CN104138751A - Chiral core-shell chromatography stationary phase and preparation method - Google Patents
Chiral core-shell chromatography stationary phase and preparation method Download PDFInfo
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- CN104138751A CN104138751A CN201310167942.4A CN201310167942A CN104138751A CN 104138751 A CN104138751 A CN 104138751A CN 201310167942 A CN201310167942 A CN 201310167942A CN 104138751 A CN104138751 A CN 104138751A
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- silica gel
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- nucleocapsid
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Abstract
The invention discloses a chiral core-shell chromatography stationary phase. The inner layer is nonporous silica gel which is coated with a hybrid mesoporous silica gel shell layer containing a chiral diaminocyclohexane group. Meanwhile, the invention also discloses a preparation method of the above chiral core-shell liquid chromatography packing. The hybrid mesoporous silica gel has characteristics of high permeability and uniform distribution of organo-functional groups, and the core-shell packing has advantages of high column efficiency and fast analysis speed. By combining the characteristics of the hybrid mesoporous silica gel and the advantages of the core-shell packing, a novel chromatography stationary phase packing is formed.
Description
Technical field
The present invention relates to porous material preparation and technical field of analytical chemistry, be specifically related to a kind of chirality nucleocapsid liquid chromatography stuffing and preparation method thereof.
Background technology
Hybrid ordered mesoporous silica gel refer to adopt organic group bridging estersil [(OR)
3siR ' Si (OR)
3] as one of silicon source, after hydrolytic-polymeric reaction, directly prepare the ordered mesoporous silica gel that contains organic group in skeleton.Hybridisation silica gel has larger specific area, regularly arranged duct, narrow pore-size distribution, and has the advantages such as better hydrothermal stability, mechanical stability and chemical stability.In recent years, chiral hybrid mesoporous silica gel shows superior prospect in the application of chipal compounds chromatographic isolation.But hybrid mesoporous silica gel organo-functional group load capacity feature high, that specific area is large increases the adsorption-desorption time of analyte on filler, has increased resistance to mass tranfer, this causes chromatographic peak broadening, and the phenomenon that post effect reduces occurs.Hybrid mesoporous silica gel layer is wrapped on atresia silica gel core, makes hud typed filler, shorten the mass transfer path of filler, can effectively improve hybrid mesoporous silicagel column and imitate low problem.
Hud typed filler, than the filler of full porous, has higher theoretical cam curve (the full loose structure post effect of the nucleocapsid of 3 μ m and sub-2 μ m is quite), shorter mass transfer path, and this also makes greatly shorten analysis time.In recent years, these advantages are paid close attention to hud typed chromatograph packing material widely.But, at present little about the research of the hud typed chromatograph packing material of chirality, also there is not the hud typed chromatograph packing material of commercial chirality.Compared with full porous material, core-shell material is due to the existence of atresia core, and specific area is little, and traditional bonding or coating method all will cause the problem that chiral selector content is low.Therefore, we are uniformly distributed in the skeleton of mesoporous silicon glue-line containing chiral radicals, improve the chiral radicals content in shell, make the hud typed chromatograph packing material of novel chirality.
Summary of the invention
Goal of the invention: the object of the present invention is to provide a kind of synthetic method of novel chirality nucleocapsid liquid chromatography stuffing, to improve problems of the prior art.
Technical scheme: in order to achieve the above object, the present invention is specifically achieved like this: adopt self-assembly method layer by layer, the hybrid mesoporous silica gel layer that contains chirality cyclohexanediamine group in atresia silica gel outer wrap multilayer.
Wherein, in the hybrid mesoporous silica gel layer of the outer parcel of described filler, except adulterating chirality cyclohexanediamine group, chiral binaphthyl diamines or chiral binaphthalene diol group also can adulterate.
