CN115626967A

CN115626967A - Bifunctional adsorption resin, preparation method and application

Info

Publication number: CN115626967A
Application number: CN202211073623.2A
Authority: CN
Inventors: 龚波林; 欧俊杰; 韩速; 黄超
Original assignee: Ningxia Bethel Active Carbon Co ltd; North Minzu University
Current assignee: Ningxia Bethel Active Carbon Co ltd; North Minzu University
Priority date: 2022-09-02
Filing date: 2022-09-02
Publication date: 2023-01-20
Anticipated expiration: 2042-09-02
Also published as: CN115626967B

Abstract

The invention belongs to the technical field of adsorption resin, and discloses a bifunctional adsorption resin, a preparation method and application thereof. The resin matrix is macroporous resin microspheres with epoxy groups on the surface, the particle size of the microspheres is 5-6 mu m, polymer brushes with olefin are grafted on the surfaces of the microspheres, and L-cysteine is introduced into the surfaces of the microspheres. The preparation method specifically adopts a seed swelling polymerization method, uses 3,4-epoxy cyclohexyl methacrylate as a monomer and tetraethyleneglycol diacrylate as a cross-linking agent to prepare the macroporous resin microsphere with epoxy groups on the surface, then utilizes an atom transfer radical polymerization technology to graft a polymer brush with olefin on the surface of the microsphere, and finally introduces L-cysteine to the surface of the microsphere through a photo-initiated mercapto-alkene click chemical reaction to prepare the bifunctional adsorption resin which can be used for metal ion adsorption and/or glycopeptide enrichment.

Description

Bifunctional adsorption resin, preparation method and application

Technical Field

The invention belongs to the technical field of adsorption resin, and particularly relates to bifunctional adsorption resin, a preparation method and application thereof.

Background

With the acceleration of the industrialization process, the pollution of heavy metal ions to the water body is increasingly serious. Copper is a typical heavy metal and is widely applied to printing and dyeing, metallurgy, electronics, nuclear power and other manufacturing industries. Cu (II) ions (Cu) generated during production and fabrication ²⁺ ) Difficult to be degraded by microorganisms, and if the wastewater is directly discharged into the environment without being treated, the wastewater can be left in water for a long time to pollute a water source. Once excessive Cu is ingested in the body ²⁺ Gene mutation may be caused due to characteristics such as difficulty in biodegradation, easiness in biological accumulation, etc., thereby causing serious health hazards such as wilson disease, alzheimer disease, etc. (documents 1.s. Bolisetty, m.peydayeye, r.mezzena, sustatin technologies for water purification from health measures; therefore, cu should be dealt with before wastewater discharge ²⁺ And (4) carrying out adsorption removal.

At present, various Cu removal technologies such as adsorption, precipitation, ion exchange, membrane technology and the like are researched ²⁺ The method of (1). Among them, the adsorption method is widely used in water treatment because of its simple operation, low cost and high efficiency (documents 2.A. Abidi, Y. Huang, Z. Ben Rejeb, A. Zaoui, C.B. Park, sustaineble and effective technologies for removal and recovery of oxygen and effective metals from wastewater:recent progress,challenges,and future perspectives,Chemosphere 292(2022)133102)。

Proteins are the main contributors and executives of various life activities. Glycosylation is one of the important post-translational modifications of proteins, and plays an important role in regulation in complex biological processes such as signal transduction, cell proliferation and homeostasis. Abnormal glycosylation is often associated with certain diseases including cancer (3.M. Rosato, S.Stringer, T.Gebuis, I.Paliukhovich, K.W.Li, D.Posthuma, P.F.Sullivan, A.B.Smit, R.E.van Kesteen, combined cells and proteins analysis resources shared neural morphology and molecular pathway pharmaceuticals for multi-schzophraria genes, mol.Psychiator.26 (2021) 784-799). Therefore, glycopeptide analysis is crucial for the diagnosis and treatment of diseases. Mass Spectrometry (MS) has become a key tool for proteomics research. However, direct mass spectrometry of glycopeptides is difficult due to the low abundance and strong interference of glycopeptides in biological samples (documents 4.L. Zhang, S.Ma, Y.Chen, Y.Wang, J.Ou, H.Uyama, M.Ye, medicine failure of biological chemistry and molecular membrane with carbohydrate-structure for the purposes of analysis of glycosylated peptides, anal. Chem.91 (2019) 2985-2993). Therefore, enrichment of low abundance glycopeptides becomes an essential step before mass spectrometry.

