CN113698598B - Nitrogen-rich porous organic polymer material, preparation and application - Google Patents

Nitrogen-rich porous organic polymer material, preparation and application Download PDF

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CN113698598B
CN113698598B CN202010440569.5A CN202010440569A CN113698598B CN 113698598 B CN113698598 B CN 113698598B CN 202010440569 A CN202010440569 A CN 202010440569A CN 113698598 B CN113698598 B CN 113698598B
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porous organic
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terephthalaldehyde
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欧俊杰
孙传盛
李亚
叶明亮
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Weigao Holding Co ltd
Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a preparation method of Porous Organic Polymer (POPs) based materials, and the POPs based materials are used for glycopeptide enrichment. Specifically, two organic monomers, namely terephthalaldehyde (pPAL) containing aldehyde groups and Carbohydrazide (CH) containing amino groups, are mixed, and then an ammonia aldehyde condensation reaction is carried out under the acid catalysis condition, so that the porous organic polymer material with high specific surface area and better crystal structure can be prepared in one step. The prepared porous organic polymer material (pPAL-CH) has relatively good stability and large specific surface area. And finally, applying the prepared porous organic polymer material to enrichment of the N-glycosylated peptide section.

Description

Nitrogen-rich porous organic polymer material, preparation and application
Technical Field
The invention particularly relates to a preparation method of a nitrogen-rich porous organic polymer material, and the porous organic polymer material can be used for glycopeptide adsorption.
Background
In recent years, Porous Organic Polymers (POPs) (Zhang y., ridean s.n. functional porous polymers for heterogeneous catalysis [ J ]. Chemical Society Reviews,2012,41(6): 2083-. Currently, different types of POPs have been developed and applied one after another. The synthesis of POPs is facilitated by the formation of strong covalent bonds between various light elements (C, Si, B, O, N). Researchers select aromatic compounds with different functional groups as building elements to synthesize various novel POPs materials. Currently, commonly used methods include palladium-catalyzed Sonogashira-Hagihara coupling (Jiang J.X., Su F., Trewin A., et al., conjugated microporus poly (aryleneethylene) networks [ J ]. Angewandte Chemie International Edition,2008,47(7): 1167) reactions and Buchwald-Hartwig coupling reactions. Because the traditional POPs synthesis method needs to use expensive catalysts and is difficult to meet the requirements of industrial production, the development of a novel POPs synthesis method with simple operation and low cost is urgently needed. The synthesis conditions based on the amino-aldehyde condensation are mild, the operation is easy, and no catalyst is needed, so the synthesis method is expected to be widely applied to the synthesis of POPs.
N-glycosylation is the most common type of protein glycosylation. However, direct analysis of N-glycosylated peptide fragments using mass spectrometry remains challenging due to the low abundance of N-glycosylation and interference from other abundant components. Thus, researchers have developed a variety of methods for specifically enriching glycopeptides, including lectin affinity chromatography, boronic acid affinity chromatography, hydrazide chemistry, and hydrophilic interaction chromatography (Xiong Z., ZHao L., Wang F., et al. Synthesis of branched PEG copolymers hydrophilic nanoparticles for the selective catalysis of N-linked glycopolypeptides [ J ]. Chemical Communications,2012,48(65): 8138-. The HILIC has the advantages of simplicity in operation, high specificity, good reproducibility and the like, and is widely applied to the research of glycosylation posttranslational modification omics.
Disclosure of Invention
The invention aims to provide a nitrogen-rich porous organic polymer material and a preparation method thereof, and the material can be applied to glycopeptide enrichment by utilizing the large specific surface area and a large number of amino functional groups.
A nitrogen-rich porous organic polymer material has a structural unit with a schematic formula as follows,
Figure BDA0002503914910000021
in order to achieve the above purpose, the technical scheme adopted by the invention specifically comprises the following contents:
the porous organic polymer with glycopeptide enrichment function has the advantages of simple preparation process, good stability and large specific surface area.
(1) Preparation of nitrogen-rich porous organic polymer materials
Weighing two terephthalaldehyde and carbohydrazide precursors with different functional groups into a 5-15 mL ampoule bottle, adding 1, 4-dioxane as a solvent, adding an acetic acid solution as a catalyst, and performing ultrasonic treatment for 5-15 min to obtain a uniform dispersion liquid. And (3) sealing the tube in vacuum, refluxing for 70-80 h in a muffle furnace at 100-140 ℃, carrying out an amino-aldehyde condensation reaction between the two monomers, washing the obtained product with N, N-dimethylformamide and anhydrous tetrahydrofuran in sequence after the reaction is finished, and then drying in a vacuum drying oven at 80-100 ℃ for 12-24 h. The prepared porous organic polymer material with large specific surface area can be applied to the enrichment of glycopeptides.
