CN1603817A - Highly effective liquid phase and organic phase integral chromatographic column for bonding cyclodextrin compounds and preparing process thereof - Google Patents
Highly effective liquid phase and organic phase integral chromatographic column for bonding cyclodextrin compounds and preparing process thereof Download PDFInfo
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- CN1603817A CN1603817A CN 200410068142 CN200410068142A CN1603817A CN 1603817 A CN1603817 A CN 1603817A CN 200410068142 CN200410068142 CN 200410068142 CN 200410068142 A CN200410068142 A CN 200410068142A CN 1603817 A CN1603817 A CN 1603817A
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Abstract
This invention relates to a bonding cyclodextrin compound high efficient liquid chromatogram organic bulk column and its process method. The bulk column quality is multiple-hole space glyceryl methacrylate and ethylidene methacrylate polymer. The liquid chromatographic column in this invention can be used in isolation of small molecule of sample, chirality compound isolation, and biological large molecule isolation.
Description
Technical field:
The invention provides the preparation of the highly effective liquid phase and organic phase integral chromatographic column of bonding cyclodextrin compounds.Integral post matrix is the glycidyl methacrylate-EDMA ethylene dimethacrylate polymkeric substance of the build of porous.It is characterized in that the cyclodextrin or derivatives thereof is bonded on the integral post matrix, can obtain to be used for the high performance liquid chromatography organic whole post of micromolecule separation and chiral resolution.
Background technology:
Integral post (monolithic column) claims overall fixed phase (monolithic stationary phase), excellent post (rod), continuous bed (continuous bed) etc. again, be in column jecket in-situ polymerization or immobilization continuous whole porous structure, can make corresponding derivatization to the surface of integral material as required, be a kind of novel in tubing string with the mode of original position (in situ) polymerization form be used for compartment analysis or as the porous medium of reactor.The integral post material that is used for high performance liquid chromatography comprises inorganic and organic polymer two classes equally.The former mainly prepares with sol-gel process; The latter mainly is divided into following a few class at present: polyacrylamide, polymethacrylate and polystyrene type.
Document (Liao J L, Zhang R, Hjert é n S.J.Chromatogr., 1991,586:21-26; ZengC M, Liao J L, Nakazato K, et al.J.Chromatogr., 1996,753:227-234) the aqueous polymerization method of report polyacrylamide integral post.Other has bibliographical information (Xie S F, Svec F, Fr é chet J MJ.J.Chromatogr.A, 1997,775:65-72; Xie S F, Svec F, Fr é chet J M J.J.Polym.Sci.A, 1997,35:1013-1021) the organic phase polymerization prepares the polyacrylamide integral post.The characteristics of this class integral post are: good bio-compatibility is arranged, be fit to the big molecule of separating bio, as albumen, nucleic acid and polysaccharide.
Document about poly-(glycidyl methacrylate-EDMA ethylene dimethacrylate) integral post is (Svec F, Fr é chet J M J.Anal.Chem., 1992,64:820-822; Svec F, Fr é chet J MJ.J.Chromatogr.A, 1995,702:89-93).For the epoxide group in the polymkeric substance, the author has adopted two kinds of derivation modes: 1. pump into the 0.5mol/mL aqueous sulfuric acid, 60 ℃ of reactions of water-bath 3h obtains containing the porous polymer that functionalized with glycols is rolled into a ball like this.2. inject the 2mL diethylamine, add thermal response, obtain containing the separable albumen of ion-exchange chromatography of 1-(N, N-diethylamide)-2-hydroxypropyl functional group.
