Dielectric barrier discharge induced Oxid-Ti3C2T x Method for preparing uiO-66-nh2 composite material and application thereof

Abstract

The application discloses a preparation method of a medium resistance discharge induced Oxid-Ti3C2T x / UIO-66-NH2 composite material, steps S1, preparing two-dimensional monolayer Ti3C2T x nanosheet, and dispersing the nanosheet in DMF to obtain a Ti3C2T x -DMF mixed solution; S2, dissolving polyvinylpyrrolidone in DMF, then adding the Ti3C2T x -DMF mixed solution, and ultrasonic dispersion to obtain a dark green transparent solution; S3, adding ZrCl4 into the dark green transparent solution, ultrasonic dispersion, fixing on a shaking table for oscillation, sequentially adding 2-amino terephthalic acid and acetic acid into the obtained mixed solution after oscillation is finished, ultrasonic dispersion for several minutes, and obtaining a reaction liquid; S4, quantitatively taking several milliliters of the reaction liquid each time for reaction in a DBD reaction glass tube, the discharge voltage is 37V, the current is 1.27A during the reaction, and the reaction time is 40 minutes, and finally, the Oxid-Ti3C2T x / UIO-66-NH2 composite material is obtained.The application realizes the super-high growth of MOF and TiO2 on the surface of Ti3C2T x by using the medium resistance discharge technology, and thereby, the phosphorylated peptides are enriched based on the IMAC and MOAC principles.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of biological materials, and particularly relates to a preparation method of a medium barrier discharge induced Oxid-Ti3C2T x / UIO-66-NH2 composite material and application of the material in phosphopeptide enrichment. BACKGROUND

[0002] Oxid-Ti3C2T x / UIO-66-NH2 composite material is composed of Ti3C2T x MXenes nanosheets, metal-organic frameworks (MOFs) and TiO2 nanoparticles. The Ti3C2T x MXenes is a two-dimensional transition metal carbide / nitride material, and the surface is rich in modifiable groups -OH, -O and -F, etc. In addition to the metal conductivity, Ti3C2T x MXenes gradually shows its application value in the field of biology and medicine due to its good hydrophilicity and biocompatibility, such as being used as a neural electrode and photochemical treatment of cancer. It is worth mentioning that Ti3C2T x In addition to the surface rich in functional groups easy to modify, MXene also contains a large amount of Ti elements in its structure composition, which shows application prospects in the specific capture of phosphopeptide molecules. However, the specific surface area of MXenes is small (17.9 m 2 / g), which limits the contact area with phosphopeptide molecules in the enrichment process, thereby limiting the enrichment effect. The combination of MXenes with MOFs and TiO2 nanoparticles makes the composite material have the advantages of large specific surface area, high porosity and rich active sites, and therefore is the best choice in the fields of drug delivery, antibiosis, protein or polypeptide separation, etc.

[0003] At present, the preparation of Oxid-Ti3C2T x / UIO-66-NH2 composite material has not been reported. In the prior art, Ti3C2T x MXene is introduced into TiO2 by calcining and oxidizing Ti3C2T x at 900 DEG C in a CO2 atmosphere; and for Ti3C2T x The combination with MOFs is generally realized by solvothermal / hydrothermal method in the few reports, and generally only involves the synthesis of MOFs with relatively mild conditions and Ti3C2T xCombination of MXene. Among them, the preparation characteristics of hydrothermal method is that the system is at normal pressure, and the reaction occurs at or below the boiling point; while the solvothermal method refers to the reaction in a closed container at self-pressure above the boiling point of the solvent. For example, Metal-Organic Framework-Derived Nickel-Cobalt Sulfide on Ultrathin Mxene Nanosheets for Electrocatalytic Oxygen Evolution (ACS Appl. Mater. Interfaces 2018, 10, 22311-22319, Haiyuan Zou et al.); In Situ Growth of Three-Dimensional MXene / Metal–Organic Framework Composites for High-Performance Supercapacitors (Angew. Chem. Int. Ed. 2022, 61, e202116282, Chunli Liu et al.). The former discloses the preparation of ZIF-67 on Ti3C2T x Surface: 0.1 g of Ti3C2T X nanosheets were dispersed in a Co(NO3)2·6H2O (75 mL, 0.1 M) methanol solution, then 2-methylimidazole (75 mL, 0.8 M) methanol solution was added, and stirred magnetically at room temperature for 30 minutes, and the product was obtained after centrifugation and washing with ethanol several times. The latter discloses the preparation of Ti3C2T X / Cu-BTC. 0.9 g of Cu(NO3)2·3H2O was dissolved in 50 mL of methanol containing 0.4 g of PVP. Then the solution was slowly added to a solution containing 20 mg of Ti3C2T X powder and 0.43 g of C 12 H 12 O6 in methanol, stirred at room temperature for 2 hours, the product was collected by centrifugation, and washed with methanol. These methods successfully realized the growth of MOFs on Ti3C2T x , but the uniformity of the growth and the crystallinity of the MOFs need to be optimized, and the preparation method is only suitable for MOFs that are not strict in temperature requirements during crystallization. In addition, it is worth noting that Cu-BTC, ZIFs are not ideal materials for enriching phosphorylated peptides. SUMMARY

