CN112831004B - Preparation method of surface polarity/charge adjustable on/off type magnetic polymer brush adsorbent - Google Patents

Preparation method of surface polarity/charge adjustable on/off type magnetic polymer brush adsorbent Download PDF

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CN112831004B
CN112831004B CN202110002546.0A CN202110002546A CN112831004B CN 112831004 B CN112831004 B CN 112831004B CN 202110002546 A CN202110002546 A CN 202110002546A CN 112831004 B CN112831004 B CN 112831004B
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polymer brush
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CN112831004A (en
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郝贻睿
卫引茂
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Northwest University
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Abstract

The invention discloses a preparation method of an on/off type magnetic polymer brush adsorbent with adjustable surface polarity/charge, which is obtained by grafting a polymer brush on magnetic ferroferric oxide by a surface-initiated atom transfer radical polymerization technology and modifying the molecular brush by using 3,3' - (6-chloro-1, 3, 5-triazine-2, 4-diyl) bis (aza-diyl) bis (3, 1-phenylene) diboronic acid molecules and delta-gluconolactone. Compared with the reference adsorbent, the on/off adsorbent has the advantages of lower leaching loss rate, obviously improved recovery rate and improved analysis accuracy.

Description

Preparation method of surface polarity/charge adjustable on/off type magnetic polymer brush adsorbent
Technical Field
The invention relates to a preparation method of an on/off type magnetic polymer brush adsorbent with adjustable surface polarity/charge, belonging to the technical field of separation and enrichment.
Background
In recent years, with the rapid development of life sciences, environmental sciences, and food and medicine health industries, the requirements of the fields of food analysis, drug research and development, environmental monitoring and the like on the detection of trace substances in a complex system are higher and higher. For the analysis of complex samples, the separation and enrichment of the sample is a very important step. Compared with solvent extraction, adsorbent extraction has higher application potential in separation and enrichment due to the advantages of small organic solvent consumption and multiple types of adsorbents.
The adsorbent material, which is the most important part of the adsorbent extraction process, determines the selectivity and efficiency of the process. The adsorbent material is generally composed of a substrate and various functional groups modified on the surface of the substrate. Common substrates include magnetic nanoparticles, silica gel, graphene oxide, monolithic columns, activated carbon, and the like. Modifying small molecules or linear polymers on the surface of a substrate to connect specific functional groups on the surface, and preparing various adsorbents. Although the small molecule modification method is simple, the introduced binding sites are limited, resulting in a low adsorption capacity. Although the linear polymer modification method is complex, the adsorption capacity is high. From the structural point of view, both small molecules and polymer molecules are in an 'open' structure on the surface of the material regardless of the modification method of the small molecules or the polymer. The process of enriching the target by the adsorbent generally comprises 3 steps of adsorption from a sample solution, rinsing the adsorbent and desorption of the target from the surface of the adsorbent. The ideal target of enrichment is that the recovery rate of the target object is close to 100% after 3 steps of adsorption, elution and resolution. However, from the view of the enrichment effect of the target, the sample recovery rate is often low by using the currently prepared adsorbent, resulting in low analyte recovery rate and low analysis accuracy. The reason for the low sample recovery occurs mainly in the washing step, and this "open" structure is the main cause of target loss during washing. In addition, the surface property of the prior adsorbent cannot be regulated and controlled, so that the enrichment selectivity is poor.
Disclosure of Invention
The invention aims to provide a preparation method of an on/off type magnetic polymer brush adsorbent with adjustable surface polarity/charge.
The realization process of the invention is as follows:
a preparation method of an on/off type magnetic polymer brush adsorbent with adjustable surface polarity/charge comprises the following steps:
(1) performing surface modification on the magnetic ferroferric oxide by using tetraethoxysilane, 3-aminopropyl triethoxysilane and 2-bromoisobutyryl bromide to obtain a bromine-containing magnetic solid initiator;
(2) grafting a polymer brush on a bromine-containing magnetic solid initiator by adopting a monomer A styrene and a monomer B sodium styrene sulfonate and utilizing a surface-initiated atom transfer radical polymerization technology (SI-ATRP), wherein the grafted copolymer brush is used as an adsorption layer, namely a copolymer brush adsorbent;
(3) reacting the copolymer brush adsorbent with ethylenediamine to obtain an amino-modified copolymer brush adsorbent;
(4) modifying 3,3' - (6-chloro-1, 3, 5-triazine-2, 4-diyl) bis (aza-diyl) bis (3, 1-phenylene) diboronic acid molecules (DBA) and delta-gluconolactone at the chain end of the amino modified copolymer brush adsorbent to obtain the surface polarity/charge controllable on/off type magnetic polymer brush adsorbent.