About poly-(styrene-divinylbenzene) integral post, existing report (Oberacher H, Parson W, Muhlmann R.Anal.Chem., 2001,73:5109-5115; Premstaller A, Oberacher H, Huber C G.Anal.Chem., 2000,72:4386-4393; Moore R E, Licklider L, SchumannD, et al.Anal.Chem., 1998,70:4879-4884) mostly be analysing protein or nucleic acid (strand and two strands).Fr é chet group report (Petro M, Svec F, Gitsov I, et al.Anal.Chem., 1996,68:315-321; Petro M, Svec F, Fr é chet J M J.J.Chromatogr.A, 1996,752:59-66; Wang Q C, Svec F, Fr é chet J M J.Anal.Chem., 1993,65:2243-2248) developed precipitation-molten again chromatogram (" On-Column " Precipitation-Redissolution Chromatography), and separated cinnamic oligomer and superpolymer at post with made polystyrene integral post.
The method that obtains the chiral resolution integral post at present mainly is polyalcohol integral pole (Matsui J, Kato T, Takeuchi T, et al.Anal.Chem., 1993, the 65:2223-2224 of the synthetic other molecule trace type of situ aggregation method; Huang Xiaodong (Huang X D) Zou Hanfa (Zhou H F) Mao Xiqin (Mao X Q). chromatogram (Chinese Journal of Chromatography), 2002,20:436-438).The present invention uses the directly method of bonded chiral selective agent on matrix, and the integral post that is obtained has wider range of application, and the fractionation that can be used for various micromolecule separation, multiple chipal compounds separates and the biomacromolecule separation.
Summary of the invention
The problem that will solve of the present invention be to provide bonding cyclodextrin compounds highly effective liquid phase and organic phase integral chromatographic column and preparation method thereof.Bonding has the cyclodextrin or derivatives thereof on this integral post, can use in high performance liquid chromatography.
The invention provides a kind of bonding cyclodextrin compounds highly effective liquid phase and organic phase integral chromatographic column, bonding has the cyclodextrin or derivatives thereof on this integral post, can use in high performance liquid chromatography.Have hydroxyl to exist before described cyclodextrin or derivatives thereof is recommended in and is bonded, this hydroxyl can be unsubstituted hydroxyl, also can be the hydroxyl on the substituted radical.Described substituted radical is recommended as C
1～C
6Alkyl, hydroxyalkyl (wherein alkyl is C
1～C
6Alkyl or alkyl ether).Described cyclodextrine derivatives can be a hydroxypropyl, 2,6-dimethyl beta-CD, permethylated β-CD, part methyl β-CD, hydroxyethyl β-CD, 2,3-dioxy acetyl β-CD, 1-(1-naphthyl) ethyl carbamyl β-CD, sulfonation β-CD, sulfobutyl-beta-CD, sulfoethyl β-CD, ethyloic β-CD, carboxyethyl β-CD, 6A-methylamino β-CD, 6A, 6D-dimethylamino β-CD and β-CD polymkeric substance; Described β-CD represents beta-schardinger dextrin-.Described cyclodextrin or derivatives thereof further is recommended as β-CD (beta-schardinger dextrin-), hydroxyethyl beta-schardinger dextrin-or HP-β-CD (the beta-schardinger dextrin-hydroxypropyl ether claims hydroxypropyl again).Described cyclodextrin or derivatives thereof further is recommended as β-CD or HP-β-CD.Described integral post matrix is recommended as the glycidyl methacrylate-EDMA ethylene dimethacrylate polymkeric substance of the build of porous.
The invention provides the preparation method of above-mentioned highly effective liquid phase and organic phase integral chromatographic column, this method is that the mode of described cyclodextrin or derivatives thereof by derivatization on the post is bonded on the integral post matrix.Promptly prepare integral post matrix earlier, the derivatization reaction potpourri is reacted with it by matrix obtain.
Wherein said integral post matrix recommends by glycidyl methacrylate (GMA) and EDMA ethylene dimethacrylate (EDM4) to obtain with azoisobutyronitrile (AIBN) initiated polymerization in the presence of pore-foaming agent lauryl alcohol and cyclohexanol.