A preparation method for chirality nucleocapsid liquid chromatography stuffing, comprises the following steps:
(1) chirality cyclohexanediamine is reacted with isocyanic acid propyl-triethoxysilicane, form two estersil: the N of chirality cyclohexanediamine, N '-bis--[(triethoxy is silica-based) propyl group]-bis--(uride)-cyclohexane (DACH-BS);
(2) get ammoniacal liquor, ethanol and deionized water be mixed and made into A liquid at 150～250: 40～80: 60～120 by volume, by A liquid and ethyl orthosilicate by volume 1～3: 1 under condition of ice bath mix and blend 0.5h～2h, the product obtaining is extremely neutral by deionized water and ethanol washing, 80～100 DEG C are dried 8～10h, obtain having the atresia silica gel of spherical morphology;
(3) 1: 1 by volume～5 mix ethanol and deionized water, add 0.1～0.8% (w/v) OTAC, 1～10% (w/v) P123 block copolymer, make B liquid;
(4) 1: 1 by volume～5 mix ethanol and deionized water, get atresia silica gel and add wherein, every 100ml solution adds 1～4g atresia silica gel, and ultrasonic 10～30min, add 28% ammoniacal liquor of above-mentioned cumulative volume 2～10%, stirring at room temperature 15～20min;
(5) B liquid is added step (4) gained solution by 1: 1 by volume～3, stir 30～50min, dropwise add the N mixing, N '-bis--[(triethoxy is silica-based) propyl group]-trans-(1R, 2R)-bis--(uride)-cyclohexane (DACH-BS) and tetraethyl orthosilicate (TEOS), wherein 10%～50% of Zhan Zonggui source, chirality silicon source content, room temperature reaction 1～5h, centrifugal product, obtains the hud typed material of coated one deck chiral hybrid mesoporous silicon glue-line;
(6) material obtaining in step (5) is continued to be scattered in ethanol, deionized water mixed liquor, repeating step (3～5) 2～15 times, obtains the hud typed material of wrapped multiple chiral hybrid mesoporous silicon glue-line;
(7) by ethanol and deionized water, hud typed step (6) gained material is washed to neutral to 60 DEG C of vacuum drying 8～24h;
(8) within 200: 3 by volume, get ethanol, concentrated hydrochloric acid is mixed into Template removal, every 1g step (7) product at room temperature stirs 24h with 200ml Template removal;
(9) step (8) products therefrom is extremely neutral with deionized water washing, 60 DEG C of vacuum drying 8～24h, obtain chirality nucleocapsid liquid chromatography stuffing.
Wherein, in described step (2), the diameter of atresia silica gel is 1 μ m～5 μ m.Wherein, the two estersil of chirality cyclohexanediamine that participate in hydrolytic polymerization in described step (5) can be by the two estersil of chiral binaphthyl diamines, and the two estersil of chiral binaphthalene diol replace.1～15 layer of the coated number of plies of the hud typed material of chirality, coated thickness is about 25～500nm.
Beneficial effect: the present invention combines the advantage of hybrid mesoporous silica gel and hud typed filler, has prepared the novel chromatograph stationary-phase stuffing of a class.Compared with chiral hybrid mesoporous silica gel, novel chiral core-shell material has post effect high, the feature that analysis speed is fast, compared with the chirality core-shell material of preparing with coating process or bonding method, organo-functional group is evenly distributed in shell, do not stop up duct, organo-functional group is difficult for running off, and also has the advantage of high, the good stability of permeability.
Detailed description of the invention
Embodiment 1:
(1), under nitrogen protection, in two mouthfuls of flasks of 250mL, add 0.38g trans-(1R, 2R)-cyclohexanediamine (DACH), the anhydrous CH of 100mL
2cl
2, 1.73g isocyanic acid propyl-triethoxysilicane (ICPTES) is added drop-wise in above-mentioned reactant liquor slowly with syringe, at room temperature react 2h, CH is removed in decompression distillation
2cl
2, obtain solid product.Then with anhydrous n-hexane washing gained solid, filter, excessive ICPTES removes with filtrate, by filter cake vacuum drying, obtain two estersil: the N of chirality cyclohexanediamine, N '-bis--[(triethoxy is silica-based) propyl group]-trans-(1R, 2R)-bis--(uride)-cyclohexane (DACH-BS) is white solid.
