CN105521771A - Preparation method and use of boric acid affinity membrane - Google Patents
Preparation method and use of boric acid affinity membrane Download PDFInfo
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- CN105521771A CN105521771A CN201510660254.0A CN201510660254A CN105521771A CN 105521771 A CN105521771 A CN 105521771A CN 201510660254 A CN201510660254 A CN 201510660254A CN 105521771 A CN105521771 A CN 105521771A
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Abstract
The invention discloses a boric acid affinity membrane separation material and a preparation method thereof. The separation material has a high adsorption capacity, good selectivity of a cis-o-dihydroxyl-containing substance and a fast mass transfer rate. The boric acid affinity membrane is used for enrichment of dopamine in urine. Through the boric acid affinity membrane, dopamine is effectively enriched and interference caused by most of substances is avoided.
Description
Technical field
The present invention relates to a kind of preparation method of boric acid affinity membrane, belong to parting material preparation field.
Background technology
Biomolecule containing cis o-dihydroxy comprises glycoprotein, sugar, nucleosides, nucleotides, catecholamine, RNA etc., and many is all the Main Analysis thing of life science, and it is significant in medical diagnosis on disease.But due in biological sample, the content of cis o-dihydroxy material is very low, and there is a large amount of chaff interference, therefore, optionally separation and concentration is the key of accurate analysis cis o-dihydroxy class material.
Between boric acid and cis o-dihydroxy material, there is Selective recognition effect, when cis o-dihydroxy material is in alkaline environment, boric acid and cis o-dihydroxy material generate five yuan or hexa-atomic cyclic ester, and when pH is down to acidity, cyclic ester dissociates and discharges cis o-dihydroxy molecule.
Membrane separation technique is as the technology of a kind of high score from, enrichment and purification, be new development in recent years get up can be used for one of new technology in chemical analysis field, there is operation sequence convenience, can directly be connected with various analytical instrument and be easy to the advantages such as on-line operation, therefore, membrane separation technique is widely used in numerous areas as a kind of new Sample Pretreatment Technique Used.According to the inventors knowledge, the report of boric acid affinity membrane is not also prepared at present.
Summary of the invention
The invention provides boric acid affinity membrane material that a kind of adsorption capacity is high, mass transfer rate is fast and preparation method thereof, this boric acid affinity membrane material can be used for the UF membrane and the membrane extraction that contain cis o-dihydroxy material.
Implementation procedure of the present invention is as follows:
The boric acid affinity separation polymer of the polyethyleneimine: amino-functionalization shown in following structural formula,
Above-mentioned
for cellulose membrane or regenerated cellulose film, n is 10-30.
The preparation method of above-mentioned material comprises the following steps:
(1) solid-phase matrix pretreatment: the grease and the coherent substance that solid-phase matrix are soaked in methyl alcohol removing surface, by drying for standby after methyl alcohol and distilled water cyclic washing, described solid-phase matrix is cellulose membrane or regenerated cellulose film;
(2) solid-phase matrix surface amination: by solid-phase matrix elder generation and epichlorohydrin reaction, is then obtained by reacting amidized solid-phase matrix with polymine;
(3) by amination solid-phase matrix and 4-formylphenylboronic acid and sodium cyanoborohydride room temperature reaction in absolute methanol, the boric acid affinity separation polymer that reaction terminates rear washing, drying obtains polyethyleneimine: amino-functionalization.
The boric acid affinity separation polymer of above-mentioned polyethyleneimine: amino-functionalization contains the application in cis o-dihydroxy biomolecule in separation and enrichment.
Advantage of the present invention and good effect: synthetic method of the present invention is simple, and preparation process is reproducible; The boric acid affinity membrane material prepared has large, selective good, the feature that mass transfer rate is fast of adsorption capacity, can effectively improve containing the separation of cis o-dihydroxy molecule and bioaccumulation efficiency.
Accompanying drawing explanation
Fig. 1 boric acid affinity membrane can contain catechol and the dopamine of cis o-dihydroxy by selective enrichment;
Fig. 2 is that boric acid affinity membrane material is to the adsorption dynamics adsorption kinetics of dopamine and desorption dynamics;
Fig. 3 is that boric acid affinity membrane material is to chromatogram before and after dopamine enrichment in urine;
Fig. 4 is the 2D microphoto of former film (a) and boric acid affinity membrane (b);
Fig. 5 is the 3D microphoto of former film (a) and boric acid affinity membrane (b).
