CN104841403A - High-capacity boron affinity separation material and preparation method and application thereof - Google Patents
High-capacity boron affinity separation material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-capacity boron affinity separation material. According to the material, surface-initiated atom transfer radical polymerization and terminal modification technologies are combined, alkene compounds containing phenylboronic acid serve as monomers to be polymerized on solid matrix surfaces, and phenylboronic acid containing alkynyl is used for polymer chain end functionalization through click chemistry, and accordingly, the separation materials containing high-density phenylboronic acid groups are obtained. The separation material is high in absorption capacity and specificity and has the advantages of being few in use material and high in recovery rate and sensitivity when being used for separating and gathering cis dihydroxylation substances. (img file= 'dest_path_image001. TIF' wi= '468' he= '224'/).
Description
Technical field
The present invention relates to high power capacity boron affinity separation polymer of a kind of phenyl boric acid functionalized polymer modification and preparation method thereof, belong to new separation material synthesis technical field.
Background technology
Boric acid can form reversible, that pH regulates and controls cyclic ester with Cis-hydroxyl groups, based on so higher characteristic of specificity, boron affinitive material has been widely used in the Selective Separation containing cis o-dihydroxy material and enrichment, the materials such as such as nucleosides, carbohydrate, glycoprotein and catecholamine.Can see, the material containing cis o-dihydroxy many to proteomics, that the research of the hot fields learned etc. in life science organized by metabolism group, sugar is relevant, the development of boron affinitive material has great importance to life science.
At present, boron affinitive material mainly reacts matrix by choosing suitable bifunctional molecules, makes bifunctional molecules one end be fixed on stromal surface, and one end just can be reacted with boronic acid ligands in addition, and boric acid base group is modified stromal surface.But the sorbing material surface binding site obtained like this is limited, and adsorption capacity is mostly unsatisfactory, can not reach the requirement of high flux processing sample, and adsorbent amount is also larger, the rate of recovery may be caused not high.In recent years, the material utilizing boric acid functionalized polymer to modify greatly enhances the adsorption capacity of boron affinitive material, as radical polymerization [ACS Applied Materials & Interfaces. 2013,5 (17): 8351-8358], emulsion polymerisation [Journal of Chromatography A. 2009,1216 (44): 7558-7563], precipitation polymerization [ACS Applied Materials & Interfaces. 2014,6 (3): 2059-2066] etc.However, the boron affinitive material developing high power capacity also needs further effort.
Research shows, surperficial Atom Transfer Radical Polymerization (SI-ATRP) reaction can control density and the chain length of solid substrate polymer molecule brush by controlling initator precursor concentration, monomer concentration and polymerization time; The more important thing is, through polymerisation, the polymer end of the chain still has active halogen atom, and the further reaction existing for polymer chain of this active halogen atom provides avtive spot, can prepare function groups polymer; Also reaction [Chemical Reviews. 2001,101 (9): 2921-2990] can be continued as macromole evocating agent.
Summary of the invention
The object of the present invention is to provide high power capacity boron affinity separation polymer that a species specificity is better, adsorption capacity is high and preparation method thereof.
The method of the present invention's application SI-ATRP, with 3-acrylamido phenyl boric acid for monomer, is polymerized at solid substrate, then utilizes end modified technology, by " click-reaction ", the phenyl boric acid part with alkynyl is bonded to polymer chain terminal.The material of the boric acid polymer chain of this surface bond end boric acid functionalization, has a more phenyl boric acid adsorption site.Parting material of the present invention is applied in the separation and concentration of trace cis o-dihydroxy material in complex sample, and sorbing material consumption is less, improves sensitivity and the accuracy of complex sample analysis.
