Amino-functionalized uiO-66(zr) and methods of making and using the same

Abstract

The application belongs to the field of metal organic framework materials (MOFs), and particularly relates to an amino-functionalized UIO-66 (Zr) and a preparation method and application thereof. The application mainly utilizes an amino ligand containing an aminobenzoic acid group and UIO-66 (Zr) to form a complex, which has good binding capacity with azoxystrobin and other pesticide molecules and saccharide substances, and can reduce the ultraviolet band gap value, so as to improve the laser desorption / ionization efficiency of the analyte. Compared with the mass spectrum peak intensity of the organic matrix, the amino-functionalized UIO-66 (Zr) material shows lower noise and detection limit and higher signal intensity in the MALDI-TOF-MS detection, which is beneficial to realize high-sensitivity and high-throughput detection of pesticides and saccharide substances.

Description

Technical Field

[0001] This invention belongs to the field of metal-organic frameworks (MOFs), specifically relating to an amino-functionalized UIO-66 (Zr), its preparation method, and its applications. Background Technology

[0002] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS) offers advantages such as speed, high throughput, high sensitivity, good salt tolerance, and small sample volume requirements, making it widely used for the analysis and detection of biomolecules such as proteins, peptides, nucleic acids, and polymers. In MALDI-TOF-MS detection, the matrix plays a crucial role in efficiently transferring laser energy, accelerating sample ionization, improving sample crystallization, and calibrating internal standards. However, common MALDI matrices (such as α-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB)) exhibit severe correlation peak interference in the detection of pesticides and sugars, and may also suffer from uneven matrix / analyte co-crystallization, leading to poor reproducibility and unreliable quantification. Therefore, these organic matrices are unsuitable for the detection of pesticides and sugars in environmental or plant samples.

[0003] To overcome the aforementioned drawbacks, various types of nanomaterials (including silicon-based nanomaterials, carbon-based nanomaterials, metal-organic frameworks (MOFs), and covalent organic frameworks) have been developed as matrices for MALDI analysis of small molecule compounds. This type of desorption ionization is known as surface-assisted laser desorption / ionization time-of-flight mass spectrometry (SALDI-TOF-MS). Chinese invention patent application CN117007667A, published on November 7, 2023, discloses a method for analyzing fluorine-containing small molecules in the environment based on MALDI-TOF-MS & MSI. It utilizes fluorine-containing covalent organic framework nanomaterials (F-COFs) as a novel fluorine-containing matrix integrating adsorption and enrichment functions. This method is applied to the detection of fluorine-containing small molecules in human serum samples and blueberry products exposed to environmental conditions, ultimately exhibiting high enrichment and excellent ionization of the analytes.

[0004] Pesticides and sugars in environmental or plant samples, such as azoxystrobin, chlorantraniliprole, indoxacarb, triazophos, fructose, and xylitol, are quite different from the aforementioned fluorine-containing small molecules. The interaction between the matrix and the analyte, as well as the desorption / ionization efficiency during detection, also differ significantly. Developing a MALDI-TOF-MS detection matrix suitable for these substances is of great significance for achieving highly sensitive and high-throughput detection of pesticide residues or sugars in environmental or plant samples. Summary of the Invention

[0005] The purpose of this invention is to provide an amino-functionalized UIO-66(Zr) to solve the problems of numerous matrix interference peaks, poor reproducibility, and low sensitivity in MALDI-TOF-MS detection of organic matrices.

[0006] A second objective of this invention is to provide a method for preparing the above-mentioned amino-functionalized UIO-66(Zr).

[0007] A third objective of this invention is to provide the application of the above-mentioned amino-functionalized UIO-66(Zr) as a matrix in SALDI-TOF-MS testing.

[0008] To achieve the first objective mentioned above, the technical solution adopted by this invention is as follows:

[0009] An amino-functionalized UIO-66(Zr) is a complex of UIO-66(Zr) and an amino ligand, the structural formula of which is shown in Formula 1:

[0010]

[0011] In Formula 1, R1 and R2 are each independently selected from H or hydroxyl groups.

[0012] This invention is pioneering, primarily utilizing an amino ligand containing an aminobenzoic acid group and UIO-66(Zr) to form a complex. This complex exhibits excellent binding ability with pesticide molecules such as azoxystrobin and sugars, and can reduce the UV band gap, thus improving the laser desorption / ionization efficiency of the analytes. Comparison of mass spectrometry peak intensities with organic matrices shows that this amino-functionalized UIO-66(Zr) material exhibits lower noise and detection limit, as well as higher signal intensity in MALDI-TOF-MS detection, which is beneficial for achieving high-sensitivity and high-throughput detection of pesticides and sugars.