(2) Applications of
1-6 mg of material is adopted to enrich glycopeptide in IgG enzymolysis liquid. The specific process comprises the steps of firstly diluting 5-20 mu g of IgG protein enzymolysis liquid by 100-400 mu L of sample loading liquid, adding the hydrophilic material (porous organic polymer material), and then oscillating for 5-15 min at room temperature. Centrifuging and removing the supernatant. And then washed by the sample loading solution to remove non-glycopeptide and other impurities. Then adding 50-200 mu L of eluent, oscillating for 15-30 min at room temperature, centrifuging the mixture, and taking supernatant to analyze by MALDI-TOF/MS.
The invention mixes two organic monomers of terephthalaldehyde (pPAL) containing aldehyde group and Carbohydrazide (CH) containing amino group respectively, and then generates ammonia aldehyde condensation reaction under the acid catalysis condition, thus preparing the porous organic polymer material with high specific surface area and better crystal structure by one step. The prepared porous organic polymer material (pPAL-CH) has relatively good stability and large specific surface area. And finally, applying the prepared porous organic polymer material to enrichment of the N-glycosylated peptide section.
The invention has the advantages of
1. The invention prepares a nitrogen-rich porous organic polymer material, and the prepared porous organic polymer can be applied to enrichment of glycopeptides.
2. The porous organic polymer material prepared by the invention is completed through an ammonia-aldehyde condensation reaction, and compared with two cross-coupling reactions of Sonogashira-Hagihara and Suzuki-Miyaura which need expensive transition metal catalysis, the porous organic polymer material prepared by the reaction can avoid using a large amount of metals, the needed reaction monomers have low price and relatively mild reaction conditions, and the preparation process is simple, controllable, green and flexible.
3. The porous organic polymer material takes terephthalaldehyde and carbohydrazide as precursors, and synthesizes a novel porous organic polymer material pPAL-CH with high specific surface area and better ordered structure through an ammonia-aldehyde condensation reaction.
4. The porous organic polymer material is applied to the enrichment of glycopeptide, and has higher adsorption capacity on N-glycopeptide.
Drawings
FIG. 1 is a schematic diagram of the preparation of a porous organic polymer material (pPAL-CH).
FIG. 2 is a Fourier transform infrared spectrum of the product pPAL-CH of example 1. Fig. 2, 1670 cm-1 is attributed to the stretching vibration of-C ═ N-in pal-CH.
FIG. 3 is a solid nuclear magnetic map of pPAL-CH from example 1. As shown, the two characteristic signals 157ppm and 161ppm are assigned to the nuclear magnetic resonance signals-C ═ N-and-C ═ O, respectively.
FIG. 4 is a powder diffraction pattern of pPAL-CH from example 1. As shown in FIG. 4, the synthesized pPAL-CH according to the first example has a better crystal structure.
FIG. 5 is a scanning electron micrograph of pPAL-CH in example 1. The appearance and size of TFB-CHEDA are observed by a scanning electron microscope image, and the result is shown in FIG. 5, and pPAL-CH is a cauliflower-like structure.
FIG. 6 shows the N of pPAL-CH in example 1 2 Adsorption/desorption isotherms and the size of the specific surface area obtained from the isotherms. As shown in the figure, the specific surface area of pPAL-CH was determined by nitrogen adsorption-desorption method, and the specific surface area of pPAL-CH was 238m calculated according to the BET (Brunauer-Emmett-Teller) model 2 /g。
FIG. 7 is the MALDI-TOF/MS mass spectrum before and after enrichment of example 1IgG enzymatic hydrolysate with pPAL-CH material. (a) Before enrichment (b) after enrichment by pPAL-CH. As shown in the figure, the abundance of non-glycopeptides before enrichment is very high; after enrichment, the non-glycopeptides are obviously reduced, and the number of glycopeptides is obviously increased.
Table 1 shows the molecular mass, glycopeptide composition and amino acid sequence of N-glycopeptides.
Detailed Description
Example 1
1. To a 5mL ampoule was added 32mg carbohydrazide.
2. 48mg of terephthalaldehyde was added to the centrifuge tube.
3. 3mL of dioxane and 0.3mL of acetic acid solution (6M) were added to the centrifuge tube.