Implementation procedure of the present invention is as follows:
Boron affinity separation polymer shown in structural formula (I),
。
The preparation method of above-mentioned high power capacity boron affinity separation polymer, comprises following steps:
(1) 3-aminobenzene boric acid is dissolved in sodium hydroxide solution, adds acryloyl chloride reaction, regulate pH 1-2 under ice bath, and filtration, washing, drying, be prepared into 3-acrylamido phenyl boric acid;
(2) 3-aminobenzene boric acid and sodium acid carbonate being dissolved in volume ratio is in the methanol/water solution of 1:1, drip the reaction of propargyl chloride formic acid esters, filter, organic phase decompression distillation, ethyl acetate redissolves, and filtration, drying obtain 3-((propyl group-2-alkynyloxy group) formamide) phenyl boric acid;
(3) be scattered in toluene by solid matrix, drip 4-chloromethyl phenyl trimethoxy silane, heating reflux reaction, suction filtration, washing, drying obtain the solid matrix of surface bond initator, and described solid matrix is the magnetic nano-particle of silica gel or gel coated;
(4) with N, N-methylene formamide is solvent, under 2,2 '-bipyridyl and cuprous bromide catalysis, the solid matrix of surface bond initator and 3-acrylamido phenyl boric acid monomer reaction, obtain the solid matrix of surface grafting polyacrylamide base phenyl boric acid through washing;
(5) solid matrix of surface grafting polyacrylamide base phenyl boric acid is scattered in DMF, adds Sodium azide reaction, through washing, the dry solid matrix obtaining end azido and modify;
(6) take oxolane as solvent, 2, under 2 '-bipyridyl and cuprous bromide catalysis, the solid matrix that end azido is modified carries out " click-reaction " with 3-((propyl group-2-alkynyloxy group) formamide) phenyl boric acid, through washing, dry must boron affinity separation polymer.
[0008]the concentration of the 4-chloromethyl phenyl trimethoxy silane described in above-mentioned steps (3) is 80-120 mM.
The mass ratio of the 3-acrylamido phenyl boric acid monomer described in above-mentioned steps (4) and the solid matrix of surface bond initator is 5 ~ 10:3 ~ 6, cuprous bromide, 2, the mol ratio of 2 '-bipyridyl and 3-acrylamido phenyl boric acid monomer is 0.5 ~ 1:1 ~ 3:50 ~ 100.
The reaction temperature of above-mentioned steps (4) is 90 DEG C, and the reaction time is 8-16 hour.
Boron affinity separation polymer prepared by the present invention can be applicable to be separated and enrichment contains the catecholamine of cis o-dihydroxy structure, nucleosides, carbohydrate and glycoprotein.
Advantage of the present invention is as follows: (1) the present invention is that the preparation of novel high-capacity boric acid affinitive material provides new method, and reaction controllability is better, and grafting amount is high, and the boron affinitive material surface functional group prepared is many, and adsorption capacity is high, and specificity is good; (2) high power capacity boron affinitive material provided by the invention can the cis o-dihydroxy material of trace in separation and concentration complex biological sample effectively, during for actual complex sample, consumption is few, the rate of recovery is high, highly sensitive, this material has a good application prospect at complex biological sample analysis field.
Accompanying drawing explanation
Fig. 1 reacts by step each in embodiment 1 and is obtained silica-Cl (a), silica-pAAPBA-Cl (b), silica-pAAPBA-N
3the infrared spectrum of (c) and silica-pAAPBA-PBA (d);
Fig. 2 is the thermogravimetric curve in embodiment 1 before and after modified Silica Gel, naked silica gel (a), silica-Cl (b), silica-PAAPBA-Cl (c)-(e) polymerization reaction time is respectively 1 h (c), 5 h (d), 16 h (e), silica-PAAPBA-PBA (f);
Fig. 3 is contrastive colours spectrogram before and after trace cis o-dihydroxy medicine adrenaline and isoprel in the boron affinitive material separation and concentration blood plasma prepared of embodiment 1; I. blank blood; II. blank blood mark-on liquid; III. eluent after enrichment.Chromatographic condition: mobile phase acetonitrile-10 mM NaH
2pO
4(pH 3.0; 8:92, v/v); Flow velocity: 1.0 mL/min; Sample size: 20 mL; Determined wavelength: 280 nm; Peak is respectively: 1. adrenaline; 2. isoprel;
Fig. 4 be embodiment 2 prepare boron affinity adsorbent to the extract and separate effect chromatogram of variable concentrations interfering material mixed solution, I does not extract mixed solution; Solution after II extracting and enriching, chromatographic condition: mobile phase, acetonitrile-10 mM NaH
2pO
4(pH 3.0; 8:92, v/v); Flow velocity, 1.0 mL/min; Sample size, 20 μ L; UV determined wavelength, 280 nm; In figure, chromatographic peak is respectively: 1. adrenaline; 2. dopamine; 3. hydroquinones; 4. serotonin; 5. aniline; 6. catechol.