[0004] In view of the lack of methods for preparing Oxid-Ti3C2T x / UIO-66-NH2 composite materials in the prior art, the present application provides a method for preparing Oxid-Ti3C2Tx A method for preparing a / UIO-66-NH2 composite material.

[0005] The present application provides a dielectric barrier discharge induced Oxid-Ti3C2T x A method for preparing a / UIO-66-NH2 composite material, the steps are as follows:

[0006] S1, preparing two-dimensional monolayer Ti3C2T x Nanoplatelets, and dispersing the prepared nanoplatelets in DMF to obtain a Ti3C2T x -DMF mixed solution, and sealing and storing at 4 DEG C.

[0007] Using a minimum strength layer peeling method, etching Al atomic layers, and preparing two-dimensional monolayer Ti3C2T x Nanoplatelets. The specific steps are as follows:

[0008] S11, fixing a polyethylene reaction container in a constant temperature oil bath pot at 35 DEG C., adding concentrated hydrochloric acid and deionized water, then slowly adding LiF under stirring conditions to obtain an HF solution;

[0009] S12, uniformly adding Ti3AlC2 into the reactor within 20 minutes, and stirring and reacting at 35 DEG C. for 24 hours;

[0010] S13, after the reaction is completed, repeatedly washing the product with deionized water and centrifugally separating, and in the washing process, peeling in a hand-shaking manner before each centrifugation to obtain stable Ti3C2T x Nanoplatelets.

[0011] S2, dissolving polyvinylpyrrolidone in DMF to obtain a clear solution, then adding Ti3C2T x -DMF mixed solution, and ultrasonically dispersing to obtain a dark green transparent solution;

[0012] S3, adding ZrCl4 into the dark green transparent solution, ultrasonically dispersing for several minutes, then fixing on a shaking bed and oscillating for several hours, and then sequentially adding 2-amino terephthalic acid and acetic acid into the obtained mixed solution, ultrasonically dispersing for several minutes to obtain a reaction liquid;

[0013] S4, each time, a certain amount of reaction liquid is taken in a DBD reaction glass tube for reaction preparation, the discharge voltage is 37V, the current is 1.27A, the reaction time is 40 minutes, and after the reaction is completed, centrifugal separation is performed to obtain a dark gray solid product, namely, Oxid-Ti3C2T x / UIO-66-NH2 composite material.

[0014] Preferably, Ti3C2T xThe mass ratio of the nanosheet and ZrCl4 is 1:14. The mass ratio of ZrCl4 and 2-amino terephthalic acid is (1.2-1.3):1.

[0015] Preferably, in step S4, the dark gray solid product obtained by centrifugal separation is washed with DMF and centrifugally separated, and vacuum dried to obtain the purified dark gray solid product Oxid-Ti3C2T x / UIO-66-NH2 composite material.

[0016] The Oxid-Ti3C2T x / UIO-66-NH2 composite material can be used as a protein separation and enrichment material.