In the step (1), the preparation method of the bromine-containing magnetic solid initiator specifically comprises the following steps:
(1) magnetic Fe 3 O 4 Reacting with tetraethyl orthosilicate to obtain magnetic nano particles coated by silicon dioxide, namely Fe 3 O 4 @SiO 2 ；
（2）Fe 3 O 4 @SiO 2 Reacting with 3-aminopropyltriethoxysilane to obtain amino-modified magnetic particles, i.e. Fe 3 O 4 @SiO 2 -NH 2 ；
（3） Fe 3 O 4 @SiO 2 -NH 2 Reacting with 2-bromoisobutyryl bromide to obtain a bromine-containing magnetic solid initiator, namely Fe 3 O 4 @SiO 2 -Br。
In the step (2), a bromine-containing magnetic solid initiator Fe 3 O 4 @SiO 2 the-Br is used as an initiator, sodium p-styrenesulfonate and styrene are used as monomers, cuprous bromide is used as a catalyst, 2, 2' -bipyridine is used as a ligand, wherein the molar ratio of the initiator to the monomers to the catalyst to the ligand is 1 (100-300) to (5-15) to (10-30), and the sodium p-styrenesulfonate and benzene are used asThe mol ratio of ethylene is 2: 1-1: 2, the solvent is methanol and water, and the volume ratio is 1: 2-2: 1.
The proportion of the monomer sodium styrene sulfonate to the styrene can be regulated, so that the charge and the polarity of the surface of the copolymer brush adsorbent can be regulated, the proportion of the sodium styrene sulfonate can be increased, the charge of the surface of the copolymer brush adsorbent can be improved, the proportion of the styrene can be increased, and the polarity of the surface of the copolymer brush adsorbent can be improved.
And (3) reacting the copolymer brush adsorbent with ethylenediamine at 55-75 ℃ for 24h under the protection of nitrogen by using N, N-dimethylformamide as a solvent and ethylenediamine as an amination reagent, and reacting the copolymer brush adsorbent with ethylenediamine to obtain the amino-modified copolymer brush adsorbent.
In the step (4), cyanuric chloride and 3-aminobenzeneboronic acid in a molar ratio of 1 (2-2.2) are fully reacted in an ice bath to obtain 3,3' - (6-chloro-1, 3, 5-triazine-2, 4-diyl) bis (azepinyl) bis (3, 1-phenylene) diboronic acid molecules,
Figure 737393DEST_PATH_IMAGE001
in the step (4), N-dimethylformamide is used as a solvent, the molar ratio of delta-gluconolactone to 3,3' - (6-chloro-1, 3, 5-triazine-2, 4-diyl) bis (azepinyl) bis (3, 1-phenylene) diboronic acid is 1:1, and the on/off magnetic polymer brush adsorbent is obtained by fully reacting at 70-90 ℃ under the protection of nitrogen.
The surface polarity/charge controllable on/off type magnetic polymer brush is applied as an adsorbent in sample pretreatment.
The invention has the advantages that: (1) compared with the traditional monomolecular layer adsorption interface, the adsorption interface of the on/off type adsorbent is of a copolymer brush structure, has the characteristics of high density of adsorption sites and high adsorption capacity, and can obtain the effect of high adsorption rate by using a small amount of adsorbent in sample pretreatment; the surface polarity/charge of the adsorbent can be adjusted and the adsorption selectivity can be adjusted by changing the ratio of the sodium styrene sulfonate to the styrene, and (3) the surface polarity/charge adjustable on/off type magnetic polymer brush adsorbent is in a closed state under the condition of alkaline leaching of the adjustable on/off type magnetic polymer brush adsorbent, so that a target object can be wrapped inside the molecular brush, and the active effects of reducing the leaching loss rate of the target object and improving the recovery rate of the target object are achieved.
Drawings
FIG. 1 is a schematic illustration of the preparation of a copolymer brush sorbent;
FIG. 2 is a schematic diagram of the preparation of an on/off type adsorbent;
FIG. 3 is a graph comparing elution losses for a control adsorbent and an on/off type adsorbent;
FIG. 4 is a graph comparing the recovery of the control adsorbent and the on/off type adsorbent.
Detailed Description
In order to understand the invention more clearly, the invention is further described in detail by the specific examples given by the inventor according to the technical scheme of the invention, and the reagents used in the invention are all commercial products.