Detailed description of the invention
Below by specific embodiment, technical scheme of the present invention is described further.Specific embodiment listed by the present invention is only limitted to the present invention is described, but not limitation of the invention.
the pretreatment of embodiment 1 regenerated cellulose film
By whole piece regenerated cellulose film (diameter 47mm, average pore size 0.45 μm, thickness 160 μm, Sai get Li Si company of Germany) be cut into 1/8 fan-shaped small pieces of formed objects, totally 8 small pieces, 15min is soaked with except striping surface oil fat and stuck foreign matter in methyl alcohol, with methyl alcohol and distilled water cyclic washing, 40 DEG C of drying for standby in vacuum drying chamber.
the epoxidation of embodiment 2 regenerated cellulose film
The regenerated cellulose film of drying is placed in the mixed liquor of 10mL epoxychloropropane and 20mL1.4mol/LNaOH, stirring reaction 2h in 60 DEG C of oil baths, after reaction terminates, repeatedly washs with sodium hydroxide solution, distilled water, obtain epoxidation cellulose membrane.
embodiment 3 polymine (PEI600) that molecular weight is 600 modifies regenerated cellulose film
Epoxidation cellulose membrane is added in three-neck flask, 1g polymine (M=600), 50mL sodium bicarbonate solution (50mM, pH9), stirring reaction 5h in 65 DEG C of oil baths, with sodium bicarbonate solution, distilled water cyclic washing, in vacuum drying chamber, 40 DEG C of dryings, obtain the cellulose membrane of PEI600 functionalization.
embodiment 4 polymine (PEI10000) that molecular weight is 10000 modifies regenerated cellulose film
Epoxidation cellulose membrane is added in three-neck flask, 1g polymine (M=10000), 50mL sodium bicarbonate solution (50mM, pH9), stirring reaction 5h in 65 DEG C of oil baths, with sodium bicarbonate solution, distilled water cyclic washing, in vacuum drying chamber, 40 DEG C of dryings, obtain the cellulose membrane of PEI10000 functionalization.
embodiment 5 polymine (PEI20000) that molecular weight is 20000 modifies regenerated cellulose film
Epoxidation cellulose membrane is added in three-neck flask, 1g polymine (M=20000), 50mL sodium bicarbonate solution (50mM, pH9), stirring reaction 5h in 65 DEG C of oil baths, with sodium bicarbonate solution, distilled water cyclic washing, in vacuum drying chamber, 40 DEG C of dryings, obtain the cellulose membrane of PEI20000 functionalization.
the boric acid functionalization of embodiment 6 cellulose membrane
The cellulose membrane of dry polyethyleneimine: amino-functionalization is added in three-neck flask; 100mL heavily steams methyl alcohol; 1.6g4-formylphenylboronic acid; 1g sodium cyanoborohydride, mol ratio is 1:3, stirred at ambient temperature reaction 12h; after reaction terminates; repeatedly wash with absolute methanol, 5% sodium bicarbonate solution, 5% sodium chloride solution respectively, 40 DEG C of vacuum drying, obtain boric acid affinity membrane parting material.
embodiment 7: boric acid affinity membrane parting material elemental analysis
Utilize elementary analysis to characterize regenerated cellulose film, epoxidised RC film, the RC film of grafting polyethylene imine, the constituent content of boric acid affinity membrane, from table 1, the changes of contents of N element can find out that polymine is successfully grafted to regenerated cellulose film surface.
embodiment 8: boric acid affinity membrane parting material adsorbs cis o-dihydroxy matter selective
With 10 μ g/mL catechols and hydroquinones (chaff interference) mixed liquor of the ammonia-ammonium chloride buffer solution preparation of 50mMpH=9, boric acid affinity membrane synthetic for two panels is placed in two 50mL centrifuge tubes respectively, add 5mL catechol and hydroquinones mixed liquor respectively, dopamine and serotonin mixed liquor, room temperature absorption 10min in shaking table, use ammonia-ammonium chloride buffer solution, the water wash of pH=9 afterwards, to remove the physical absorption on film surface, by the film 2mL5% acetic acid wash-out 10min handled well, eluent carries out HPLC detection.