4. And (4) carrying out ultrasonic treatment on the centrifuge tube for 15min to uniformly mix the components in the centrifuge tube.
5. And (4) sealing the tube of the mixed solution obtained in the step (4) in a vacuum state.
6. And (3) placing the sealed ampoule bottle in the step 5 into a 120 ℃ gas phase furnace for reaction for 72 hours.
7. And cleaning the material by using N, N-dimethylformamide and anhydrous tetrahydrofuran in sequence to remove the reaction solvent and the small molecular oligomer.
8. Taking the specific surface area obtained in the step 7 as 238m 2 2mg of POP material/g is put in a centrifugal tube of 600 mu L, then 15 mu g of immunoglobulin G (IgG) enzymolysis liquid after trypsin enzymolysis is added in the centrifugal tube, the centrifugal tube is incubated for 30min in a constant temperature oscillator of 25 ℃ and 1500rpm, then the mass spectrum analysis is carried out on the enriched glycopeptide through rinsing and elution respectively, the mass spectrum takes a non-glycopeptide peak as the main part, the non-glycopeptide is almost completely removed after pPAL-CH enrichment, and the molecular mass and glycopeptide composition of 15 glycopeptides are detected, wherein the molecular mass and glycopeptide composition of the N-glycopeptide are shown in Table 1.
Table 1 molecular mass and glycopeptide composition of N-glycopeptides (N x represents N glycosylation site).
Figure BDA0002503914910000061
Example 2
1. To a 5mL ampoule was added 32mg carbohydrazide.
2. 48mg of terephthalaldehyde was added to the centrifuge tube.
3. To the tube was added 3mL of dioxane and 0.3mL of aqueous acetic acid (6M).
4. And (4) carrying out ultrasonic treatment on the centrifuge tube for 15min to uniformly mix the components in the centrifuge tube.
5. And (4) sealing the tube of the mixed solution obtained in the step (4) in a vacuum state.
6. And (3) placing the sealed ampoule bottle in the step 5 into a gas phase furnace at 80 ℃ for reaction for 72 h.
7. And cleaning the material by using N, N-dimethylformamide and anhydrous tetrahydrofuran in sequence to remove the reaction solvent and the small molecular oligomer.
8. Taking the specific surface area obtained in the step 7 as 94m 2 2mg of POP material/g is put into a 600 mu L centrifuge tube, then 15 mu g of immunoglobulin (IgG) enzymolysis liquid subjected to trypsin enzymolysis is added into the centrifuge tube, the mixture is incubated for 30min in a constant temperature oscillator at 25 ℃ and 1500rpm, then the mass spectrum analysis is carried out on the enriched glycopeptides through rinsing and elution respectively, the mass spectrum takes a non-glycopeptide peak as the main part, the non-glycopeptides are almost completely removed after pPAL-CH enrichment, and 3 glycopeptides are detected, wherein the mass-to-charge ratios of the glycopeptides are m/z 2633.99, 2796.05 and 2958.10 respectively.
Example 3
1. To a 5mL ampoule 22mg carbohydrazide was added.
2. 32mg of terephthalaldehyde was added to the centrifuge tube.
3. 2mL of dioxane and 0.2mL of aqueous acetic acid (6M) solution were added to the centrifuge tube.
4. And (4) carrying out ultrasonic treatment on the centrifuge tube for 15min to uniformly mix the components in the centrifuge tube.
5. And (4) sealing the tube of the mixed solution obtained in the step (4) in a vacuum state.
6. And (3) placing the sealed ampoule bottle in the step 5 into a gas phase furnace at 100 ℃ for reaction for 72 h.
7. And cleaning the material by sequentially using N, N-dimethylformamide and anhydrous tetrahydrofuran to remove the reaction solvent and the micromolecular oligomer.
8. Taking the specific surface area obtained in the step 7 as 161m 2 2mg of POP material/g is put in a centrifugal tube of 600 mu L, then 15 mu g of immunoglobulin G (IgG) enzymolysis liquid after trypsin enzymolysis is added in the centrifugal tube, the centrifugal tube is incubated for 30min in a constant temperature oscillator of 1500rpm at 25 ℃, then the mass spectrum analysis is carried out on the enriched glycopeptide through rinsing and elution respectively, the mass spectrum takes a non-glycopeptide peak as the main, the non-glycopeptide is almost completely removed after pPAL-CH enrichment, and 8 glycopeptides are detected. The mass/charge ratios are 2602.01, 2633.99, 2764.04, 2796.05, 2839.06, 2926.10, 2999.11 and 2958.10 respectively.