Example 1: preparation of magnetic solid initiator
Fe 3 O 4 @SiO 2 The synthesis method comprises the following steps: firstly, ferroferric oxide is synthesized by a hydrothermal method. 1.35g of anhydrous ferric chloride, 0.45g of trisodium citrate dihydrate were dissolved in 30ml of ethylene glycol. Then, 2.4g of anhydrous sodium acetate was added to the mixture, stirred uniformly (30 min), and the resulting mixture was charged into a reaction vessel (200 ℃ C.) and heated for 12 hours. After cooling to room temperature, the resulting Fe was 3 O 4 Washed three times with ethanol and water alternately. Washing the Fe 3 O 4 Dispersing in 100 mL distilled water, ultrasonic treating for 45 min, magnetically separating, and sequentially treating Fe with 1M hydrochloric acid (100 mL), water (100 mL) and 20% trisodium citrate dihydrate (100 mL) 3 O 4 And (5) processing the surface. Fe after treatment 3 O 4 Dispersing in mixed solution of distilled water (144 mL) and anhydrous ethanol (576 mL), ultrasonically stirring for a certain time, rapidly adding concentrated ammonia water (7.5 mL), adding 1mL of ethyl orthosilicate by using a syringe, stirring at room temperature for 12h, and finally obtaining Fe 3 O 4 @SiO 2 . With ethanolWashing with water alternately, and vacuum drying at 50 deg.C.
Adding 1.0g Fe into a three-mouth bottle 3 O 4 @SiO 2 The particles and 20 mL of redistilled toluene were mechanically stirred and heated to 110 ℃.3 mL of 3-Aminopropyltriethoxysilane (APTES) was dispersed in 10 mL of redistilled toluene and added dropwise to a three-necked flask for 12h reaction. The product Fe 3 O 4 @SiO 2 -NH 2 Washed with toluene, methanol and distilled water in this order and dried under vacuum at 50 ℃.
Mixing 1g of Fe 3 O 4 @SiO 2 -NH 2 Dispersing in 40 mL redistilled tetrahydrofuran, stirring for 30min under ice bath condition, adding 2 mL of 2-bromine isobutyryl bromide into a three-necked flask, stirring for 3 h, transferring into a 35 ℃ water bath kettle for reaction for 12h, and reacting the reaction product Fe after the reaction is finished 3 O 4 @SiO 2 -Br was washed alternately with tetrahydrofuran, methanol and water and dried under vacuum at 50 ℃.
Example 2: preparation of copolymer brush adsorbents
0.2 g of Fe 3 O 4 @SiO 2 -Br particles, 40 mg of 2, 2' -bipyridine, 3.08 g of sodium p-styrenesulfonate and 0.9 mL of styrene (the molar ratio of sodium p-styrenesulfonate to styrene is 2: 1) dispersed in 10 mL of a mixed solution of methanol and water, using a freezing-vacuumizing-nitrogen-introducing cycle twice to remove oxygen in the reaction system, rapidly adding 18.4 mg of cuprous bromide, and after repeating the above cycle twice, reacting the reaction system at 40 ℃ for 24 hours. The crude product obtained is treated with Na 2 EDTA (15 mL) solution. Finally washed alternately with methanol and water and dried under vacuum at 50 ℃.
The synthesized copolymer brush adsorbent is shown in figure 1, and the method of the invention can graft monomer sodium p-styrenesulfonate and styrene to Fe 3 O 4 @SiO 2 -Br surface, this example only gives a molar ratio of sodium p-styrenesulfonate to styrene of 2:1, the surface charge and polarity of the copolymer brush adsorbent can be regulated and controlled by regulating the proportion of the monomer sodium styrene sulfonate and the styrene, the proportion of the sodium styrene sulfonate can be increased, and the surface charge and polarity of the copolymer brush adsorbent can be regulated and controlledThe surface charge of the copolymer brush adsorbent is increased, the proportion of styrene is increased, and the polarity of the surface of the copolymer brush adsorbent can be improved.
Example 3: synthesis of 3,3' - (6-chloro-1, 3, 5-triazine-2, 4-diyl) bis (azepinyl) bis (3, 1-phenylene) diboronic acid micromolecule
0.84 g (4.5 mmol) of cyanuric chloride is first dissolved in 20 mL of glacial acetic acid, and then 1.39 g (9.0 mmol) of 3-aminophenylboronic acid and 0.92 g (11.25 mmol) of sodium acetate are dissolved in 10 mL of aqueous glacial acetic acid (v/v = 1/1). Mixing the two solutions at room temperature, slowly cooling the mixed solution to below 25 deg.C, reacting for 3 hr to obtain white solution, washing with glacial acetic acid and water, purifying by thin layer chromatography, and vacuum drying at 50 deg.C. HRMS calculated value C 15 H 14 B 2 ClN 5 O 4 [MK] + m/z 424.0552, found 424.0461.