[0013] Preferably, in formula (1), R1 and R2 are both hydroxyl groups. That is, the amino ligand is 3-amino-4,5-dihydroxybenzoic acid.

[0014] Preferably, the mass ratio of UIO-66(Zr) to the amino ligand is 8:(3-4).

[0015] To achieve the second objective mentioned above, the technical solution adopted by the present invention is as follows:

[0016] The preparation method of the above-mentioned amino-functionalized UIO-66(Zr) includes the following steps: stirring UIO-66(Zr) and amino ligand in water, and then obtaining it by solid-liquid separation.

[0017] The method for preparing amino-functionalized UIO-66(Zr) of the present invention promotes the uniform compounding of UIO-66(Zr) and amino ligands through an aqueous phase system, resulting in amino-functionalized UIO-66(Zr) materials with excellent stability and uniformity. Furthermore, this preparation method is simple, does not use organic solvents, is environmentally friendly, and is suitable for large-scale industrial applications.

[0018] Preferably, the reaction is carried out at room temperature for more than 1 hour.

[0019] Preferably, the amount of water used is 20-30 mL for every 80 mg UIO-66(Zr).

[0020] To achieve the third objective mentioned above, the technical solution adopted by this invention is as follows:

[0021] The above-mentioned amino-functionalized UIO-66(Zr) was used as a matrix in SALDI-TOF-MS testing.

[0022] Using the above-mentioned amino-functionalized UIO-66(Zr) as the detection matrix for SALDI-TOF-MS testing effectively solves the interference of related peaks in the low-mass region (<500 DA) of organic matrices such as CHCA and DHB, improves the reproducibility and reliability of analytical results, and expands the application range of SALDI-TOF-MS testing.

[0023] Preferably, the compound to be tested is a pesticide or a sugar.

[0024] More preferably, the pesticide includes one or more of the following: dimethoate, phorate, 3-hydroxycarbofuran, sulfonium sulfoxide, oxadixyl, ethionyl sulfoxide, benzylphos, triazophos, benzyl sulfoxide, benzyl sulfoxide, phorate sulfone, piperonyl butyl ether, phosmet, pyraclostrobin, chlorantraniliprole, and indoxacarb.

[0025] More preferably, the sugar substance includes one or both of fructose and xylitol. Attached Figure Description

[0026] Figure 1 The infrared spectra of UIO-66(Zr) and UIO-66(Zr)-NH2 in Example 1 of the present invention;

[0027] Figure 2 XPS and high-resolution XPS spectra of UIO-66(Zr) and UIO-66(Zr)-NH2 in Example 1 of this invention;

[0028] Figure 3 The above are SEM images of UIO-66(Zr) (3a) and UIO-66(Zr)-NH2 (3b) in Embodiment 1 of the present invention;

[0029] Figure 4 The XRD patterns of UIO-66(Zr) and UIO-66(Zr)-NH2 in Embodiment 1 of the present invention are shown below.

[0030] Figure 5 This is a TAG diagram of UIO-66(Zr) and UIO-66(Zr)-NH2 in Embodiment 1 of the present invention;

[0031] Figure 6 The nitrogen adsorption-desorption curves and pore size distribution diagrams of UIO-66(Zr) and UIO-66(Zr)-NH2 in Example 1 of this invention are shown.

[0032] Figure 7 The ultraviolet band gap spectra of UIO-66(Zr) and UIO-66(Zr)-NH2 in Example 1 of this invention;

[0033] Figure 8 The images shown are SALDI-TOF-MS images of CHCA, DHB, and UIO-66(Zr)-NH2 as matrices for pesticide detection in Example 1 of this invention.

[0034] Figure 9 This is a comparison of mass spectrometry peak intensities for UIO-66(Zr) and UIO-66(Zr)-NH2 as matrices in Example 1 of the present invention.

[0035] Figure 10 The image shows the SALDI-TOF-MS chromatograms of six pesticides at a concentration of 1 mg / mL as detected by UIO-66(Zr)-NH2 in Example 1 of this invention.