So far, the hydrophilic interaction chromatography (HILIC) strategy for exploring hydrophilic interaction between glycopeptide and adsorbent has been an ideal glycopeptide enrichment strategy due to its good selectivity, unbiased property and high compatibility with MS (document 5.Y. Tian, R. Tang, X. Wang, J.ZHou, X.Li, S.Ma, B.Gong, J.Ou, bioinpired dandelion-lipid nanoparticles modified with L-glutathione for high efficiency engineering applications, anal. Chim. Acta 3 (2021) 8978 zft 8978), based on which a bifunctional resin with good water adsorption is proposed in the present application.

Disclosure of Invention

The invention relates to a bifunctional adsorption resin, in particular to a resin matrix which is a macroporous resin microsphere with an epoxy group on the surface, the particle size of the microsphere is 5-6 mu m, a polymer brush with olefin is grafted on the surface of the microsphere, and L-cysteine is introduced into the surface of the microsphere.

The invention relates to a preparation method of bifunctional adsorption resin, which specifically adopts a seed swelling polymerization method, takes 3,4-epoxy cyclohexyl methacrylate as a monomer and tetraethyleneglycol diacrylate as a cross-linking agent to prepare macroporous resin microspheres with epoxy groups on the surfaces, then utilizes an atom transfer radical polymerization technology to graft polymer brushes with olefin on the surfaces of the microspheres, and finally introduces L-cysteine to the surfaces of the microspheres through a photoinitiated sulfydryl-ene click chemical reaction to prepare the bifunctional adsorption resin which can be used for metal ion adsorption and/or glycopeptide enrichment.

The preparation process comprises the following steps:

s1, preparing macroporous resin microspheres with epoxy groups on surfaces

Mixing and emulsifying poly glycidyl methacrylate, 3,4-epoxy cyclohexyl methacrylate, tetraethylene glycol diacrylate, n-propyl alcohol, 1,4-butanediol, azodiisobutyronitrile and water phase according to the proportion of 9-11 mL/6-8 mL/0.4-0.6 g/150-170 mL;

reacting at room temperature for 12-18 h, then heating to 60-80 ℃ and continuing to react for 12-18 h;

and (3) performing Soxhlet extraction for 24-48 h after reaction, then washing with absolute ethyl alcohol and deionized water for 3-5 times respectively, and finally performing vacuum drying at 60 ℃ for 12-20 h to obtain the macroporous resin microspheres with epoxy groups on the surfaces.

S2, grafting a polymer brush with olefin on the surface of the microsphere

Taking macroporous resin microspheres with epoxy groups on the surfaces, dispersing the macroporous resin microspheres in a sulfuric acid solution, reacting for 10-12 h at 40-60 ℃, then washing the product after the reaction to be neutral, and drying in vacuum;

dissolving the dried microspheres in dichloromethane, adding triethylamine, 2-bromoisobutyryl bromide and 4-dimethylaminopyridine under an ice bath condition, reacting at room temperature, and washing to obtain a macroinitiator;

dispersing a macroinitiator, 2,2' -bipyridine and allyl methacrylate in a mixed solvent of ethanol and deionized water according to the proportion of 1.0-1.2 g/50-60 mg/0.4-0.6 mL/8-12 mL, wherein the volume ratio of ethanol to deionized water in the mixed solvent of ethanol and deionized water is 4/1;

removing oxygen in the solvent through operations of freezing, vacuumizing and filling nitrogen, adding a cuprous bromide catalyst into the solvent according to the proportion of 8-12 mL/25-30 mg, carrying out catalytic reaction for 20-24 h at 50-70 ℃ in the nitrogen atmosphere, and washing for 3-5 times by using ethanol, deionized water and an ethylene diamine tetraacetic acid aqueous solution in sequence after the reaction to obtain the microsphere with the surface grafted with the olefin-containing polymer brush.