Example 4: preparation of "on/off" adsorbents
0.2 g of the molecular brush particles were dispersed in 10 mL of a dry tetrahydrofuran solvent, and 0.22 mL of anhydrous ethylenediamine and 12.36 mg of potassium carbonate were added thereto, and the system was reacted at 65 ℃ for 24 hours under a nitrogen atmosphere. After the reaction is finished, washing the reaction product by tetrahydrofuran, methanol and water for three times in sequence, and drying the reaction product in vacuum at 50 ℃ to obtain the amino-modified molecular brush particles.
0.2 g of the above molecular brush particles was dispersed in 10 mL of N, N-dimethylformamide solvent, and 0.27g of DBA, 0.125g of delta-gluconolactone and 0.35 mL of triethylamine were added thereto, and reacted at 90 ℃ under a nitrogen atmosphere for 24 hours. After the reaction is finished, washing the mixture by using N, N-dimethylformamide, methanol and water for three times in sequence, and drying the mixture in vacuum at 50 ℃ to obtain the 'on/off' adsorbent.
As shown in FIG. 2, the copolymer brush adsorption layer designed by the invention is obtained by the SI-ATRP technology with controllable activity. The SI-ATRP can not only control the length of a polymer chain on the surface of a particle through polymerization time and monomer concentration, but also has multiple monomer types applied to SI-ATRP reaction, and can form an adsorbent interface with adjustable polarity/charge through adjusting and controlling the properties (such as hydrophobicity, electrical property and the like) of the monomers, so that the adsorption layer has the advantage of adjustable and controllable adsorption selectivity.
Example 5: use of on/off adsorbents
Preparing PBS buffer solutions (pH5.5, 20 mmol/L) of quinolone with different concentrations, and establishing a standard curve by using liquid chromatography; adding 10 mg of magnetic adsorbent into 2 mL of quinolone mixed mother liquor with the concentration of 1ug/mL and the pH value of 5.5, carrying out ultrasonic dispersion, shaking for 30min, carrying out magnetic separation, and removing supernatant; then, leaching twice by using 1mL of PBS buffer solution with the pH value of 8.5, and transferring the leaching solution of the two times; then adding 0.3 mL acetonitrile and 0.7 mL 10% acetic acid aqueous solution for elution for 30min, and transferring the eluent for high performance liquid chromatography analysis. The adsorption rates of the control adsorbent and the "on/off" adsorbent under the same adsorption conditions (ph 5.5) were substantially the same; the surface state of the reference adsorbent is always in an 'open' state, the 'on/off' adsorbent is in an 'off' state under weak alkaline washing liquid, and the target objects can be wrapped inside the molecular brush, so that the washing loss rate of the 'on/off' adsorbent to the three target objects is lower than that of the reference adsorbent by 26%, 23% and 23% (figure 4), and the recovery rate of the 'on/off' adsorbent to the three target objects reaches 64.36%, 58.27% and 64.70%.
As can be seen from the above examples, the present invention constructs an on/off type magnetic polymer brush adsorbent with controllable surface polarity/charge. Firstly, a high-density molecular brush polymer is grafted on the surface of a magnetic ferroferric oxide substrate by a surface-initiated atom transfer radical polymerization technology, the polymer molecular brush is obtained by polymerizing two functional monomers, and the defect that the polarity/charge property and other properties of the traditional polymer are uncontrollable can be overcome by adjusting the proportion and the property of the functional monomers. Then, modifying micromolecules containing the bis-phenylboronic acid and the cis-dihydroxy at the tail end of a molecular brush by utilizing the characteristic that a borate ester bond formed by the phenylboronic acid and the cis-dihydroxy under the weak alkaline condition can be reversibly dissociated under the weak acidic condition to obtain the surface polarity/charge-controllable 'on/off' type magnetic polymer brush-type adsorbent. Under the condition of weakly acidic adjustment of the sample solution, phenylboronic acid and cis-dihydroxy on the on/off adsorbent are not combined, and the analyte enters the inside of the on/off adsorbent and is adsorbed. The adsorbent is then rinsed with an alkaline solution to remove impurities. Under the condition of alkali liquor, the phenylboronic acid at the tail end of the polymer brush is combined with the cis-dihydroxy, the polymer chain is closed, and the target object is wrapped inside the molecular brush. Finally, the adsorbent is placed in a weakly acidic solution to desorb the target. Under the acid liquor condition, the phenylboronic acid and the cis-dihydroxy at the tail end of the polymer brush are opened, the polymer chain is in an open structure, and the target object is desorbed. According to the knowledge of the inventor, the invention is the first report of the preparation method of the surface polarity/charge controllable on/off type magnetic polymer brush adsorbent, and aims to reduce the loss in the target object washing process, improve the enrichment recovery rate and simultaneously improve the enrichment selectivity.