[0036] Figure 11 This is a SALDI-TOF-MS image of D-(-)-fructose detected by UIO-66(Zr)-NH2 in Example 1 of the present invention;

[0037] Figure 12 This is a SALDI-TOF-MS image of xylitol detected by UIO-66(Zr)-NH2 in Example 1 of the present invention. Detailed Implementation

[0038] MOFs are porous nanomaterials composed of metal ions or metal clusters and organic ligands through coordination bonds. They are widely used due to their advantages such as high specific surface area, high porosity, uniform crystal structure, and easy functionalization. Some MOF materials have excellent absorption performance in the ultraviolet-visible light range, which meets the requirements for LDI matrix.

[0039] The amino-functionalized UIO-66(Zr) material constructed in this invention contains numerous functional groups capable of forming hydrogen bonds with analytes. These functional groups enhance the interaction between the matrix and the analytes. Furthermore, the amino ligands, all possessing aminobenzoic acid structures, improve the UV absorption capacity of UIO-66(Zr) and promote electron and energy transfer, thus enhancing the desorption / ionization efficiency in LDI detection. This provides a solution to the inherent defects of traditional organic matrices in MALDI-TOF-MS analysis of pesticides and sugars.

[0040] Furthermore, when 3-amino-4,5-dihydroxybenzoic acid is selected as the amino ligand, two hydroxyl, amino, and carboxyl groups are simultaneously attached to the benzene ring, which can better bind to pesticides, sugars, etc., with a lower binding energy, and exhibits excellent detection performance in SALDI-TOF-MS testing.

[0041] The implementation process of the present invention will be described in detail below with reference to specific embodiments.

[0042] I. Specific Examples of the Amino-functionalized UIO-66(Zr) and its Preparation Method of the Present Invention

[0043] Example 1

[0044] The amino-functionalized UIO-66(Zr) of this embodiment is a complex of UIO-66(Zr) and 3-amino-4,5-dihydroxybenzoic acid, with a mass ratio of UIO-66(Zr) to 3-amino-4,5-dihydroxybenzoic acid of 8:3.

[0045] The preparation method of amino-functionalized UIO-66(Zr) in this embodiment adopts the following steps: 80 mg of UIO-66(Zr) is added to 20 ml of deionized water and stirred for 10 min to form a uniform suspension. 30 mg of 3-amino-4,5-dihydroxybenzoic acid is added as a ligand to the above suspension, and the mixture is stirred at room temperature for 1 h. The precipitate obtained after the reaction is washed three times with deionized water and methanol respectively. The washed precipitate is placed in a vacuum oven at 60 °C and dried overnight to obtain a light brown powder, namely UIO-66(Zr)-NH2.

[0046] Example 2

[0047] The amino-functionalized UIO-66(Zr) of this embodiment is a complex formed by UIO-66(Zr) and an amino ligand in a mass ratio of 8:3. The structural formula of the amino ligand is shown in Formula 1, wherein R1 is H and R2 is a hydroxyl group.

[0048] Example 3

[0049] The amino-functionalized UIO-66(Zr) of this embodiment is a complex formed by UIO-66(Zr) and an amino ligand in a mass ratio of 8:3. The structural formula of the amino ligand is shown in Formula 1, wherein R1 is a hydroxyl group and R2 is H.

[0050] The amino-functionalized UIO-66(Zr) of Examples 2 and 3 can be prepared by referring to the method of Example 1.

[0051] II. Application of the Amino-functionalized UIO-66(Zr) of the Present Invention as a Matrix in SALDI-TOF-MS Testing: Example 4

[0052] This embodiment illustrates the application of the above-mentioned basic functionalized UIO-66(Zr) in SALDI-TOF-MS testing, specifically using the following steps:

[0053] S1. Dissolve the UIO-66(Zr)-NH2 powder from Example 1 in a mixed solvent of ethanol and water at a ratio of 1 mg / mL to 4:1, and sonicate for 15 min to completely dissolve it, thus obtaining a matrix solution.

[0054] S2. Spot 1 mL of matrix solution onto the matching target plate, dry it at room temperature, then add 1 mL of sample solution. After the solvent evaporates and crystallizes, perform SALDI-TOF-MS analysis and detection directly.

[0055] Typical sample solutions can be prepared as follows:

[0056] 1. Environmental water sample: Concentrate 15 mL of water sample to dryness under vacuum, redissolve in 200 μL of 70% (v / v) acetone-water solution, then add 2 μL of 1 μg / mL TPP solution (solvent: 70% (v / v) acetone-water solution) to the redissolved solution to obtain a test solution with an internal standard concentration of 10 ng / mL. Centrifuge at 14000 rpm for 10 min, and retain the supernatant for analysis.