Wherein GMA is a monomer, and EDMA is a crosslinking chemical, and lauryl alcohol and cyclohexanol are as pore-foaming agent, and AIBN is as initiating agent.It is pure that GMA, EDMA, lauryl alcohol, cyclohexanol are at least homemade analysis, recommends through decompression distillation before using; It is pure that AIBN is recommended as analysis, recommends through recrystallization before using.The polymerization of recommending is GMA: EDMA=2: 3-3 with the composition and the proportioning of potpourri: 2 (mass ratioes), lauryl alcohol: cyclohexanol=9: 1-7: 3 (mass ratioes), monomer and crosslinking chemical: pore-foaming agent=1: 3-1: 1 (mass ratio), AIBN are the 0.5-2% (mass percent) of monomer and crosslinking chemical.Be recommended in to mix afterwards and use behind the helium injection gas 15min.Recommend all now with the current at every turn.Recommendation pours in the pipe after polymerization is mixed in proportion with potpourri, and seal at two ends, vertically is put in to carry out polyreaction in the water-bath.Polymeric reaction condition is recommended as follows: polymerization temperature 55-60 ℃, preferred value is 57 ℃; Reaction time 10-48h.
After polymerization finishes the integrated substrate post that makes being packed into, (described column sleeve is Z-MODULE for example for column sleeve
TMRadial Compression Separation System, available from Waters company, Waters Corporation, MA01757 USA), recommends to utilize ethanol, recommend flow velocity 0.5mL/min flushing 2-3h, not reacted monomer, crosslinking chemical and pore-foaming agent are rinsed well fully.Afterwards, recommending with ACN is moving phase, flow velocity is recommended as 1mL/min, recommend 254nm to detect, recommend with biphenyl, naphthalene and ethyl benzoate as the micromolecule sample, post effect to integral post matrix is done preliminary evaluation, recommends to select the matrix post that post is imitated more than 400NTP/10cm to do further derivatization experiment.
The derivatization reagent compound method is recommended as: β-CD or HP-β-CD are dissolved in DMSO/ACN (volume ratio is 2: 1-1: 3, preferred 1: the 1) mixed solution, and wherein the amount ratio of β-CD or HP-β-CD and DMSO/ACN is recommended as/100 milliliters of 3-15 grams, adds BF
3Et
2O (BF
3Content be recommended as 46.8-47.8%), BF wherein
3Et
2The consumption of O is recommended about 1-10% (percent by volume), preferred 3.5%.Utilize the HPLC infusion to go in the integrated substrate post derivatization reagent, the realization under the room temperature circulates in the post derivatization.Behind the recommendation response 48h, utilize the HPLC pump that the DMSO/ACN mixed solution of equal volume ratio is injected integral post, material and unreacted derivatization reagent that possible derivatization produces are replaced out.
After the integral post preparation is finished, carry out conventional post and imitate evaluation (recommend: moving phase is ACN, and flow velocity 1mL/min, sample are micromolecular compounds such as naphthalene), and estimate before and after the derivatization variation of same sample retention behavior on pillar.For the chiral resolution ability of integral post, can utilize chirality samples such as styrax, moving phase is recommended as ACN/H
2O=75: 25, under 254nm, detect.
The preparation method of high performance liquid chromatography organic whole post provided by the invention can at room temperature be bonded to β-CD or HP-β-CD on the integrated substrate post, is used for the analysis of micromolecule sample, and chiral resolution.Liquid-phase chromatographic column provided by the invention can be used for the analysis of micromolecule sample separation, chipal compounds splits and separates with biomacromolecule.
Description of drawings:
1, Fig. 1 is the liquid phase spectrogram that β-CD integral post is separated naphthalene, ethyl benzoate and Pa Zuosha star potpourri
2, Fig. 2 is the liquid phase spectrogram that HP-β-CD integral post is separated biphenyl, ethyl benzoate and dinaphthol potpourri.