[0017] Preferably, the Oxid-Ti3C2T x / UIO-66-NH2 composite material is used as an enrichment material for phosphorylated peptide fragments. The enrichment method of the phosphorylated peptide fragments is as follows:

[0018] The Oxid-Ti3C2T x / UIO-66-NH2 composite material is used as an enrichment material, and the enrichment material is washed with an enrichment solution for multiple times. During enrichment, a solution containing phosphorylated peptide fragments is added to the washed enrichment material, and vortex is performed to fully mix the enrichment material and the solution, and then the mixture is placed in a shaking bed for incubation at 37℃ for 30 minutes. After the incubation, the supernatant is removed by centrifugation, and the lower solid is washed with the enrichment solution and centrifuged to remove non-specifically adsorbed impurities on the surface of the material. The eluent is added to the washed material, vortex is performed to fully contact the material and the eluent, and the mixture is fixed in a shaking bed for incubation at 37℃ for 30 minutes. After the incubation, the supernatant is obtained by centrifugation.

[0019] Compared with the prior art, the present application has the following advantages:

[0020] (1) In view of the problem that there is no one-pot method for rapidly and efficiently growing UIO-66-NH2 and TiO2 nanoparticles on MXenes at present, the present application utilizes dielectric barrier discharge technology (DBD) to rapidly and efficiently grow MOFs with uniform particle size and high crystallinity on the surface of Ti3C2T x nanosheets. At the same time, Ti3C2T x MXenes are partially oxidized to obtain TiO2 nanoparticles, and finally a new Oxid-Ti3C2T x / UIO-66-NH2 composite material is obtained, which has a heterostructure. The method is simple in operation and high in efficiency.

[0021] (2) The preparation method of the present invention greatly improves the in-situ growth rate of MOF, shortening it from the traditional 24 hours to 40 minutes, and obtains uniform, excellently crystalline, and high specific surface area (905.1 m2 / g) UIO-66-NH2 nanoparticles. In addition, during the DBD treatment, Ti3C2T x MXene is partially oxidized, eventually forming TiO2 on the surface of the nanosheets while maintaining the integrity of the nanosheet structure.

[0022] (3) Preparation of Oxid-Ti3C2T x The / UIO-66-NH2 composite material has a large specific surface area, multiple affinity sites, and is rich in active sites (Zr-O clusters, metal active sites, and TiO2 nanoparticles). The composite material is used as an enrichment material for phosphorylated peptides. Based on the IMAC and MOAC principles, the enrichment of phosphorylated peptides showed high sensitivity (0.1 fmol μL -1 ) and relatively ideal selectivity (α-casein: BSA = 1:100, molar ratio). In addition, the composite material showed excellent application potential when detecting low-abundance phosphorylated peptides in complex biological samples (skim milk, human saliva, human serum).

[0023] Other advantages, objectives and features of the present invention will be reflected in part from the following description and will be understood by those skilled in the art through study and practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 , Oxid-Ti3C2T of the present invention x Schematic diagram of the synthesis process of / UIO-66-NH2 composite material.

[0025] Figure 2 、Ti3AlC2、Ti3C2T x SEM images of nanosheets, (a) is Ti3AlC2, (b) is Ti3C2T x .

[0026] Figure 3 、Ti3C2T x HRTEM image of nanosheets.

[0027] Figure 4 、Ti3C2T x AFM characterization of nanosheets.

[0028] Figure 5 , SEM images of products prepared with different MOF precursor additions. (a), (b), (c), (d), and (e) are SEM images of product 1, product 2, product 3, product 4, and product 5, respectively.

[0029] Figure 6 SEM images of Oxid-Ti3C2T x / UIO-66-NH2.

[0030] Figure 7 SEM images of Oxid-Ti3C2T x / UIO-66-NH2.

[0031] Figure 8 TEM images of Oxid-Ti3C2T x / UIO-66-NH2.

[0032] Figure 9 Ti3AlC2, Ti3C2T x and Oxid-Ti3C2T x XRD patterns of Oxid-Ti3C2T

[0033] Figure 10 XRD patterns of Ti3C2T x and Oxid-Ti3C2T x XPS patterns of Oxid-Ti3C2T

[0034] Figure 11 Raman spectra of Ti3C2T x treated with DBD technique at different times.

[0035] Figure 12 Raman spectra of Ti3C2T x treated with DBD technique at different times.

[0036] Figure 13 N2adsorption-desorption and pore size distribution of Oxid-Ti3C2T x / UIO-66-NH2composites.