Example 4
1. To a 5mL ampoule was added 32mg carbohydrazide.
2. 48mg of terephthalaldehyde was added to the centrifuge tube.
3. To the tube was added 1.5mL of dioxane, 1.5mL of mesitylene, and 0.3mL of aqueous (6M) acetate solution.
4. And (4) carrying out ultrasonic treatment on the centrifuge tube for 15min to uniformly mix the components in the centrifuge tube.
5. And (4) sealing the tube of the mixed solution obtained in the step (4) in a vacuum state.
6. And (3) placing the sealed ampoule bottle in the step 5 into a 120 ℃ gas phase furnace for reaction for 72 hours.
7. And cleaning the material by using N, N-dimethylformamide and anhydrous tetrahydrofuran in sequence to remove the reaction solvent and the small molecular oligomer.
8. PXRD characterization tests were performed to verify that the two monomers did not form a good crystalline structure under this solvent system, and only a broad peak was present at 2 θ ═ 20 °. Therefore, the solvent system is not suitable for preparing POP with the crystal form ordered structure.
Example 5
1. To a 5mL ampoule was added 32mg carbohydrazide.
2. 48mg of terephthalaldehyde was added to the centrifuge tube.
3. To the tube was added 3mL mesitylene and 0.3mL acetic acid solution (6M).
4. And (4) carrying out ultrasonic treatment on the centrifuge tube for 15min to uniformly mix the components in the centrifuge tube.
5. And (4) sealing the tube of the mixed solution obtained in the step (4) in a vacuum state.
6. And (4) placing the sealed ampoule bottle in the step 5 into a gas phase furnace at 120 ℃ for reaction for 72 h.
7. And cleaning the material by sequentially using N, N-dimethylformamide and anhydrous tetrahydrofuran to remove the reaction solvent and the micromolecular oligomer.
8. PXRD characterization tests were performed to verify that the two monomers did not form a good crystalline structure under this solvent system, with only one broad peak present at 2 θ ═ 20 °. Therefore, the solvent system is also not suitable for preparing POP with the crystal form ordered structure.

Claims (8)

1. A preparation method of a nitrogen-rich porous organic polymer material is characterized by comprising the following steps:
the preparation method comprises the following steps of preparing a nitrogen-rich porous organic polymer material pPAL-CH in a dioxane solution by taking terephthalaldehyde and carbohydrazide as precursors, wherein the structural units of the material are shown in the following schematic formula:
Figure 229103DEST_PATH_IMAGE001
；
the preparation method comprises the following steps: weighing terephthalaldehyde and carbohydrazide precursors into a 5-15 mL ampoule bottle, adding 1, 4-dioxane as a solvent, adding an acetic acid solution as a catalyst, and performing ultrasonic treatment for 5-15 min to obtain a uniform dispersion liquid; and (3) sealing the tube in vacuum, refluxing for 70-80 h in a muffle furnace at 100-140 ℃, carrying out an amino-aldehyde condensation reaction between the two monomers, washing the obtained product with N, N-dimethylformamide and anhydrous tetrahydrofuran in sequence after the reaction is finished, and then drying for 12-24 h in a vacuum drying oven at 80-100 ℃.
2. The method of claim 1, wherein: the mol ratio of amino and aldehyde functional groups participating in the amino-aldehyde condensation reaction in carbohydrazide and terephthalaldehyde is as follows: 0.5 to 1.5.
3. The method according to claim 1, characterized in that: the volume of the 1, 4-dioxane solution is 1-3 mL.
4. The method of claim 1, wherein: the concentration of the catalyst acetic acid is 2-8 mol/L, and the volume is 0.3 mL.
5. The production method according to claim 2, characterized in that: the molar ratio of amino functional groups and aldehyde functional groups participating in the amino-aldehyde condensation reaction in the carbohydrazide and the terephthalaldehyde is 1: 1.
6. A nitrogen-rich porous organic polymeric material obtained by the production method according to any one of claims 1 and 2.
7. The nitrogen-rich porous organic polymer material according to claim 6, wherein the porous organic polymer has a specific surface area of 100 to 400 m 2 The number of PXRD peaks is 3-8.
8. Use of the nitrogen-rich porous organic polymeric material of claim 1, wherein: the nitrogen-rich porous organic polymer material is used for enriching glycopeptide in the protein enzymolysis liquid.
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