF increased. The fluorescence quantum yield (QY) of UiO-PSM was 15.56%, indicating that it could be used as a fluorescent sensor.51 The dependence of fluorescence intensity on pH and time was studied. As shown in Figure S5, the change of fluorescence intensity could be neglected in the pH range from 4 to 10. pH of 7 was chosen as the buffer pH. Furthermore, the sensor displayed high inter-day stability within 2 weeks (Figure 3B). In addition, the inset in Figure 3B indicated that the fluorescence of sensor maintained stable after continuously irradiated with a UV lamp for 60 min. Finally, the day-today water stability of UiO-PSM was explored by PXRD spectra (Figure S6). The results showed that the structure of UiO-PSM remained intact after soaking in water for a week, which indicated that UiO-PSM had a good water stability.

8


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Figure 3. (A) Fluorescence spectra of UiO-PSM. Inset: photograph of UiO-PSM under 365 nm UV light. (B) Inter-day stability of UiO-PSM. Inset: Changes of the fluorescence intensity of UiO-PSM during continuous excitation with a UV lamp for 60 min. (C) Fluorescent emission spectra of UiO-PSM (a) before and (b) after introducing UA. Inset: CIE chromaticity diagram. (D) Fluorescence intensity of UiO-PSM after adding UA at different response time.

3.3. Sensing of UA.

After exploring the features of UiO-PSM, we further studied its sensing performance toward UA. The fluorescence of UiO-PSM was significantly quenched by UA (Figure 3C), indicating that UiO-PSM could be used as a fluorescence sensor for UA detection. In addition, in order to study the sensing ability of UiO-PSM toward UA, we measured the fluorescence intensity of NH2-BDC, UiO-66-NH2, and UiO-PSM in the absence and presence of UA, 9



respectively. As illustrated in Figure S7, a slight decrease of UiO-66-NH2 fluorescence intensity appeared, which was due to the weak interaction between UA and unsaturated metal sites (Zr).36 However, UA caused significant decrease of UiO-PSM fluorescence because the latter could provide more suitable recognition sites, leading to its high specificity and sensitivity toward UA. The response time of UiO-PSM in the presence of UA was investigated. The intensity of UiO-PSM decreased rapidly after adding 200 μM UA and tended to be stable after 1 min reaction (Figure 3D). Therefore, the response time for UA determination was selected to be 1 min. In clinical enzyme based assay for UA detection, at least 30 min of incubation time was required.18 Hence, the developed sensor had a faster response to UA and had great potential in clinical diagnosis. It could be seen from Figure 4A that the fluorescence intensity of UiO-PSM decreased with the increase of UA content. Furthermore, as shown in Figure 4B, the fluorescence intensity ratio (I0 / I) of the sensor was linear within UA concentration from 0.01 to 400 μM (y = 0.1247x + 1.1034, R2 = 0.9986). The detection limit (DL) was determined as 2.3 nM (3S/N), which was much lower than the normal concentration of UA in serum (0.13−0.46 mM) and urine (1.49−4.50 mM) of healthy human.52 In addition, the UiO-PSM sensor was compared with other sensors reported previously. As shown in Table S2, the synthesized sensor had a wide linear range and a low detection limit.

10


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Figure 4. (A) Fluorescence spectra and (B) Fluorescence intensity ratios (I0 / I) of UiO-PSM after adding various concentrations of UA (0−400 μM).

Furthermore, to study the specific fluorescence sensing of UiO-PSM sensors toward UA, we measured the fluorescence intensity of UiO-PSM after adding different potential interferences including glycine (Gly), L-cysteine (L-Cys), adenine (Adn), guanine (Gua), glucose (Glu), urea, ascorbic acid (AA), Na+, and K+ in the absence and presence of UA. The potential interferences caused negligible changes in fluorescence intensity (Figure 5). These results corroborated that the UiO-PSM sensor had high specificity and anti-interference ability for UA detection, indicating that the present sensor could be used for the quantitative sensing of UA.

Figure 5. Fluorescence intensity of UiO-PSM after adding different foreign substances in the absence (blue) and presence (red) of UA.

Good recyclability is a necessary factor for the design of low-cost sensors. Therefore, we studied the reusability of UiO-PSM sensor. After UA quenching fluorescence, the probe solution was centrifuged, ultrasonic washing, and finally dried in vacuum. As shown in Figure

11



S8, the developed sensor could be recycled in four runs of UA sensing, indicating that the recyclability of UiO-PSM was good. To evaluate the application value of the developed UiO-PSM sensor in real samples assay, we determined UA in human serum and urine samples. The results were exhibited in Table S3, the recovery was from 96.94% to 104.58% and the RSD was less than 2.21% (n = 3). Such results indicated the reliability and accuracy of UiO-PSM for detecting UA.