Claims (8)

1. A preparation method of an on/off type magnetic polymer brush adsorbent with adjustable surface polarity/charge is characterized by comprising the following steps:
(1) magnetic Fe 3 O 4 Reacting with tetraethyl orthosilicate to obtain magnetic nano particles coated by silicon dioxide, namely Fe 3 O 4 @SiO 2 ；
（2）Fe 3 O 4 @SiO 2 Reacting with 3-aminopropyltriethoxysilane to obtain amino-modified magnetic particles, i.e. Fe 3 O 4 @SiO 2 -NH 2 ；
（3）Fe 3 O 4 @SiO 2 -NH 2 Reacting with 2-bromoisobutyryl bromide to obtain bromine-containing magnetic solid initiator, namely Fe 3 O 4 @SiO 2 -Br；
(4) Grafting a polymer brush on a bromine-containing magnetic solid initiator by adopting a monomer A styrene and a monomer B sodium styrene sulfonate and utilizing a surface-initiated atom transfer radical polymerization technology, wherein the grafted copolymer brush is used as an adsorption layer, namely a copolymer brush adsorbent;
(5) reacting the copolymer brush adsorbent with ethylenediamine to obtain an amino-modified copolymer brush adsorbent;
(6) modifying 3,3' - (6-chloro-1, 3, 5-triazine-2, 4-diyl) bis (aza-diyl) bis (3, 1-phenylene) diboronic acid molecules and delta-gluconolactone at the chain end of the amino modified copolymer brush adsorbent to obtain the surface polarity/charge controllable on/off type magnetic polymer brush adsorbent.
2. The method for preparing a magnetic polymer brush adsorbent according to claim 1, wherein in the step (4), a magnetic solid initiator Fe containing bromine is used 3 O 4 @SiO 2 The catalyst is characterized in that-Br is used as an initiator, sodium p-styrenesulfonate and styrene are used as monomers, cuprous bromide is used as a catalyst, and 2, 2' -bipyridine is used as a ligand, wherein the molar ratio of the initiator to the monomers to the catalyst to the ligand is (100-300) to (5-15) to (10-30).
3. The method of preparing a magnetic polymer brush sorbent according to claim 2, wherein: the molar ratio of the sodium p-styrenesulfonate to the styrene is 2: 1-1: 2.
4. The method of preparing a magnetic polymer brush sorbent according to claim 2, wherein: a mixed solvent of methanol and water is used in the reaction, and the volume ratio of the mixed solvent to the water is 1: 2-2: 1.
5. The method of making a magnetic polymer brush sorbent according to claim 1, wherein: in the step (5), N-dimethylformamide is used as a solvent, ethylenediamine is used as an ammoniation reagent, the reaction is carried out for 24 hours at the temperature of 55-75 ℃ under the protection of nitrogen, and the copolymer brush adsorbent is reacted with ethylenediamine to obtain the amino-modified copolymer brush adsorbent.
6. The method of making a magnetic polymer brush sorbent according to claim 1, wherein: in the step (6), cyanuric chloride and 3-aminobenzeneboronic acid in a molar ratio of 1 (2-2.2) are fully reacted in an ice bath to obtain 3,3' - (6-chloro-1, 3, 5-triazine-2, 4-diyl) bis (azepinyl) bis (3, 1-phenylene) diboronic acid molecules.
7. The method of making a magnetic polymer brush sorbent according to claim 1, wherein: in the step (6), N-dimethylformamide is used as a solvent, the molar ratio of delta-gluconolactone to 3,3' - (6-chloro-1, 3, 5-triazine-2, 4-diyl) bis (azepinyl) bis (3, 1-phenylene) diboronic acid is 1:1, and the on/off magnetic polymer brush adsorbent is obtained by fully reacting at 70-90 ℃ under the protection of nitrogen.
8. Use of the magnetic polymer prepared according to claim 1 as an adsorbent in the treatment of samples.
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