3, Fig. 3 is that HP-β-CD integral post is separated benzoic liquid phase spectrogram.
Embodiment:
Embodiment one
The polymerization configuration of potpourri and the preparation of integrated substrate post:
It is now with the current to share potpourri, gets GMA8g, EDMA12g, and cyclohexanol 27g, lauryl alcohol 3g and AIBN0.2g mix, and use behind the helium injection gas 15min.Polymerization pours in the nylon column jecket of internal diameter 8mm, effective length 10cm with potpourri, and seal at two ends, vertically is put in 57 ℃ the water-bath to react 12h.The integrated substrate post that the makes column sleeve (Z-MODULE that packs into
TMRadial Compression SeparationSystem, available from Waters company, Waters Corporation, MA 01757, USA) in, receive on the HPLC pump, with flow velocity 0.5mL/min, flushing 2-3h removes unreacted intact monomer, crosslinking chemical and pore-foaming agent fully with ethanol.Afterwards, be moving phase with ACN, flow velocity is 1mL/min, 254nm detects, as the micromolecule sample, the post effect of integral post matrix is done preliminary evaluation with biphenyl, naphthalene and ethyl benzoate, select the matrix post that post is imitated more than 400NTP/10cm to do further derivatization experiment.
The preparation method of β-CD integral post:
Preparation derivatization solution (moving phase): use anhydrous Na
2SO
4DMSO/ACN (volume ratio is 1: 1) the mixed solution 100mL that handles 24h is positioned in the beaker of 250mL; Add BF while stirring
3Et
2O (content is 46.8-47.8%) 3.3mL; Add dry β-CD6.17g while stirring and (be equivalent to 5.4 * 10
-3Mol), treat that it dissolves fully.Derivatization solution is gone in the integrated substrate post room temperature moving phase/derivatization reagent circulation two days of ordering, flow velocity 0.3mL/min with the HPLC infusion; Use the moving phase of DMSO/ACN (volume ratio is 1: 1) that the β-CD in the pillar is rinsed well then, last, wash with ACN.
The high performance liquid chromatogram experiment condition is as follows:
Use ultraviolet 254nm to detect, room temperature is used ACN/H
2((volume ratio) is moving phase to O=75/25, and flow velocity is 1mL/min.
Sample is naphthalene, ethyl benzoate and the Pa Zuosha star mixed solution with the moving phase preparation.
β-CD integral post is separated the liquid phase spectrogram of naphthalene, ethyl benzoate and Pa Zuosha star biased sample, as shown in Figure 1.
Embodiment two
The configuration of polymerization usefulness potpourri and the preparation of integrated substrate post are with embodiment one.
The preparation method of HP-β-CD integral post:
Method at the post derivatization is similar to embodiment one: derivatization solution is the DMSO/ACN (volume ratio is 1: 1) of 155mL, contains HP-β-CD 8.18g, BF
3Et
2O (content is 46.8-47.8%) is 5mL.Under the room temperature, make derivatization solution circulation two days; The moving phase of using DMSO/ACN (volume ratio is 1: 1) is then rinsed the β of the HP-in the pillar-CD flushing well at last with ACN, carry out the evaluation of derivatization rear pillar.
The high performance liquid chromatogram experiment condition is as follows:
Use ultraviolet 254nm to detect, room temperature is used ACN/H
2O=75/25 (volume ratio) is a moving phase, and flow velocity is 1.0mL/min.
Sample is biphenyl, ethyl benzoate and the dinaphthol mixed solution with the moving phase preparation.
HP-β-CD integral post is separated the liquid phase spectrogram of biphenyl, ethyl benzoate and dinaphthol potpourri, as shown in Figure 2.
Use ultraviolet 254nm to detect, room temperature is used ACN/H
2O=75/25 (volume ratio) is a moving phase, and flow velocity is 0.8mL/min.
Sample is the styrax enantiomorph solution with the moving phase preparation.