[0057] 2. Tobacco extract aqueous sample: Place 20 mg of lyophilized tobacco powder in a 2 mL centrifuge tube, add 1 mL of 80% (v / v) methanol-water solution, add internal standard TPP solution (triphenyl phosphate) to the internal standard concentration of 10 ng / mL, sonicate under ice bath conditions for half an hour, and then centrifuge at 4℃ and 14000 r / min for 10 min. Take the supernatant for testing.

[0058] SALDI-TOF-MS testing conditions: 5800M SALDI-TOF / TOF TM(AB SCIEX, USA) mass spectrometer, positive ion scanning mode; scanning range: 100-600 DA; employs an ND:YAG high peak power high pulse energy laser, 1000 Hz high frequency laser, and obtains MS spectra by averaging 400 shots per position.

[0059] III. Experimental Examples

[0060] Experimental Example 1: Characterization and Properties Study of UIO-66(Zr)-NH2 Material

[0061] Infrared analysis was performed on UIO-66(Zr) and UIO-66(Zr)-NH2 in Example 1, and their FT-IR spectra are shown below. Figure 1 As shown. Among them, 1660 and 1589cm -1 The peaks at 1400 and 746 cm⁻¹ are characteristic vibrations of the C=O bond. -1 The peaks at 1246 cm⁻¹ represent the CC and CHC vibrations on the aromatic ring, respectively. In addition to the characteristic peaks shared by these two MOFs, the amino-modified UIO-66(Zr)-NH₂ has an additional peak at 1246 cm⁻¹. -1 2590cm -1 and 3210cm -1 The peak is due to the CN bond vibration, CH bond and NH stretching vibration of the aromatic amine, which proves that the amino ligand has been successfully bound to the structure of UIO-66(Zr).

[0062] X-ray photoelectron spectroscopy (XPS) analysis was performed on UIO-66(Zr) and UIO-66(Zr)-NH2 in Example 1, and their XPS spectra are shown below. Figure 2 As shown, compared to UIO-66(Zr), the UIO-66(Zr)-NH2 material exhibits high-resolution N1s peaks at 396.8 and 398.8 eV, corresponding to NH2 and NC, indicating the presence of amino groups in UIO-66(Zr)-NH2. The high-resolution C1s peak at 282 eV is divided into three parts: 280.0 eV, 281.3 eV, and 283.9 eV, corresponding to CC / CN, C=C, and CO in UIO-66(Zr)-NH2. These characterization data demonstrate the successful modification of UIO-66(Zr) with amino ligands.

[0063] The UIO-66(Zr) and UIO-66(Zr)-NH2 in Example 1 were characterized by SEM, and their SEM images are shown below. Figure 3 As shown. UIO-66(Zr)( Figure 3 a) exhibits the typical octahedral configuration of MOF materials, while UIO-66(Zr)-NH2 obtained after modification with 3-amino-4,5-dihydroxybenzoic acid... Figure 3(b) UiO-66(Zr)-NH2 retains the general morphology of UiO-66(Zr), but its surface is rougher. These changes are due to the attachment of amino ligands to the surface of UiO-66(Zr)-NH2.

[0064] XRD analysis was performed on UIO-66(Zr) and UIO-66(Zr)-NH2 in Example 1, and the results are as follows: Figure 4 As shown, both UIO-66(Zr) and UIO-66(Zr)-NH2 exhibit major characteristic diffraction peaks (7.3°, 8.4°, 25.7°), further confirming the structures of UIO-66(Zr) and UIO-66(Zr)-NH2.

[0065] Thermogravimetric analysis was performed on UIO-66(Zr) and UIO-66(Zr)-NH2 in Example 1, and the results are as follows: Figure 5 As shown in the figure. The results indicate that the thermogravimetric curves of the two MOF materials are basically the same, suggesting that the introduction of amino groups has almost no effect on the thermal stability of UIO-66(Zr).

[0066] The specific surface area and pore size distribution of UIO-66(Zr) and UIO-66(Zr)-NH2 in Example 1 were determined using a 77K N2 adsorption-desorption isotherm. The results are as follows: Figure 6 As shown, both UIO-66(Zr) and UIO-66(Zr)-NH2 exhibit typical type I adsorption isotherms. The decrease in specific surface area of ​​UIO-66(Zr)-NH2 after modification with amino ligands indicates that the introduction of amino groups leads to the aggregation of UIO-66(Zr) and pore blockage.