Detailed description of the invention
Embodiment 1: the preparation taking silica gel as the high power capacity boron affinitive material of matrix
(1) silica gel after 5.0 grams of activation is taken, then be dispersed in 100 mL heavily to steam in toluene, 2.0 mL concentration are 82.5 mM 4-chloromethyl phenyls trimethoxy silane (4-CPTS), 110 DEG C of reaction 12 h, toluene, methyl alcohol and acetone washed product 3-4 time is used successively after reaction terminates, 50 DEG C of vacuum drying, obtain the silica gel (being called for short silica-Cl) of surface bond initator;
(2) take above-mentioned silica-Cl 1.0 grams, ultrasonic disperse, in DMF, adds 1.6 grams of 3-acrylamido phenyl boric acids and 0.20 gram 2,2 '-bipyridyl; Mixture by repeatedly freezing-vacuumize-thaw cycles, add 0.10 gram of cuprous bromide under nitrogen protection fast; Keep agitation, 90 DEG C are reacted first alcohol and water after 8-16 hour and wash successively.In order to thoroughly clean residual catalyst, the silica gel particle obtained is scattered in 60 mL methyl alcohol/0.25 M EDTANa
2in (1:1, v/v) solution, 40 DEG C of complexing 4 h, then use the repeated multiple times washing of first alcohol and water, 50 DEG C of vacuum drying, obtain polymer-modified silica gel (being called for short silica-pAAPBA-Cl);
(3) above-mentioned Silica-pAAPBA-Cl 0.5 gram and 0.16 gram of NaN
3add 20 mL DMF dispersed, 80 DEG C of reaction 16 h, successively with the washing of water, methyl alcohol and acetone after reaction, 50 DEG C of vacuum drying, obtain silica gel (the abbreviation silica-pAAPBA-N that end azido is modified
3);
(4) 0.5 gram of silica-pAAPBA-N is taken
3ultrasonic disperse is at 25 mL oxolanes, add 0.38 gram of 3-((propyl group-2-alkynyloxy group) formamide) phenyl boric acid and 0.072 gram of cuprous bromide, freezing-to vacuumize-thaw two to circulate, then add 0.156 gram 2,2 '-bipyridyl, 40 DEG C of reaction 48 h.Ice-water bath cooling stops reaction, and with oxolane, methanol wash, 50 DEG C of vacuum drying, obtain high power capacity boron affinity separation polymer (abbreviation silica-pAAPBA-PBA).
By FTIR spectrum method and thermogravimetry, sorbing material is characterized respectively.As shown in Figure 1, with initator fix silica gel (spectrogram a) compared with, the spectrogram (spectrogram b) of silica-pAAPBA-Cl is at 1675cm
-1with 1555 cm
-1there is the characteristic absorption that amide Ⅰ and acid amides II are with respectively in place, meanwhile, and 1342 cm
-1there is the absworption peak of B-O in place, 704 cm
-1the dibasic characteristic absorption in position between place's phenyl ring, shows that AAPBA has successfully been grafted to the surface of silica gel.For silica-pAAPBA-N
3(spectrogram c), 2101 cm
-1the characteristic absorption peak of the azido that place occurs illustrates that the chlorine atom success of polymer chain terminal is replaced by azido.After click-reaction, 2101 cm
-1the characteristic absorption peak of place's azido disappears (spectrogram d), illustrates that azido is obtained by reacting adsorbent silica-pAAPBA-PBA with the phenyl boric acid with alkynyl.