[0037] Figure 14 Mass spectra of α-casein before (a) and after enrichment with Oxid-Ti3C2T x / UIO-66-NH2.

[0038] Figure 15 Mass spectra of skimmed milk (a), human serum (c), human saliva (e) before enrichment; skimmed milk (b), human serum (d), human saliva (f) after enrichment with Oxid-Ti3C2T x / UIO-66-NH2. DETAILED DESCRIPTION

[0039] The preferred embodiments of the present application are described below in conjunction with the accompanying drawings, in which it is to be understood that the preferred embodiments described herein are merely illustrative and explanatory and are not intended to limit the present application.

[0040] Example 1

[0041] The Oxid-Ti3C2T x The preparation method of the Oxid-Ti3C2T / UiO-66-NH2 composite material is as follows:

[0042] S1, preparation of single-layer Ti3C2T x nanosheet:

[0043] A clean polyethylene reaction container was fixed in a constant temperature oil bath at 35°C, 15 mL of concentrated hydrochloric acid and 5 mL of deionized water were measured in the reaction container, and magnetic stirring was started. 1 g of LiF was slowly added to the reaction container during stirring, thereby obtaining an HF solution. 1 g of Ti3AlC2 was uniformly added to the reactor within 20 minutes, the magnetic stirring speed was adjusted to 500 rpm, and the reaction was carried out at 35°C for 24 hours. After the reaction was completed, the product was repeatedly washed with deionized water and separated by high-speed centrifugation, the centrifugal speed was 8500-9500 rpm, until the supernatant pH was neutral. During the washing process, the peeling was carried out by hand shaking before each centrifugation to obtain stable Ti3C2T x nanosheet, and finally the nanosheet was dispersed in DMF to obtain Ti3C2T x -DMF mixture, Ti3C2T x The concentration was 10 mg / mL, and it was stored at 4°C in a sealed state.

[0044] S2, 20 mg of polyvinylpyrrolidone was weighed in 17.5 mL of DMF, and a clear solution was obtained by ultrasonic dispersion. 0.5 mL of Ti3C2T x -DMF mixture was added to the clear solution obtained above, and a dark green transparent solution was obtained by ultrasonic dispersion.

[0045] S3, 70 mg of ZrCl4 was added to the above dark green transparent solution, ultrasonic dispersion was carried out for 5 minutes, and then it was fixed on a digital shaking bed for oscillation for 6 hours. After oscillation, 54.35 mg of 2-amino terephthalic acid and 2.5 mL of acetic acid were added to the obtained mixture in turn, ultrasonic dispersion was carried out for 5 minutes, thereby obtaining a reaction liquid.

[0046] S4, during the reaction, 5 mL of the reaction liquid was taken each time to prepare in a DBD reaction glass tube, the discharge voltage was 37 V, the current was 1.27 A, the reaction time was 40 minutes, and after the reaction was completed, post-treatment was carried out, finally a dark gray solid product Oxid-Ti3C2T was obtained.x / UIO-66-NH2 composite. Post-reaction treatment: centrifugation to obtain dark gray solid product, then washed with DMF and centrifuged three times at 6000 rpm, and finally dried in a vacuum drying box to obtain purified Oxid-Ti3C2T x / UIO-66-NH2 composite.

[0047] The Oxid-Ti3C2T x / UIO-66-NH2 composite. The synthesis process principle is as shown in Figure 1 .

[0048] The morphology of the single-layer Ti3C2T x nanosheet prepared in step S1 was characterized by SEM and AFM, as shown in Figures 2-4 . The SEM photos show that the sample morphology changes from blocky to nanosheet with a thin silk-like feel before and after exfoliation, with a lateral size of several hundred nanometers to several microns. AFM shows that the film surface roughness is about 2.4 nm, and the single-layer film thickness is about 2 nm. In addition, the Ti3C2T x MXene nanosheet surface will produce a large number of functional groups such as -OH, -O- and -F, and the Ti3C2T x MXene surface potential is -20.9 mV, and the negative nature of its surface is conducive to the later fixation of metal ions, so as to grow MOFs in situ on its surface.