HP-β-CD integral post is separated the liquid phase spectrogram of styrax enantiomorph, as shown in Figure 3.
Claims (11)
1. a highly effective liquid phase and organic phase integral chromatographic column is characterized in that bonding has the cyclodextrin or derivatives thereof on this organic phase integral post.
2. highly effective liquid phase and organic phase integral chromatographic column according to claim 1 is characterized in that described cyclodextrin or derivatives thereof has hydroxyl to exist before being bonded, this hydroxyl can be the hydroxyl on unsubstituted hydroxyl or the substituted radical, and described substituted radical is C
1～C
6Alkyl, hydroxyalkyl.
3. highly effective liquid phase and organic phase integral chromatographic column according to claim 1, it is characterized in that described cyclodextrine derivatives is a hydroxypropyl, 2,6-dimethyl beta-CD, permethylated β-CD, part methyl β-CD, hydroxyethyl β-CD, 2,3-dioxy acetyl β-CD, 1-(1-naphthyl) ethyl carbamyl β-CD, sulfonation β-CD, sulfobutyl-beta-CD, sulfoethyl β-CD, ethyloic β-CD, carboxyethyl β-CD, 6A-methylamino β-CD, 6A, 6D-dimethylamino β-CD and β-CD polymkeric substance; Described β-CD represents beta-schardinger dextrin-.
4. highly effective liquid phase and organic phase integral chromatographic column according to claim 1 is characterized in that described cyclodextrine derivatives is hydroxypropyl or hydroxyethyl beta-schardinger dextrin-.
5. highly effective liquid phase and organic phase integral chromatographic column according to claim 1 is characterized in that the glycidyl methacrylate-EDMA ethylene dimethacrylate polymkeric substance of the build that described integral post matrix is porous.
6. the preparation method of highly effective liquid phase and organic phase integral chromatographic column according to claim 1 is characterized in that the mode of cyclodextrin or derivatives thereof by derivatization on the post is bonded on the integral post matrix.
7. the preparation method of highly effective liquid phase and organic phase integral chromatographic column according to claim 6 is characterized in that described cyclodextrin or derivatives thereof is at boron trifluoride (BF
3) catalysis down with integral post matrix on epoxide group react.
8. the preparation method of highly effective liquid phase and organic phase integral chromatographic column according to claim 6 is characterized in that the cyclodextrin or derivatives thereof is that to be dissolved in volume ratio be 2: 1-1: in the mixed solution of 3 dimethyl sulfoxide (DMSO) (DMSO)/acetonitrile (ACN), at BF
3Catalysis under with in the mode of post derivatization and the reaction of the epoxide group on the integral post matrix; BF
3Content in the mixed solution of DMSO/ACN is in 0.5-5% (mass percent).
9. the preparation method of highly effective liquid phase and organic phase integral chromatographic column according to claim 6 is characterized in that the mixed solution of DMSO/ACN must be through removing water treatment.
10. the preparation method of highly effective liquid phase and organic phase integral chromatographic column according to claim 6, it is characterized in that described integral post matrix be by glycidyl methacrylate (GMA) and EDMA ethylene dimethacrylate (EDMA) in the presence of pore-foaming agent lauryl alcohol and cyclohexanol, obtain with azoisobutyronitrile (AIBN) initiated polymerization.
11. preparation method according to claim 6 or 10 described highly effective liquid phase and organic phase integral chromatographic columns, it is characterized in that polymerization is GMA: EDMA=2: 3-3 with the composition and the proportioning of potpourri: 2 (mass ratioes), lauryl alcohol: cyclohexanol=9: 1-7: 3 (mass ratioes), monomer GMA and crosslinking chemical EDMA: pore-foaming agent=1: 3-1: 1 (mass ratio), AIBN are the 0.5-2% (mass percent) of monomer and crosslinking chemical; Polymerization temperature is 55-60 ℃, and the reaction time is 10-48h.