Can see from thermogravimetric curve (Fig. 2), be 3.0% when temperature is elevated to 700 DEG C of naked silica gel weightlessness; Silica gel silica-Cl weightlessness 9.3% fixed by initator; The silica gel silica-pAAPBA-Cl weightlessness 15.5%, 25.9% and 31.2% respectively of ATRP polymerization time 1 h, 5 h and 16 h, the content that can estimate AAPBA according to the loss in weight is respectively 0.65 mmol/g, 1.20 mmol/g and 1.48 mmol/g, prolongation along with polymerization time is described, the AAPBA being grafted to Silica Surface increases gradually; Compared with silica-pAAPBA-Cl, the mass loss of the adsorbent silica-pAAPBA-PBA after end modified increases 33.0% from 31.2%, illustrates that PCAPBA is successfully bonded to polymer chain terminal.To sum up, can think that the polymerization of 3-acrylamido phenyl boric acid and 3-((propyl group-2-alkynyloxy group) formamide) the end modified of phenyl boric acid are all successful.
Embodiment 2: the preparation of the high power capacity boron affinity separation polymer being matrix with the magnetic nano-particle of gel coated
(1) 2.0 grams are hydrolyzed coated silica gel ferroferric oxide magnetic nano-particles by ethyl orthosilicate is taken, then be dispersed in 100 mL heavily to steam in toluene, 2.0 mL concentration are 120.2 mM 4-chloromethyl phenyls trimethoxy silane (4-CPTS), 110 DEG C of reaction 12 h, toluene, methyl alcohol and acetone washed product 3-4 time is used successively after reaction terminates, 50 DEG C of vacuum drying, obtain the magnetic nano-particle of surface bond initator;
(2) take above-mentioned magnetic particle 1.0 grams, ultrasonic disperse, in DMF, adds 1.6 grams of 3-acrylamido phenyl boric acids and 0.20 gram 2,2 '-bipyridyl; Mixture by repeatedly freezing-vacuumize-thaw cycles, add 0.10 gram of cuprous bromide under nitrogen protection fast; Keep agitation, after 90 DEG C of reaction regular hours, first alcohol and water washs successively.In order to thoroughly clean residual catalyst, the silica gel particle obtained is scattered in 60 mL methyl alcohol/0.25 M EDTANa
2in (1:1, v/v) solution, 40 DEG C of complexing 4 h, then use the repeated multiple times washing of first alcohol and water, and 50 DEG C of vacuum drying, obtain polymer-modified magnetic nano-particle;
(3) above-mentioned magnetic nano-particle 0.5 gram and 0.16 gram of NaN
3add 20 mL DMF dispersed, 80 DEG C of reaction 16 h, successively with the washing of water, methyl alcohol and acetone after reaction, 50 DEG C of vacuum drying, obtain the magnetic nano-particle that end azido is modified;
(4) magnetic nano-particle that 0.5 gram of azido is modified is taken, ultrasonic disperse is at 25 mL oxolanes, add 0.38 gram of 3-((propyl group-2-alkynyloxy group) formamide) phenyl boric acid and 0.072 gram of cuprous bromide, freezing-to vacuumize-thaw two to circulate, add 0.156 gram 2 again, 2 '-bipyridyl, 40 DEG C of reaction 48 h.Ice-water bath cooling stops reaction, and with oxolane, methanol wash, 50 DEG C of vacuum drying, and obtaining take magnetic nano-particle as the high power capacity boron affinity separation polymer of matrix.