[0067] The UIO-66(Zr) and UIO-66(Zr)-NH2 in Example 1 were analyzed by ultraviolet absorption spectroscopy, and their TAUC plots are shown below. Figure 7 As shown in the figure. The results indicate that after modification with amino ligands, the band gap of UIO-66(Zr) decreased from 3.94 eV to 1.90 eV. The lower band gap allows the MOF to absorb light over a wider wavelength range, indicating that the introduction of amino groups lowers the laser absorption threshold, which is beneficial for improving the laser desorption / ionization (LDI) efficiency of the analyte.

[0068] Experiment Example 2: Comparison of Background Noise and Signal Strength

[0069] This experimental example compares the background noise and signal strength when CHCA, DHB, and UIO-66(Zr)-NH2 from Example 1 are used as the matrix.

[0070] Preparation of CHCA matrix: CHCA was dissolved in 70% (v / v) acetonitrile-water solution at a ratio of 10 mg / mL.

[0071] Preparation of DHB matrix: Dissolve DHB in 50% (v / v) acetonitrile-water solution at a ratio of 10 mg / mL.

[0072] The preparation of the UIO-66(Zr)-NH2 matrix solution is the same as in Example 1.

[0073] Azoxystrobin (AZ), triphenyl phosphate (TPP), and ethyl phosphonium sulfoxide (DS) were diluted to a concentration of 1 mg / mL with 70% (v / v) acetone-water solution as test samples. TPP was also used as an internal standard for pesticide detection.

[0074] The SALDI-TOF-MS detection conditions were the same as in Example 1. Detection results for different matrices are summarized below. Figure 8 middle.

[0075] When CHCA( Figure 8 When a1, b1, and c1 are used as matrices, SALDI-TOF-MS mass spectrometry exhibits numerous matrix-related background noises that interfere with the detection of analytes, such as [M+H]. + [M+Na] + and [M+K] + Use DHB ( Figure 8 When a2, b2, c2) are used as the matrix, the background noise is less than that of CHCA, but the signal intensity is lower. This may be because the crystallization of DHB with the analyte is uneven, and it cannot effectively transfer laser energy to promote the LDI process. Meanwhile, UIO-66(Zr)-NH2( Figure 8 When a3, b3, and c3 are used as matrices, mass spectrometry peaks with low background interference and high signal intensity are obtained. Less matrix effect avoids the suppression of analyte ionization and signal intensity.

[0076] The pesticides azoxystrobin (AZ), benzalkonium chloride (BX), and monocrotophos (MCP) were diluted with 70% (v / v) acetone-water solution to a concentration of 1 mg / mL as test samples. SALDI-TOF-MS was performed under the same conditions, and the results are as follows: Figure 9 As shown. Taking azoxystrobin (AZ) as an example, the SALDI-TOF-MS mass spectrum using UIO-66 (Zr) as the matrix shows [AZ+Na]. + Signal strength is 81, [AZ+K] + The signal strength is 232. When using UIO-66(Zr)-NH2 as the matrix, [AZ+Na] + The signal strength increased to 58606, [AZ+K] + The value increased to 70821. This indicates that the modification with amino groups significantly improved the LDI process of the material, resulting in a higher signal intensity.

[0077] To further verify the feasibility of using UIO-66(Zr)-NH2 to detect more pesticide compounds, six pesticides (azoxystrobin AZ, indoxacarb INX, triazophos TZP, dimethoate OMT, chlorpyrifos FSO2, and piperonyl butyl ether PBO) were tested by SALDI-TOF-MS in positive ion mode. During sample preparation, the six pesticides were diluted with 70% (v / v) acetone-water solution to a final concentration of 1 mg / mL. The SALDI-TOF-MS results in positive ion mode are shown below. Figure 10 As shown in the figure. The results indicate that this method successfully detected all pesticide standards at a concentration of 1 mg / mL with high signal intensity and low background interference. [M+Na] + and [M+K] + The peaks all have high signal strength.

[0078] To verify the analytical performance of SALDI-TOF-MS based on UIO-66(Zr)-NH2 in pesticide detection, linearity (R0) of 16 pesticides was determined using UIO-66(Zr)-NH2 as the matrix. 2 The limits of detection (LOD) and quantitation (LOQ) were determined. 10 ng / mL of TPP was added as an internal standard to each standard solution to ensure accurate pesticide quantification. Standard curves were plotted against the ionic strength of TPP based on the ionic strength of each pesticide standard, and the results are shown in Table 1.