S3, preparing the bifunctional adsorption resin

Dissolving photoinitiator benzoin dimethyl ether in an ethanol-deionized water solution, wherein the volume ratio of ethanol to deionized water in the ethanol-deionized water solution is 1/1;

adding a resin matrix of a polymer brush grafted with olefin on the surface of the microsphere, performing ultrasonic dispersion, and then adding L-cysteine; wherein the mixing proportion of the benzoin dimethyl ether, the solution of ethanol-deionized water, the resin matrix of the polymer brush grafted with olefin on the surface of the microsphere and the L-cysteine is 20-30 mg/20-30 mL/300-400 mg;

irradiating for 20-40 min under 365nm ultraviolet light, washing with ethanol and deionized water for 3-5 times respectively, and drying at room temperature to obtain the bifunctional adsorption resin.

Compared with the prior art, the invention has the following beneficial effects:

1. the bifunctional adsorption resin takes macroporous resin MAR microspheres with epoxy groups on the surfaces as a matrix, adopts an atom transfer radical polymerization technology to graft polymer brushes with olefin on the surfaces of the microspheres, and finally introduces L-cysteine to the surfaces of the microspheres through a photo-initiated sulfydryl-ene click chemical reaction, wherein the L-cysteine has functional groups such as amino, carboxyl and the like, so that the whole resin microspheres keep good hydrophilicity, and not only can effectively enrich glycopeptides, but also can provide rich binding sites for the enrichment of metal ions.

2. The preparation method is simple, the raw materials are cheap and easy to obtain, and the prepared product is pure, monodisperse and uniform in pore size.

Drawings

FIG. 1 is a flow chart of the preparation of the bifunctional adsorbent resin of the present invention;

FIG. 2 is a helium ion electron microscope image of macroporous resin microspheres (a) and bifunctional adsorption resin (b);

FIG. 3 is an infrared representation of macroporous resin microspheres, microspheres with olefin-containing polymer brushes grafted on the surface, and bifunctional adsorbent resins;

FIG. 4 is an X-ray diffraction electron energy spectrum: the full spectrogram of (a) microspheres grafted with polymer brushes containing olefin on the surface, (b) the full spectrogram of a bifunctional adsorption resin, (c) an N-1S high resolution energy spectrogram of the bifunctional adsorption resin, and (d) an S-2p high resolution energy spectrogram of the bifunctional adsorption resin;

FIG. 5 is an analysis chart of the bifunctional adsorption resin before and after enrichment of IgG trypsin digestion solution: (a) pre-enrichment analysis, (b) post-enrichment analysis of 10 μ g IgG trypsin digest, (c) post-deglycosylation analysis, (d) post-enrichment analysis of 10fmol IgG trypsin digest, (e) signal intensity analysis of 4 selected N-glycopeptides enriched in different amounts; the graph indicates the N-glycopeptide;

FIG. 6 shows a bifunctional adsorption resin pair of Cu ²⁺ An adsorption isotherm curve (a) and a kinetic curve (d) and fitted by (b) a Langmuir model, (c) a Freundlich model, (e) a quasi-primary model, and (f) a quasi-secondary model.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

1. Preparation of bifunctional adsorption resin

S1, preparing macroporous resin microspheres with epoxy groups on surfaces

Mixing 8mL of 3,4-Epoxycyclohexylmethacrylate (EMA), 8mL of tetraethyleneglycol diacrylate (TEGDA), 8mL of n-propanol, 8mL of 1,4-butanediol, 0.5g of azobisisobutyronitrile and 160mL of an aqueous phase after ultrasonic disruption and emulsification with 10mL of a solution of polyglycidyl methacrylate (seeds), wherein the aqueous phase comprises Sodium Dodecyl Sulfate (SDS) with a concentration of 0.2% and polyvinyl alcohol (PVA) with a concentration of 0.5%;

reacting at room temperature for 16h, and then heating to 70 ℃ to continue reacting for 16h;

performing Soxhlet extraction for 24h after reaction, then washing with absolute ethyl alcohol and deionized water for 3 times respectively, and finally performing vacuum drying for 12h at 60 ℃ to obtain the macroporous resin Microspheres (MAR) with epoxy groups on the surface.