[0049] On the basis of the preparation method steps of Example 1, the amount of MOF precursor (ZrCl4 and 2-amino terephthalic acid) was changed, and different composites were finally obtained. When the addition amount of ZrCl4 and 2-amino terephthalic acid was 0 mg, i.e. step S3 of Example 1 was deleted, step S4 was directly carried out, and a dark green product was finally obtained, which was named product 1. When the addition amount of ZrCl4 and 2-amino terephthalic acid was 21 mg and 16 mg respectively, product 2 was obtained. When the addition amount of ZrCl4 and 2-amino terephthalic acid was 35 mg and 27 mg respectively, product 3 was obtained. When the addition amount of ZrCl4 and 2-amino terephthalic acid was 70 mg and 54.35 mg respectively, product 4 was obtained, i.e. the product prepared in Example 1. When the addition amount of ZrCl4 and 2-amino terephthalic acid was 91 mg and 70.66 mg respectively, product 5 was obtained.

[0050] The prepared products 1-5 were characterized by SEM, and the results are shown in Figure 5 . After 40 minutes of DBD treatment, some TiO2 nanoparticles appeared on the Oxid-Ti3C2T x nanosheet without MOF precursor, and the Ti3C2T xThe nanosheet morphology is still well preserved; when the feed of MOF increases, in addition to TiO2, UIO-66-NH2 also grows on Ti3C2T x , and the particle size, crystal form and growth density of UIO-66-NH2 are proportional to the amount of precursor, so when the precursor is 91mg and 70.66mg, it can be seen that Ti3C2T x It is completely covered by UIO-66-NH2, even accompanied by some free UIO-66-NH2 nanoparticles. x As the surface particle content changes, the increasing number of UIO-66-NH2 nanoparticles will slowly cover or replace the Ti3C2T x The originally exposed metal sites and TiO2 nanoparticles are grown until they are covered with UIO-66-NH2. At this time, the metal sites and TiO2 nanoparticles are almost completely covered or replaced, with only Zr-O. Therefore, 70 mg and 54.35 mg are the most ideal feed ratios, that is, the composite material Oxid-Ti3C2T prepared in Example 1 x / UIO-66-NH2.

[0051] The composite material Oxid-Ti3C2T prepared in Example 1 x / UIO-66-NH2 was used for morphological characterization, and the results are shown in Figure 6 、 Figure 7 and Figure 8 . Figure 6 The SEM images show that the Ti3C2T x A large number of nanoparticles with geometric morphology are dispersed on the surface of the nanosheets, and their particle size is about 200 nm. In addition, the morphology of the nanosheets is complete, indicating that DBD treatment for 40 minutes can effectively improve the performance of Ti3C2T x UIO-66-NH2 was in situ grown on the nanosheets without affecting the Ti3C2T x The original morphology of the nanosheets. Figure 7 The high-resolution TEM (HRTEM) image of the Ti3C2T nanostructured TiO2O3 was observed to have lattice fringes with a lattice spacing of 0.46 nm, which is consistent with the lattice fringes of UIO-66-NH2. x Uniform growth of UIO-66-NH2 on nanosheets. Oxid-Ti3C2T x High-angle annular dark field (HAADF) image of / UIO-66-NH2 and the corresponding element distribution map ( Figure 8 , EDXS) further confirmed that the C, O, Ti, and Zr elements in the composite material were evenly distributed, indicating that the DBD technology was successfully used to transform Ti3C2T xand UIO-66-NH2 together. In addition, particles with a size of about 10 nm were observed in the HRTEM image, which is obviously different from the morphology of UIO-66-NH2. By measuring the lattice fringes, it was found that the interplanar spacing of the particles was 0.229 nm, which was consistent with the (200) crystal plane of TiO2. Therefore, Ti3C2T x itself generates a certain oxidation effect, thereby growing TiO2nanoparticles on its surface and maintaining the structure of Ti3C2T x The structure of Ti3C2T x itself does not collapse.