(1) Fig. 1's is boric acid affinity membrane material in the 10 μ g/mL catechols and hydroquinones (chaff interference) mixed liquor of ammonia-ammonium chloride buffer solution preparation of pH=9, and selective enrichment contains the catechol of cis o-dihydroxy; (2) be boric acid affinity membrane material in the 50 μ g/mL dopamines and serotonin (chaff interference) mixed liquor of ammonia-ammonium chloride buffer solution preparation of pH=9, selective enrichment contains the dopamine of cis o-dihydroxy.Chromatographic condition: chromatographic column 4.6 × 150mmC18 post; Mobile phase: (1) 50mmol/LHAc/ methyl alcohol=80:20; (2) sodium dihydrogen phosphate/acetonitrile=99:1; Flow velocity: 1.0mL/min; Column temperature: room temperature; UV detect wavelength: 280nm.In the A of Fig. 1,1 is hydroquinones, and 2 is catechol, and in chromatogram, a is that catechol mixes with hydroquinones and marks liquid, and b is eluent after absorption; In B, 1 is dopamine, and 2 is serotonin, and in chromatogram, a is that dopamine mixes with serotonin and marks liquid, and b is eluent after absorption.
embodiment 9: boric acid affinity membrane parting material adsorption dynamics adsorption kinetics measures
The cellulose membrane of 5mg boration is added in the dopamine solution of the ammonia of 2mL100 μ g/mL50mMpH=9-ammonium chloride buffer solution preparation and adsorbs, adsorption time is respectively 1,3,10,30,120min, Aspirate supernatant carries out HPLC analysis.As shown in Fig. 2 (A), be adsorbed on 1min and just can reach balance.
embodiment 10: boric acid affinity membrane parting material desorption kinetic determination
5mg boric acid affinity membrane is added to the ammonia of 2mL100 μ g/mL50mMpH=9-ammonium chloride buffer solution preparation dopamine solution in adsorb 10min, after the ammonia-ammonium chloride buffer solution of pH=9, water wash, with 200 μ L5% acetic acid wash-outs, elution time is respectively 1,3,10,30,120min, eluent carries out HPLC analysis, as shown in Fig. 2 (B), desorption just can reach balance at 1min.
embodiment 11: boric acid affinity membrane material is to the enrichment of dopamine in urine
2mL acetonitrile precipitation albumen is added in 10mL urine, the centrifugal 5min of 10000rpm removes precipitation, regulate supernatant pH to 8.0 with 1mol/LNaOH afterwards, add the boric acid affinity membrane absorption of 5mg polyethyleneimine: amino-functionalization, after drip washing, with 200 μ L5% acetic acid wash-outs, eluent carries out HPLC analysis, as shown in Figure 3, after this boric acid affinity membrane process, dopamine obtains effective enrichment, and eliminates the interference of large absolutely number material.
embodiment 12: boric acid affinity membrane parting material AFM characterizes
Utilize the surface topography between the former film of AFM Analysis and boric acid affinity membrane and roughness value to change, as shown in Figure 4, a figure is former film, and b figure is the 2D microphoto of boric acid affinity membrane.As can be seen from the figure, compared with former film, the aperture of boric acid affinity membrane is less, this is because grafting polyethylene imine makes aperture diminish to film surface.Fig. 5 is the 3D microphoto of former film (a) and boric acid affinity membrane (b),
rqthe parameter weighing surface roughness,
rqbe worth larger, instruction card surface roughness is larger, the former film of RC
rqvalue for 233nm, the boric acid affinity membrane after grafting polymine
rqvalue reduces to 169nm, and after grafting polyethylene imine is described, film surface is more level and smooth.
embodiment 13
bibliography:
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[2]HuaLi,YuanhongShan,LizhenQiao,AboDou,XianzheShi,andGuowangXu,FacileSynthesisofBoronate-DecoratedPolyethyleneimine-GraftedHybridMagneticNanoparticlesfortheHighlySelectiveEnrichmentofModifiedNucleosidesandRibosylatedMetabolites,Anal.Chem,85(2013)11585-11592.