S2, grafting a polymer brush with olefin on the surface of a microsphere

Dispersing macroporous resin microspheres with epoxy groups on the surface in a sulfuric acid solution, reacting for 12 hours at 60 ℃, washing the product after the reaction to neutrality, and drying in vacuum;

dispersing 1.0g of macroinitiator, 50mg of 2,2' -bipyridine and 0.5mL of Allyl Methacrylate (AMA) in 10mL of ethanol-deionized water mixed solvent, wherein the volume ratio of ethanol to deionized water in the ethanol-deionized water mixed solvent is 4/1;

the freezing, vacuumizing and nitrogen charging operations are performed 3 times in a cycle to remove oxygen in the solvent, and then 25mg of cuprous bromide catalyst is added;

and (3) performing freezing, vacuumizing and nitrogen filling operations repeatedly, performing catalytic reaction at 60 ℃ for 24 hours in a nitrogen atmosphere, and washing the reaction product for 3 times by using ethanol, deionized water and an ethylene diamine tetraacetic acid disodium aqueous solution in sequence to obtain microspheres (poly (AMA) @ MAR microspheres) with the surface grafted with the polymer brush containing olefin.

S3, preparing the bifunctional adsorption resin

Dissolving 30mg of photoinitiator benzoin dimethyl ether in 25mL of ethanol-deionized water solution, wherein the volume ratio of ethanol to deionized water in the ethanol-deionized water solution is 1/1;

adding 300mg of poly (AMA) @ MAR microsphere, performing ultrasonic dispersion, adding 400mg of L-cysteine (L-Cys), irradiating for 30min under 365nm ultraviolet light, washing with ethanol and deionized water for 3 times respectively, and drying at room temperature to obtain the bifunctional adsorption resin (Cys @ poly (AMA) @ MAR).

2. Material characterization

FIG. 2 is a helium ion electron microscope image of macroporous resin Microspheres (MAR) and bifunctional adsorption resin (Cys @ poly (AMA) @ MAR). As can be seen, monodisperse MAR microspheres with a diameter of about 5 μm were successfully prepared by seed swelling polymerization (FIG. 2 a), while the modified microsphere morphology (FIG. 2 b) was similar to the original MAR (FIG. 2 a) and the particle surface was slightly rough, indicating the successful preparation of Cys @ poly (AMA) @ MAR.

FIG. 3: the macroporous resin Microspheres (MAR), the microspheres grafted with the polymer brush containing olefin on the surface (poly (AMA) @ MAR microspheres), and the bifunctional adsorption resin (Cys @ poly (AMA) @ MAR) were characterized by Fourier transform attenuated total reflectance infrared spectroscopy (ATR-FTIR), as shown in FIG. 3:

in the spectrum of the MAR, 910cm-1 is the characteristic peak of the epoxy groups, which is absent in the other spectra, indicating that the epoxy groups on the surface of the modified MAR have been depleted.

In the poly (AMA) @ MAR spectrum, a characteristic peak at 3531cm-1 corresponds to stretching vibration of-OH, and a weak peak at 1634cm-1 corresponds to C = C stretching vibration, and these two characteristic peaks do not appear in the Cys @ poly (AMA) @ MAR spectrum.

In the spectrum of Cys @ poly (AMA) @ MAR, two characteristic peaks of 3540cm-1 and 1580cm-1 are-NH 2 corresponding to tensile vibration and deformation vibration, respectively, and a weak peak of 1625cm-1 corresponds to stretching vibration of-COOH, thereby indicating that L-cysteine (L-Cys) is successfully grafted on the surface of MAR.

FIG. 4 is an XPS spectrum, in particular:

the microsphere (poly (AMA) @ MAR microsphere) spectrogram (4 a) grafted with the polymer brush containing olefin on the surface is free of N, S peaks, and the bifunctional adsorption resin (Cys @ poly (AMA) @ MAR) spectrogram (4 b) has N, S peaks, so that the surface Cys @ poly (AMA) @ MAR is successfully prepared.