[0052] The crystal structure of the composite material obtained in Example 1 was characterized by XRD, and the results are shown in Figure 9 The XRD patterns of Ti3AlC2 and Ti3C2T x were compared. The peak of the (104) crystal plane of Ti3AlC2 at 38.9° disappeared, indicating that Al in Ti3AlC2 was successfully etched. At the same time, in the XRD spectrum of Ti3C2T x , the (002) diffraction peak position moved from 9.5° to a lower angle of 6.9°, which indicated that the interlayer distance of Ti3C2T x increased after exfoliation. The XRD pattern of Oxid-Ti3C2T x / UIO-66-NH2 showed a strong peak at 6.9° of Ti3C2T x , and a series of new peaks were observed at 8.1°, 11.6°, 16.6° and 25.3°, respectively, which were consistent with the peak positions of UIO-66-NH2, confirming the presence of UIO-66-NH2 in the composite material. However, in the spectrum of Oxid-Ti3C2T x / UIO-66-NH2, no characteristic peak of TiO2 was observed, and the reason may be that the content of UIO-66-NH2 in the composite material was much higher than that of TiO2, and the characteristic peak of the latter was completely covered.

[0053] The structure and chemical properties of the obtained composite material were characterized by XPS and Raman spectroscopy with higher sensitivity, and the results are shown in Figure 10 . The XPS full spectrum results showed that Ti3C2T x was composed of C, Ti, O and F, and Oxid-Ti3C2T x / UIO-66-NH2 was composed of C, Ti, O, F and Zr. The binding energies of F1s, O1s, Ti2p, C1s and Zr3d were 531.77, 458.72, 284.80 and 182.74 eV, respectively. At the same time, because the MOFs accounted for a high proportion in Oxid-Ti3C2T x / UIO-66-NH2, in the XPS spectrum, the peaks of Ti3C2Tx The Ti2p and F1s peak intensities are significantly weakened. The specific information on the composition of each material is listed in Table 1. It can be seen that after the introduction of UIO-66-NH2, the proportion of Ti decreased from the original 32.87% to 1.93%, which is consistent with the results of the full spectrum. This is also the reason why there is no obvious TiO2 peak in the XRD.

[0054] Table 1. Ti3C2T x and Oxid-Ti3C2T x Binding energy and atomic proportion of different elements in UIO-66-NH2

[0055]

[0056] Processing Ti3C2T with DBD technology x Ti high-resolution XPS spectra at time 0 min (a), 10 min (b), 40 min (c), and 60 min (d) are shown in Figure 11 . Figure 11 It is further confirmed that DBD treatment will oxidize Ti3C2T x Produce TiO2, as shown in the figure, without DBD treatment, Ti3C2T x Peaks corresponding to Ti-C, Ti-O(II) and TiO2 appeared at 455.7, 457.0 and 459.0 eV respectively. After 10 minutes of treatment, the peak at 459.0 eV belonging to TiO2 was enhanced, accompanied by the strengthening of the Ti-O(II) peak, indicating that DBD treatment for 10 minutes can effectively reduce the surface area of ​​Ti3C2T x A certain degree of oxidation occurred on the surface, and Ti-O(II) can be regarded as an intermediate of TiO2. When the DBD treatment time was 40 minutes, TiO2 became the dominant peak in the entire spectrum. When the treatment time reached 60 minutes, the Ti-C and Ti-O(II) peaks almost disappeared, leaving only the strong TiO2 peak. This series of experiments clearly revealed the effect of DBD treatment on Ti3C2T x oxidation, and further confirmed that Oxid-Ti3C2T x / The presence of TiO2 in UIO-66-NH2.

[0057] Raman spectroscopy was used to analyze Ti3C2T treated with DBD for different times. x Information on the composition and surface groups of Figure 12 In all spectra, 152.6 cm -1 , 412.3cm -1 and 617.7cm -1 Strong peaks are observed at the same positions, which are caused by Ti, C, T x A 1g and Tx =O's E g After DBD treatment, there are two -1 The broad peaks of the band appear, which belong to the characteristic peaks of D-modes amorphous carbon and G-modes graphene carbon respectively. As the treatment time becomes longer, the D and G peaks become more obvious. After 60 minutes of treatment, the center position of the D band is 1405 cm -1 , the maximum half-peak width is 250cm -1 , the center position of G band is 1575cm -1 The maximum half-peak width is 114 cm -1 I D / I G The value of is 0.96, which indicates that highly disordered carbon is formed in the sample after DBD treatment for 60 minutes. This is because during the DBD treatment, Ti3C2T x The Ti atoms in the inner layer of the structure migrate outward to react with oxygen, and there is C inside. 0 The nucleation of clusters and the formation of aggregated samples of amorphous carbon eventually led to the formation of carbon flakes covered by TiO2 particles, which is consistent with the previous TEM characterization.