3.4. Sensing Mechanism.

The mechanism of UA detection by UiO-PSM was discussed. From Figure S1B and C, the size and cubic morphology of the UIO-PSM crystals changed little after adding UA. It also discovered that after the introduction of UA, the PXRD spectra diffraction peaks had a neglectable change, implying that UiO-PSM maintained good crystallinity during the quenching process (Figure 6A). The results proved that the addition of UA did not change the crystal shape of UiO-PSM. So, the fluorescence quenching mechanism could be deduced: (1) the coordination between the amino groups of UA and unsaturated metal sites (Zr)36,53 and (2) hydrogen bonding and π-π interaction between UA and UiO-PSM.18,42,54 FT-IR spectra of sensor after adding UA were shown in Figure 6B. After introducing UA, the peak of amide C=O had a blue shift from 1657 cm−1 (curve a) to 1671 cm−1 (curve b) accompanied by an increase of peak width. Meanwhile, the peak of pyridine N at 1308 cm−1 shifted to 1327 cm−1. The results proved that the amide linkages and pyridine N of UiO-PSM interacted with the functional groups of UA by hydrogen bonding.18 It could also be observed that the out of plane bending vibration peak of aromatic C−H bond at 1095 cm−1 in the spectrum of UiO-PSM disappeared after interacting with UA. Such results clearly demonstrated the existence of π-π interaction between UA and UiO-PSM.54 The UV-vis absorption spectra were 12


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investigated and displayed in Figure S9, demonstrating that the absorption peak at 290 nm appeared after adding UA. In addition, the absorption peak of UiO-PSM shifted from 354 nm to 363 nm with a little decrease of intensity, indicating the hydrogen bonding and π-π interaction between UA and UiO-PSM.55 Based on the above discussions, it could be determined that UA was associated with UiO-PSM via coordination, hydrogen bonding, and π-π interactions.

Figure 6. (A) PXRD patterns and (B) FT-IR spectra of UiO-PSM in the (a) absence and (b) presence of UA. (C) Stern-Volmer plots for UiO-PSM in the presence of UA at 288, 298, and 308 K. (D) Fluorescent lifetime of UiO-PSM in the (a) absence and (b) presence of UA.

Fluorescence quenching mechanisms include dynamic quenching and static quenching, which are differentiation by fluorescence quenching constant and excited fluorescent lifetime.56 Stern-Volmer equation: I0 / I = KSVC + 1 = Kqτ0C + 1 13



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where KSV is the Stern-Volmer quenching constant. C is the concentration of UA. Kq is the bimolecular quenching constant. τ0 is the fluorescence decay time of UiO-PSM before adding the quencher. The Stern-Volmer curves at 288, 298, and 308 K were displayed in Figure 6C. Generally, with the increase of temperature, KSV values of static fluorescence quenching decreased, while KSV of dynamic fluorescence quenching was the opposite.57 As shown in Table 1, the Kq values decreased with the increase of system temperature. In addition, the Kq values were far greater than 2.0 × 1010 L mol−1 s−1, which was the maximum dynamic quenching constant.58 So, UiO-PSM detected UA by static quenching. To further verify the mechanism, the fluorescent lifetime of the sensor were investigated and illustrated in Figure 6D. After adding UA, the fluorescent lifetime of UiO-PSM did not change, confirming that the detection of UA by UiO-PSM followed the static quenching mechanism.

Table 1. Stern-Volmer quenching constants for the sensing system at different temperatures. T (K)

Stern-Volmer equation

KSV (L mol−1)

Kq (L mol−1 s−1)

R2

288

I0 / I = 0.1395C + 1.4438

1.395 × 105

9.257 × 1012

0.9944

298

I0 / I = 0.1247C + 1.1034

1.247 × 105

8.275 × 1012

0.9986

308

I0 / I = 0.1082C + 1.2715

1.082 × 105

7.180 × 1012

0.9972

4. CONCLUSIONS

For the first time, a fluorescent UiO-PSM sensor with high specificity and sensitivity was successfully designed and applied to the direct detection of UA. The static quenching mechanism of UiO-PSM induced by UA was validated with FT-IR, UV-vis, Stern-Volmer equation, and time-resolved fluorescence decay experiments in detail. The sensor had a wide linear range (0.01‒400 μM) with DL of 2.3 nM and fast response time of 1 min. Moreover, the 14


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practicality of the sensor was evaluated by the detection of UA in serum and urine samples. It can be expected that the sensor has great application prospects in detection of related diseases.

ASSOCIATED CONTENT

Supporting Information

The Supporting Information is available free of charge on the ACS Publications website at DOI: Experimental details including reagents and instruments, preparation of UiO-66-NH2, analysis of UA in real samples, SEM images, 1H NMR spectra, XPS spectra, PXRD spectra, UV-vis spectra, elemental analysis, methods comparison, real samples assay, and other fluorescence data

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected].

ORCID

Qiong Jia: 0000-0002-3799-0576

Notes

15



The authors declare no competing financial interest.

ACKNOWLEDGEMENTS

This work was financially supported by State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, China (2019-4).

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Detection of Purine Metabolite Uric Acid with Picolinic Acid

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