In the high resolution N-1s spectrum of Cys @ poly (AMA) @ MAR (FIG. 4C), the characteristic peaks of 399.1eV and 401eV are assigned to C-N and N-H, respectively; in the high resolution S-2p spectrum of Cys @ poly (AMA) @ MAR (FIG. 4 d), the characteristic peaks of 163.4eV and 164.6eV belong to the 3/2p orbital and 1/2p orbital of the sulfur atom, based on which the success of Cys @ poly (AMA) @ MAR preparation is further demonstrated.

3. Glycopeptide enrichment

Placing 5mg of bifunctional adsorption resin (Cys @ poly (AMA) @ MAR) in a centrifuge tube, firstly activating with 200 μ L of sample solution (acetonitrile ACN/water H2O/trifluoroacetic acid TFA =87/12/1, volume ratio), and then placing in 200 μ L of sample solution containing a certain amount of protein digestive juice to incubate at room temperature for 30min;

oscillating and centrifuging at room temperature, and removing supernatant; shaking was sufficient, and shaking was generally carried out for 8 hours.

Washing with the sample solution three times to remove non-glycopeptide adsorbed on the material;

finally, the glycopeptide enriched on the material was eluted with an eluent (acetonitrile ACN/water H2O/trifluoroacetic acid TFA =30/69/1, volume ratio) and the resulting eluent was analyzed by matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF-MS).

4. Adsorption of metal ions

Dynamic adsorption: dispersing 10mg of bifunctional adsorbent resin (Cys @ poly (AMA) @ MAR) into 10mL (6 mmol/L) of Cu ²⁺ In aqueous solution. After 20, 40, 60, 90, 120, 150, 180, 240, 300min of incubation, the supernatant was taken for atomic absorption spectrophotometry analysis through a membrane.

Static adsorption: 10mg of bifunctional adsorbent resin (Cys @ poly (AMA) @ MAR) was dispersed in 10mL of Cu at various concentrations (1.0, 3.0, 5.0, 6.0, 7.0, 8.0, 9.0 mmol/L) ²⁺ The aqueous solution was incubated at 25 ℃ for 12h and then filtered through a 0.22 μm filter and the collected filtrate was analyzed by atomic absorption spectrophotometer.

Example 2

Preparation of bifunctional adsorption resin

S1, preparing macroporous resin microspheres with epoxy groups on surfaces

Mixing 6mL of 3,4-Epoxycyclohexylmethacrylate (EMA), 6mL of tetraethyleneglycol diacrylate (TEGDA), 6mL of n-propanol, 6mL of 1,4-butanediol, 0.4g of azobisisobutyronitrile and 150mL of an aqueous phase with 9mL of a solution of polyglycidyl methacrylate (seed) after ultrasonication and emulsification, wherein the aqueous phase comprises Sodium Dodecyl Sulfate (SDS) with a concentration of 0.2% and polyvinyl alcohol (PVA) with a concentration of 0.5%;

reacting at room temperature for 12h, then heating to 60 ℃ and continuing to react for 12h;

S2, grafting a polymer brush with olefin on the surface of a microsphere

Dispersing macroporous resin microspheres with epoxy groups on the surface in a sulfuric acid solution, reacting for 12 hours at 60 ℃, washing the product after reaction to be neutral, and drying in vacuum;

and (2) performing freezing, vacuumizing and nitrogen filling operation for 3 times in a recycling manner, performing catalytic reaction for 24 hours at 60 ℃ in a nitrogen atmosphere, and washing for 3 times by using ethanol, deionized water and an ethylene diamine tetraacetic acid disodium water solution in sequence after the reaction to obtain microspheres (poly (AMA) @ MAR microspheres) with olefin-containing polymer brushes grafted on the surfaces.

S3, preparing the bifunctional adsorption resin

The operation of enriching glycopeptide and adsorbing metal ion with the bifunctional adsorption resin (Cys @ poly (AMA) @ MAR) of this example was the same as that of example 1.