Embodiment 3: be that the high power capacity boron affinity separation polymer of matrix is to the absorption of catechol with silica gel
What to take in a series of 20 milligrams of embodiments 1 preparation take silica gel as the high power capacity boron affinitive material of matrix, add 5 mL variable concentrations catechol solution respectively, ultrasonic disperse, 25 DEG C of constant temperature oscillators (150 r/min), 10 min that vibrate reach adsorption equilibrium, centrifugal, collect supernatant, carry out chromatography.This boron affinitive material is 513.6 μm of ol/g to the maximal absorptive capacity of catechol.
Embodiment 4: the high power capacity boron affinity separation polymer being matrix with the magnetic nano-particle of gel coated is to the absorption of fructose
Take the high power capacity boron affinitive material being matrix with the magnetic nano-particle of gel coated of preparation in a series of 10 milligrams of embodiments 2, add 5 mL variable concentrations fructose solns respectively, ultrasonic disperse, 25 DEG C of constant temperature oscillators (150 r/min) are vibrated and are reached adsorption equilibrium in 3 hours, externally-applied magnetic field collects supernatant, is detected by three components competitive assay sepectrophotofluorometer.This boron affinitive material is 736.8 μm of ol/g to the maximal absorptive capacity of fructose.
Embodiment 5: silica gel is that the high power capacity boron affinitive material of matrix is to the enrichment of cis o-dihydroxy medicine in blood plasma
Blank plasma, by healthy rabbits heart puncturing extracting blood, stirs and removes fibrinogen, and centrifugal 10 min of 10000 rpm collect supernatant and namely obtain blank rabbit plasma ,-20 DEG C of freezen protective.Get 0.9 mL blank plasma, add adrenaline and isoprel standard liquid, add 100 μ L 10% solution of trichloroacetic acid again, vortex oscillation 1 min, the centrifugal 10 min protein precipitations of 10000 rpm, collect supernatant, regulate pH to add 2.0 mg silica-pAAPBA-PBA ultrasonic disperse after 8.5,25 DEG C of constant temperature oscillator 150 r/min, 10 min that vibrate reach adsorption equilibrium, abandoning supernatant, after buffer solution drip washing three times, add 1.0 mL 5% acetate methanol solution, vibration wash-out 10 min, collects eluent, nitrogen dries up, 200 μ L NH
4cl – NH
3buffer solution redissolves, and gets 20 μ L sample introductions, and HPLC-UV detects.Result is as Fig. 3, and show that this boron affinitive material specificity is higher, can remove the interference of complex matrices, meanwhile, because materials adsorption capacity is high, during extraction, the consumption of material is little.
Embodiment 6: magnetic high power capacity boron affinity separation polymer is to the Selective Separation of o-dihydroxy material
With the NH of 50 mM
4cl – NH
3the mixed solution of six kinds of materials of a series of variable concentrations prepared respectively by buffer solution (pH 8.5), and the material wherein containing cis o-dihydroxy has catechol, dopamine and adrenaline, and in four groups of solution, concentration is 5 μ g/mL; Interfering material not containing cis o-dihydroxy has aniline, hydroquinones and serotonin, and the concentration of these three kinds of interfering materials increases gradually, is respectively 5,50,250 and 500 μ g/mL in 4 groups of solution.In 20.0 mg embodiments 2, the magnetic boron affinitive material of preparation adds in the above-mentioned different mixed liquor of 5.0 mL, ultrasonic disperse, 25 DEG C of constant temperature oscillator 150 r/min, 10 min that vibrate reach adsorption equilibrium, abandoning supernatant, after buffer solution drip washing three times, adds 1.0 mL 5% acetate methanol solution, vibration wash-out 10 min, collect eluent, nitrogen dries up, 200 μ L NH
4cl – NH
3buffer solution redissolves, and gets 20 μ L sample introductions, and HPLC-UV detects.Result is as Fig. 4, and this adsorbent is selective higher, effectively isolates the material containing o-dihydroxy of taking advantage of a situation.