[0058] The specific surface area and porous structure of the composite material were tested by nitrogen adsorption and desorption experiments. Figure 13 As shown in the figure, the composite material has a typical type I adsorption isotherm, which is consistent with the nitrogen adsorption and desorption characteristics of UIO-66-NH2 rich in microporous structure. In addition, the Brunauer-Emmett-Teller (BET) specific surface area of ​​the composite material is also measured to be 905 m 2 / g, Nonlocal density functional theory (NLDFT) simulation calculations show that Oxid-Ti3C2T x The pore size of / UIO-66-NH2 is distributed around 1.3nm. The above results show that UIO-66-NH2 and Ti3C2T x The combination of these gives the composite material a high specific surface area and a porous structure.

[0059] The following experimental protocol was used to selectively enrich phosphopeptides from standard protein digests, skim milk digests, human saliva, and serum enrichment samples:

[0060] The composite material of Example 1 was used as the enrichment material, and the enrichment material was washed with 200 μL of enrichment solution (50% ACN-H2O, 1% TFA) three times. During the enrichment, 200 μL of the enrichment sample was added to the washed enrichment material, and the material and the enrichment sample were mixed by vortexing, and then the mixture was incubated at 37°C on a shaker for 30 minutes. After the incubation, the supernatant was removed by centrifugation, and the material was washed with the enrichment solution (50% ACN-H2O, 1% TFA) three times by centrifugation to remove the non-specifically adsorbed impurities on the surface of the material. 20 μL of eluent (10% NH3·H2O) was added to the washed material, and the material and the eluent were mixed by vortexing and then incubated at 37°C on a shaker for 30 minutes. After the incubation, the supernatant was removed by centrifugation and used for mass spectrometry detection.

[0061] The experimental results are shown in Figure 14 and Figure 15 It can be concluded that, for the enrichment of phosphorylated peptides, the composite material is rich in active sites (Zr-O clusters, metal active sites and TiO2 nanoparticles), and exhibits excellent sensitivity (0.1 fmol μL -1 ) and relatively ideal selectivity (α-casein:BSA=1:100, molar ratio). In addition, when applied to complex biological samples, the material can enrich 24 phosphorylated peptides from skimmed milk, 15 endogenous phosphorylated peptides from human saliva and all 4 endogenous phosphorylated peptides from human serum, showing excellent enrichment effect, which proves the superior practicability of Oxid-Ti3C2T x / UIO-66-NH2, indicating its great application potential in the field of phosphorylated proteomics.

[0062] In summary, the present application first uses dielectric barrier discharge technology to promote the nucleation and rapid growth of UIO-66-NH2 and TiO2 nanoparticles on the surface of Ti3C2T x MXene nanosheets at room temperature and normal pressure. In terms of the synthesis method, the present application discards the reaction kettle in the traditional solvothermal method and uses a glass tube as the reaction container to realize the rapid growth of MOFs with high crystallinity and octahedral morphology on the surface of Ti3C2T x MXene nanosheets in an open system. During the growth of UIO-66-NH2, the DBD technology also causes a certain oxidation of MXenes, forming TiO2 nanoparticles, thereby obtaining Oxid-Ti3C2T x / UIO-66-NH2 composite material. The composite material combines the advantages of MOFs, Ti3C2T x MXene and TiO2 nanoparticles, such as the high porosity, large specific surface area and three-dimensional active site distribution characteristics of MOFs. xMXene and TiO2 nanoparticles contain a large number of exposed metal sites, low binding potential and high mass transfer efficiency. In the process of phosphopeptide enrichment, the components of the composite material complement each other and efficiently enrich phosphopeptides. When the amount of MOF precursor is changed, the density of Ti3C2T x The density of MOFs distributed on the surface of MXene is different, which affects the active sites of Zr-O, Ti-O and Ti for interaction with phosphopeptides, thereby realizing the controllable enrichment of phosphopeptides.