Material applications

(1) Application of bifunctional adsorption resin (Cys @ poly (AMA) @ MAR) in glycopeptide enrichment

IgG trypsin digestive juice is taken as a sample, the bifunctional adsorption resin (Cys @ poly (AMA) @ MAR) prepared in the embodiment 1 is used for enrichment, and due to the introduction of L-cysteine (L-Cys), a large number of polar groups (such as amino groups and carboxyl groups) are arranged on the surface of the bifunctional adsorption resin, so that the Cys @ poly (AMA) @ MAR has strong hydrophilicity and can be used as a hydrophilic interaction chromatography (HILIC) adsorbent for enriching glycopeptides. The enriched glycopeptides were assayed by MALDI-TOF-MS and the results are shown in FIG. 5:

before enrichment (FIG. 5 a) the non-glycopeptide signal heavily masked the N-glycopeptide signal;

after 10 μ g of IgG trypsin digestion solution was enriched with Cys @ poly (AMA) @ MAR prepared in example 1, as shown in FIG. 5b, glycopeptide signal was significantly increased (signal intensity 1018.3), and interference of non-glycopeptide signal was weak;

deglycosylated PNGase-F with the eluted glycopeptide with the loading solution (acetonitrile ACN/water H2O/trifluoroacetic acid TFA =87/12/1, volume ratio), as shown in fig. 5c, the glycopeptide signal disappeared and only two deamidated peptides (1158 m/z and 1190 m/z) were detected, thereby indicating that all disappeared glycopeptide signals belong to N-glycopeptide;

as shown in FIG. 5d, the enriched 7 typical N-glycopeptides (2601 m/z, 2633m/z, 2764m/z, 2795m/z, 2805m/z, 2925m/z and 2957 m/z) were clearly recognized, and the glycopeptide signal intensity was 402.4 when the sample size of IgG trypsin digest was reduced to 10fmol, thus indicating that Cys @ poly (AMA) @ MAR has a higher sensitivity to N-glycopeptides.

By enriching IgG trypsin digestive juice with different contents by Cys @ poly (AMA) @ MAR and selecting N-glycopeptide consisting of 2601, 2633, 2763 and 2795 as a marker, as shown in figure 5e, the strength of four markers is correspondingly increased along with the increase of the IgG trypsin digestive juice, and when the IgG trypsin digestive juice is increased to 45 mu g, the strength of the markers is not increased any more, thereby indicating that the maximum adsorption quantity of Cys @ poly (AMA) @ MAR is 9mg/g.

(2) Bifunctional adsorption resin (Cys @ poly (AMA) @ MAR) in Cu ²⁺ Application in adsorption

The maximum adsorption capacity is a key index for evaluating the adsorption performance of the material.

In order to evaluate the adsorption capacity of bifunctional adsorption resin (Cys @ poly (AMA) @ MAR) for metal ions, the adsorption capacity of the bifunctional adsorption resin for metal ions at different concentrations was tested, and an isothermal adsorption curve thereof was plotted (FIG. 6 a), from which: when Cu ²⁺ When the concentration is less than 6mmol/L, the adsorption amount of Cys @ poly (AMA) @ MAR is dependent on Cu ²⁺ The concentration increases rapidly; when Cu ²⁺ When the concentration is higher than 6mmol/L, the adsorption isotherm reaches a plateau, and Cys @ poly (AMA) @ MAR is calculated for Cu ²⁺ The maximum adsorption amount of (2) was 63mg/g.

To study Cu ²⁺ The adsorption mechanism on Cys @ poly (AMA) @ MAR was fitted with a Langmuir model and a Freundlich model to an adsorption isotherm, and as a result, as shown in FIGS. 6b and 6c, it was found that the Langmuir model and the Freundlich model had linear correlation coefficients of 0.9981 and 0.9594, respectively. Apparently Cys @ poly (AMA) @ MAR vs. Cu ²⁺ The adsorption type of (1) is more consistent with a Langmuir model and is a monomolecular layer adsorption mode.