[0079] Table 1. SALDI-TOF-MS detection results of 16 pesticides

[0080]

[0081] As shown in Table 1, the regression coefficients for all analytes were within the acceptable range of 0.90–0.99. The limits of quantitation and detection were 2.04–130.31 μg / L and 0.064–130.313 μg / L, respectively. The LOQ for phosmet (MCP) and phosmet sulfone (FSO2) reached 2.04 μg / L, and the signal-to-noise ratio (S / N) for all analytes was greater than or equal to 3. This demonstrates that the method for analyzing pesticides according to the present invention has high sensitivity and acceptable linearity.

[0082] Experimental Example 3: Determination of Pesticides in Environmental Water

[0083] Water samples from a certain region were selected and the content of each pesticide was tested according to the method in Example 1. The test samples were prepared according to the environmental water sample method in Example 1. Based on the standard curve in Table 1, the specific test results are shown in Table 2.

[0084] Table 2. Content of each pesticide in water samples from a certain region.

[0085]

[0086] As shown in Table 2, the RSD range of the three repeated determinations was 2.0% to 11.0%, which proves that the method has high accuracy and can effectively and quickly determine pesticide residues in actual water samples.

[0087] Experiment 4: Detection of Carbohydrates

[0088] Using the amino-functionalized UIO-66(Zr) from Example 1 as a matrix, two sugar compounds (D-(-)-fructose and xylitol) were detected by SALDI-TOF-MS. The concentration of the analytes was 1 mg / mL, dissolved in an 80% methanol aqueous solution. UIO-66(Zr)-NH2 powder was dissolved at a ratio of 1 mg / mL in a mixed solvent of ethanol and water at a volume ratio of 4:1, and sonicated for 15 min to ensure complete dissolution, thus completing the preparation of the matrix solution.

[0089] 1 μL of matrix solution was spotted onto the matching target plate, dried at room temperature, and then 1 μL of the analyte solution was added. After the solvent evaporated and crystallized, SALDI-TOF-MS analysis was performed directly. Positive ion scanning mode was used during the test; the scanning range was 100-600 DA; equipped with an ND:YAG high peak power high pulse energy laser, providing 1000 Hz high frequency laser, and the MS spectrum was obtained by averaging 400 shots per position.

[0090] The detection spectrum of D-(-)-fructose (CAS: 57-48-7) is shown below. Figure 11 As shown, the detection spectrum of xylitol (CAS: 87-99-0) is as follows. Figure 12 As shown.

[0091] The detection results of carbohydrate compounds showed that there were basically no matrix interference peaks, while the target compounds exhibited high signal intensity, indicating that the amino-functionalized UIO-66(Zr) material can be used as a matrix for SALDI-TOF-MS analysis and achieve highly sensitive detection of carbohydrates.

[0092] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An amino-functionalized UIO-66(Zr), characterized in that, It is a complex of UIO-66(Zr) and an amino ligand, the structural formula of which is shown in Formula 1: In Formula 1, R1 and R2 are each independently selected from H or hydroxyl groups.

2. The amino-functionalized UIO-66(Zr) as described in claim 1, characterized in that, In formula (1), R1 and R2 are both selected as hydroxyl groups.

3. The amino-functionalized UIO-66(Zr) as described in claim 1 or 2, characterized in that, The mass ratio of UIO-66(Zr) to the amino ligand is 8:(3-4).

4. A method for preparing amino-functionalized UIO-66(Zr) as described in any one of claims 1 to 3, characterized in that, The process includes the following steps: stirring UIO-66(Zr) and an amino ligand in water, followed by solid-liquid separation.

5. The method for preparing amino-functionalized UIO-66(Zr) as described in claim 4, characterized in that, The reaction was carried out at room temperature for more than 1 hour.

6. The method for preparing amino-functionalized UIO-66(Zr) as described in claim 4 or 5, characterized in that, The corresponding water dosage for every 80 mg UIO-66 (Zr) is 20–30 mL.

7. The application of amino-functionalized UIO-66(Zr) as a matrix in SALDI-TOF-MS testing as described in any one of claims 1 to 3.

8. The application as described in claim 7, characterized in that, The compound to be tested is either a pesticide or a sugar.

9. The application as described in claim 8, characterized in that, The pesticides include one or more of the following: dimethoate, phorate, 3-hydroxycarbofuran, sulfonium sulfoxide, oxadixyl, ethionyl sulfoxide, benzylphos, triazophos, benzyl sulfoxide, benzyl sulfone, phorate sulfone, piperonyl butyl ether, phosmet, pyraclostrobin, chlorantraniliprole, and indoxacarb.

10. The application as described in claim 8, characterized in that, The sugars include one or both of fructose and xylitol.

Images