[0063] The above is only the preferred embodiment of the present application, not any form of limitation on the present application, although the present application has been disclosed as above, however, not to limit the present application, any person skilled in the art, without departing from the scope of the technical scheme of the present application, can make some changes or modifications of the above disclosed technical content for equivalent embodiments, but as long as it does not deviate from the content of the technical scheme of the present application, according to the technical essence of the present application, any simple modification, equivalent change and modification of the above embodiments are still within the scope of the technical scheme of the present application.

Claims

1. A method for preparing a dielectric barrier discharge induced Oxid-Ti3C2T x / UIO-66-NH2 composite material, characterized by, The steps are as follows: S1, preparing two-dimensional monolayer Ti3C2T x nanosheets, and dispersing the prepared nanosheets in DMF to obtain Ti3C2T x -DMF mixture solution, and storing at 4°C in a sealed manner; S2, polyvinylpyrrolidone was dissolved in DMF to obtain a clear solution, then Ti3C2T was added into the clear solution x -DMF mixture, ultrasonic dispersion to obtain a transparent ink green solution; S3, ZrCl4 is added to the cyan transparent solution, ultrasonic dispersion for several minutes, and then fixed on a shaking table for several hours. After the shaking is completed, 2-amino terephthalic acid and acetic acid are added to the obtained mixture in sequence, and ultrasonic dispersion is performed for several minutes to obtain a reaction liquid. In the formula, Ti3C2T x The mass ratio of the nanosheet and ZrCl4 is 1:14, and the mass ratio of ZrCl4 and 2-amino terephthalic acid is (1.2-1.3):

1. S4, each time take a few milliliters of reaction liquid in DBD reaction glass tube preparation, reaction discharge voltage is 37V, the current is 1.27A, reaction time is 40 minutes, after the reaction centrifugal separation, get dark gray solid product, namely Oxid-Ti3C2T x / UIO-66-NH2 composite material.

2. The dielectric barrier discharge induced Oxid-Ti3C2T x composite material of claim 1, characterized by a method for its preparation, characterized by In step S1, a two-dimensional monolayer Ti3C2T is prepared by etching Al atomic layer using minimum strength layer peeling method. x nanosheets.

3. The dielectric barrier discharge induced Oxid-Ti3C2T x composite material of claim 2, characterized by The specific steps of step S1 are as follows: S11, fix the polyethylene reaction container in a constant temperature oil bath pot at 35°C, add concentrated hydrochloric acid and deionized water, then slowly add LiF under stirring to obtain an HF solution; S12, uniformly add Ti3AlC2 into the reactor within 20 minutes, and stir the reaction at 35°C for 24 hours; S13, After the reaction, the product was repeatedly washed with deionized water and centrifuged. During the washing process, the product was stripped by hand shaking before each centrifugation to obtain stable Ti3C2T x nanosheets.

4. The dielectric barrier discharge induced Oxid-Ti3C2T x composite material of claim 1, characterized by a preparation method of In step S4, the obtained dark gray solid product was centrifuged, washed with DMF and centrifuged, and vacuum dried to obtain a purified dark gray solid product Oxid-Ti3C2T x / UIO-66-NH2 composite.

5. Oxid-Ti3C2T prepared by the method according to any one of claims 1 to 4 x Use of the composite material Oxid-Ti3C2T / UIO-66-NH2, characterized in that Use as a protein separation and enrichment material.

6. The Oxid-Ti3C2T of claim 5 x Use of the Oxid-Ti3C2T Use as an enrichment material for phosphorylated peptides.

7. The Oxid-Ti3C2T of claim 6 x Use of the Oxid-Ti3C2T The enrichment method of phosphorylated peptides is as follows: Oxid-Ti3C2T x As an enrichment material, the / UIO-66-NH2 composite material is first cleaned with an enrichment solution for multiple times. During enrichment, a solution containing a phosphated peptide segment is added to the cleaned enrichment material, and vortex is performed to mix the enrichment material and the solution thoroughly. Then, the mixture is placed in a shaking table for incubation at 37°C for 30 minutes. After the incubation, the supernatant is removed by centrifugation, and the lower solid is cleaned with the enrichment solution and centrifuged to remove the non-specifically adsorbed impurities on the surface of the material. The eluent is added to the cleaned material, vortex is performed to allow the material and the eluent to contact thoroughly, and the mixture is fixed in the shaking table for incubation at 37°C for 30 minutes. After the incubation, the supernatant is obtained by centrifugation.

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