The speed of the material reaching the adsorption equilibrium is also an important index for researching the material as an adsorbent, so the dynamic adsorption process of Cys @ poly (AMA) @ MAR is also researched. As shown in FIG. 6d, cys @ poly (AMA) @ MAR vs. Cu ²⁺ The adsorption quantity of the material is rapidly increased in the first 120min, and the adsorption quantity is basically unchanged after the adsorption quantity exceeds 120min, so that the adsorption sites on the surface of the material are all occupied, and the adsorption equilibrium is reached. According to the suctionFitting a quasi-first-order and a quasi-second-order kinetic model by using an attached curve, as shown in FIG. 6e and FIG. 6 f: the linear fitting correlation coefficient of the quasi-first order model is 0.8837, and the linear fitting correlation coefficient of the quasi-second order model is 0.9974. Apparently, the pseudo-second order kinetic model is more suitable for describing Cu ²⁺ Kinetic adsorption process on Cys @ poly (AMA) @ MAR.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A bifunctional adsorbent resin characterized by:

the resin matrix is macroporous resin microspheres with epoxy groups on the surface;

the surface of the microsphere is grafted with a polymer brush with olefin, and L-cysteine is introduced into the surface of the microsphere.

2. The bifunctional adsorbent resin of claim 1, wherein: the particle size of the macroporous resin microspheres with epoxy groups on the surface is 5-6 microns.

3. The preparation method of the bifunctional adsorption resin is characterized by comprising the following steps:

preparing macroporous resin microspheres with epoxy groups on the surfaces, and taking the macroporous resin microspheres as a resin matrix;

grafting a polymer brush with olefin on the surface of the microsphere by utilizing an atom transfer radical polymerization technology;

introducing L-cysteine to the surface of the microsphere through a photo-initiated 'mercapto-alkene' click chemical reaction to obtain the bifunctional adsorption resin.

4. The preparation method according to claim 3, wherein the step of preparing the macroporous resin microspheres with epoxy groups on the surfaces comprises the following steps:

the method comprises the steps of taking polyglycidyl methacrylate as seeds, 3,4-epoxy cyclohexyl methacrylate as a monomer, tetraethyleneglycol diacrylate as a cross-linking agent, n-propanol and 1,4-butanediol as pore-forming agents, azodiisobutyronitrile as an initiator, and sodium dodecyl sulfate with the concentration of 0.2% and polyvinyl alcohol with the concentration of 0.5% as water phases, and preparing the macroporous resin microspheres with epoxy groups on the surfaces by utilizing a seed swelling polymerization mode.

5. The method of claim 4, wherein:

mixing and emulsifying poly glycidyl methacrylate, 3,4-epoxy cyclohexyl methacrylate, tetraethylene glycol diacrylate, n-propanol, 1,4-butanediol, azobisisobutyronitrile and a water phase according to the proportion of 9-11 mL/6-8 mL/0.4-0.6 g/150-170 mL;

6. The method according to claim 3, wherein the step of grafting the polymer brush with olefin on the surface of the microsphere by using an atom transfer radical polymerization technique comprises:

taking macroporous resin microspheres with epoxy groups on the surface, dispersing the macroporous resin microspheres in a sulfuric acid solution, reacting for 10-12 h at 40-60 ℃, washing the product after reaction to be neutral, and drying in vacuum;

7. The method of claim 3, wherein the step of introducing L-cysteine to the surface of the microsphere by photoinitiating a "thiol-ene" click chemistry reaction comprises:

dissolving a photoinitiator benzoin dimethyl ether in an ethanol-deionized water solution, wherein the volume ratio of ethanol to deionized water in the ethanol-deionized water solution is 1/1;

adding a resin matrix of a polymer brush grafted with olefin on the surface of the microsphere, performing ultrasonic dispersion, and then adding L-cysteine;

irradiating for 20-40 min under 365nm ultraviolet light, washing for 3-5 times with ethanol and deionized water respectively, and drying at room temperature to obtain the bifunctional adsorption resin.

8. The method for producing according to claim 7, characterized in that: the mixing ratio of the benzoin dimethyl ether, the ethanol-deionized water solution, the resin matrix of the polymer brush grafted with olefin on the surface of the microsphere and the L-cysteine is 20-30 mg/20-30 mL/300-400 mg.

9. Use of the bifunctional adsorbent resin of claim 1 or 2 for metal ion adsorption.

10. Use of the bifunctional adsorbent resin of claim 1 or 2 for separation, enrichment and purification of glycopeptide fragments.