The foregoing is only better embodiment of the present invention, all modifications changed on an equal basis according to the present patent application the scope of the claims, all belong to covering scope of the present invention.
Claims (6)
1. the boron affinity separation polymer shown in structural formula (I),
。
2. the preparation method of high power capacity boron affinity separation polymer according to claim 1, is characterized in that comprising following steps:
(1) 3-aminobenzene boric acid is dissolved in sodium hydroxide solution, adds acryloyl chloride reaction, regulate pH 1-2 under ice bath, and filtration, washing, drying, be prepared into 3-acrylamido phenyl boric acid;
(2) 3-aminobenzene boric acid and sodium acid carbonate being dissolved in volume ratio is in the methanol/water solution of 1:1, drip the reaction of propargyl chloride formic acid esters, filter, organic phase decompression distillation, ethyl acetate redissolves, and filtration, drying obtain 3-((propyl group-2-alkynyloxy group) formamide) phenyl boric acid;
(3) be scattered in toluene by solid matrix, drip 4-chloromethyl phenyl trimethoxy silane, heating reflux reaction, suction filtration, washing, drying obtain the solid matrix of surface bond initator, and described solid matrix is the magnetic nano-particle of silica gel or gel coated;
(4) with N, N-methylene formamide is solvent, under 2,2 '-bipyridyl and cuprous bromide catalysis, the solid matrix of surface bond initator and 3-acrylamido phenyl boric acid monomer reaction, obtain the solid matrix of surface grafting polyacrylamide base phenyl boric acid through washing;
(5) solid matrix of surface grafting polyacrylamide base phenyl boric acid is scattered in DMF, adds Sodium azide reaction, through washing, the dry solid matrix obtaining end azido and modify;
(6) take oxolane as solvent, 2, under 2 '-bipyridyl and cuprous bromide catalysis, the solid matrix that end azido is modified carries out " click-reaction " with 3-((propyl group-2-alkynyloxy group) formamide) phenyl boric acid, through washing, dry must boron affinity separation polymer.
3. the preparation method of boron affinity separation polymer according to claim 2, is characterized in that: the concentration of the 4-chloromethyl phenyl trimethoxy silane described in step (3) is 80-120 mM.
4. the preparation method of boron affinity separation polymer according to claim 2, it is characterized in that: the mass ratio of the 3-acrylamido phenyl boric acid monomer described in step (4) and the solid matrix of surface bond initator is 5 ~ 10:3 ~ 6, cuprous bromide, 2, the mol ratio of 2 '-bipyridyl and 3-acrylamido phenyl boric acid monomer is 0.5 ~ 1:1 ~ 3:50 ~ 100.
5. the preparation method of boron affinity separation polymer according to claim 2, is characterized in that: the reaction temperature of step (4) is 90 DEG C, and the reaction time is 8-16 hour.
6. boron affinity separation polymer according to claim 1 is being separated and enrichment contains application in the catecholamine of cis o-dihydroxy structure, nucleosides, carbohydrate and glycoprotein.
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| CN113318482A (en) * | 2020-02-28 | 2021-08-31 | 北方民族大学 | Hydrophilic hybrid material and preparation method and application thereof |
| WO2021248302A1 (en) * | 2020-06-09 | 2021-12-16 | 苏州赛分科技有限公司 | Chromatography medium for separating boron-containing substances |
| CN111777699A (en) * | 2020-06-17 | 2020-10-16 | 中国科学院青岛生物能源与过程研究所 | Preparation method of boric acid functional group resin |
| CN111777699B (en) * | 2020-06-17 | 2022-09-09 | 中国科学院青岛生物能源与过程研究所 | Preparation method of boric acid functional group resin |
| CN112552395A (en) * | 2020-11-26 | 2021-03-26 | 北京化工大学 | Method for rapidly separating and enriching lactoferrin in dairy product |
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