[3]PengDou,LiangLiang,JiangangHe,ZhenLiu,Hong-YuanChen,Boronatefunctionalizedmagneticnanoparticlesandoff-linehyphenationwithcapillaryelectrophoresisforspecificextractionandanalysisofbiomoleculescontainingcis-diols,J.Chromatogr.A,1216(2009)7558-7563.
[4]QianjinLi,ChenchenLü,HengyeLi,YunchunLiu,HeyeWang,XinWang,ZhenLiu,Preparationoforganic-silicahybridboronateaffinitymonolithiccolumnforthespecificcaptureandseparationofcis-diolcontainingcompounds,J.Chromatogr.A,1256(2012)114-120.
[5]FanYang,ZianLin,XiwenHe,LangxingChen,YukuiZhang,Synthesisandapplicationofamacroporousboronateaffinitymonolithiccolumnusingametal-organicgelasaporogenictemplateforthespecificcaptureofglycoproteins,J.Chromatogr.A,1218(2011)9194-9201.
[6]ZhifengXu,KhanMohammadAhsanUddin,TriptaKamra,JoachimSchnadt,andLeiYe,FluorescentBoronicAcidPolymerGraftedonSilicaParticlesforAffinitySeparationofSaccharides,ACSAppl.Mater.Interfaces,6(2014)1406-1414。
By the comparison of the affine sorbing material of different boric acid to cis o-dihydroxy species adsorbs capacity, as shown in table 2, the boric acid affinity membrane that this experiment obtains has high adsorption capacity, and mass transfer rate is fast.
Claims (3)
1. the boric acid affinity separation polymer of following polyethyleneimine: amino-functionalization shown in structural formula,
Above-mentioned
for cellulose membrane or regenerated cellulose film, n is 10-30.
2. the preparation method of material described in claim 1, is characterized in that comprising the following steps:
(1) solid-phase matrix pretreatment: the grease and the coherent substance that solid-phase matrix are soaked in methyl alcohol removing surface, by drying for standby after methyl alcohol and distilled water cyclic washing, described solid-phase matrix is cellulose membrane or regenerated cellulose film;
(2) solid-phase matrix surface amination: by solid-phase matrix elder generation and epichlorohydrin reaction, is then obtained by reacting amidized solid-phase matrix with polymine;
(3) by amination solid-phase matrix and 4-formylphenylboronic acid and sodium cyanoborohydride room temperature reaction in absolute methanol, the boric acid affinity separation polymer that reaction terminates rear washing, drying obtains polyethyleneimine: amino-functionalization.
3. the boric acid affinity separation polymer of polyethyleneimine: amino-functionalization according to claim 1 contains the application in cis o-dihydroxy biomolecule in separation and enrichment.
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| CN106422809A (en) * | 2016-06-19 | 2017-02-22 | 贵州省材料产业技术研究院 | Fast and efficient boron removal hollow fiber composite membrane and preparation method thereof |
| CN109225177A (en) * | 2018-09-06 | 2019-01-18 | 中国海洋大学 | A kind of preparation method and applications of the hyperbranched agar glycosyl boron affinitive material of polyethyleneimine |
| CN115364830A (en) * | 2022-07-11 | 2022-11-22 | 苏州赛分科技股份有限公司 | Synthesis method of high-load boric acid affinity separation material and separation material |
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| CN109225177A (en) * | 2018-09-06 | 2019-01-18 | 中国海洋大学 | A kind of preparation method and applications of the hyperbranched agar glycosyl boron affinitive material of polyethyleneimine |
| CN109225177B (en) * | 2018-09-06 | 2021-04-13 | 中国海洋大学 | Preparation method and application of polyethyleneimine hyperbranched agarose-based boron affinity material |
| CN115364830A (en) * | 2022-07-11 | 2022-11-22 | 苏州赛分科技股份有限公司 | Synthesis method of high-load boric acid affinity separation material and separation material |
| CN115364830B (en) * | 2022-07-11 | 2023-09-12 | 苏州赛分科技股份有限公司 | Synthesis method of boric acid affinity separation material and separation material |
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