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| CN101537344B (en) * | 2009-04-23 | 2011-05-18 | 中国科学院化学研究所 | Monolithic column, preparation method and application thereof |
| CN101348577B (en) * | 2007-07-17 | 2011-07-27 | 中国科学院化学研究所 | Porous integral medium, preparation and use thereof |
| CN101077894B (en) * | 2006-05-26 | 2011-10-19 | 广州研创生物技术发展有限公司 | Beta-cyclodextrins chiral selecting agent and preparation method thereof |
| CN102924708A (en) * | 2012-11-01 | 2013-02-13 | 天津奥顺达科技有限公司 | Synthesis and application of novel cyclodextrin polymer chiral resolving agents |
| CN102940979A (en) * | 2012-10-22 | 2013-02-27 | 暨南大学 | Method and application for preparing cyclodextrin organic polymer capillary monolithic column via one-step method |
| CN104415740A (en) * | 2013-09-04 | 2015-03-18 | 北京蛋白质组研究中心 | Hydrophilic chromatographic packing as well as preparation method and application thereof |
| CN105092764A (en) * | 2015-09-14 | 2015-11-25 | 浙江工业大学 | Method for detecting migration quantity of methacrylic acid in food plastic packaging material by using online derivatization-gas chromatography |
| CN107709251A (en) * | 2015-06-16 | 2018-02-16 | 安捷伦科技有限公司 | For analyzing the composition and method of sample preparation |
| CN110636899A (en) * | 2017-06-30 | 2019-12-31 | 昭和电工株式会社 | Packing material for liquid chromatography and column for liquid chromatography |
| CN114280134A (en) * | 2021-09-30 | 2022-04-05 | 宁波大学 | Reagent and method for analyzing enantiomer structures of two-paired binaphthyl derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101077894B (en) * | 2006-05-26 | 2011-10-19 | 广州研创生物技术发展有限公司 | Beta-cyclodextrins chiral selecting agent and preparation method thereof |
| CN101348577B (en) * | 2007-07-17 | 2011-07-27 | 中国科学院化学研究所 | Porous integral medium, preparation and use thereof |
| CN101537344B (en) * | 2009-04-23 | 2011-05-18 | 中国科学院化学研究所 | Monolithic column, preparation method and application thereof |
| CN102940979A (en) * | 2012-10-22 | 2013-02-27 | 暨南大学 | Method and application for preparing cyclodextrin organic polymer capillary monolithic column via one-step method |
| CN102924708A (en) * | 2012-11-01 | 2013-02-13 | 天津奥顺达科技有限公司 | Synthesis and application of novel cyclodextrin polymer chiral resolving agents |
| CN104415740A (en) * | 2013-09-04 | 2015-03-18 | 北京蛋白质组研究中心 | Hydrophilic chromatographic packing as well as preparation method and application thereof |
| CN104415740B (en) * | 2013-09-04 | 2017-02-08 | 北京蛋白质组研究中心 | Hydrophilic chromatographic packing as well as preparation method and application thereof |
| CN107709251A (en) * | 2015-06-16 | 2018-02-16 | 安捷伦科技有限公司 | For analyzing the composition and method of sample preparation |
| CN105092764A (en) * | 2015-09-14 | 2015-11-25 | 浙江工业大学 | Method for detecting migration quantity of methacrylic acid in food plastic packaging material by using online derivatization-gas chromatography |
| CN110636899A (en) * | 2017-06-30 | 2019-12-31 | 昭和电工株式会社 | Packing material for liquid chromatography and column for liquid chromatography |
| CN110636899B (en) * | 2017-06-30 | 2023-03-24 | 昭和电工株式会社 | Packing material for liquid chromatography and column for liquid chromatography |
| CN114280134A (en) * | 2021-09-30 | 2022-04-05 | 宁波大学 | Reagent and method for analyzing enantiomer structures of two-paired binaphthyl derivatives |
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