(2) within 200: 56: 80 by volume, get ammoniacal liquor, ethanol and deionized water and be mixed and made into A liquid, in 50ml round-bottomed flask, add 2ml A liquid+1ml ethyl orthosilicate (TEOS), under ice-water bath condition, stir 5min, dropwise add A liquid and TEOS with the flow velocity of 24ml/h and 12ml/h respectively with constant flow pump at ambient temperature.After 50min, stop dripping.By deionized water and ethanol washing for the product obtaining, 90 DEG C of dry 8h.The atresia silica gel obtaining is about 2 μ m.
(3) get the atresia silica gel that 0.5g has synthesized, be scattered in the mixed solution of 12ml ethanol and 24ml deionized water, ultrasonic 20 minutes and stir 20 minutes, add 1.2ml ammoniacal liquor.In another beaker, take 0.7g P123 and 0.03g C18TMACl, add in 3.9ml ethanol and 7.4ml deionized water, stir it is dissolved, make surfactant mixed solution.Surfactant mixed solution is added in scattered nonporous silicon sol solution, stir 30 minutes.0.15g DACH-BS (0.25mmol) and 0.23ml TEOS (1 mmol) are dissolved in lml ethanol, make and mix silicon source solution.Add in the nonporous silicon sol solution of absorption surface activating agent mixing silicon source solution, stir 3 hours.After completion of the reaction, the silica gel product that centrifugal acquisition has been reacted, washes away unnecessary surfactant with ethanol, the silica gel of acquisition is dropped into again to the mixed solution of 12ml ethanol and 24ml deionized water, as the core of next step reaction, continues parcel, repeating step 4 times.Having obtained bridged bond in shell has the hud typed material of chirality cyclohexanediamine group, and with ethanol and deionized water washing, 80C dries 8h.
(4) end product obtaining add the above-mentioned reaction of 1g in 200ml Template removal (ethanol-concentrated hydrochloric acid=200: 3 (v/v)) in, stirs 24h under room temperature.G6 sand core funnel filters, and for filter cake, absolute ethyl alcohol, deionized water are fully washed, in 60 DEG C of vacuum drying.
Embodiment 2:
(1), under nitrogen protection, in two mouthfuls of flasks of 250mL, add 0.38g trans-(1R, 2R)-cyclohexanediamine (DACH), the anhydrous CH of 100mL
2cl
2, 1.73g isocyanic acid propyl-triethoxysilicane (ICPTES) is added drop-wise in above-mentioned reactant liquor slowly with syringe, at room temperature react 2h, CH is removed in decompression distillation
2cl
2, obtain solid product.Then with anhydrous n-hexane washing gained solid, filter, excessive ICPTES removes with filtrate, by filter cake vacuum drying, obtain two estersil: the N of chirality cyclohexanediamine, N '-bis--[(triethoxy is silica-based) propyl group]-(1R, 2R)-bis--(uride)-cyclohexane (DACH-BS) is white solid.
(2) within 200: 60: 100 by volume, get ammoniacal liquor, ethanol and deionized water and be mixed and made into A liquid, by A liquid and 2: 1 by volume mix and blend 1.5h under condition of ice bath of ethyl orthosilicate, the product obtaining is extremely neutral by deionized water and ethanol washing, 80～100 DEG C of dry 9h, obtaining diameter is the atresia silica gel of 3 μ m.
(3) get the atresia silica gel that 0.5g has synthesized, be scattered in the mixed solution of 12ml ethanol and 24ml deionized water, ultrasonic 20 minutes and stir 20 minutes, add 0.6ml ammoniacal liquor.In another beaker, take 0.7g P123 and 0.03g C18TMACl, add in 3.9ml ethanol and 7.4ml deionized water, stir it is dissolved, make surfactant mixed solution.Surfactant mixed solution is added in scattered nonporous silicon sol solution, stir 30 minutes.0.3g DACH-BS (0.5mmol) and 0.46ml TEOS (2mmol) are dissolved in 1ml ethanol, make and mix silicon source solution.Add in the nonporous silicon sol solution of absorption surface activating agent mixing silicon source solution, stir 3 hours.After completion of the reaction, the silica gel product that centrifugal acquisition has been reacted, washes away unnecessary surfactant with ethanol, the silica gel of acquisition is dropped into again to the mixed solution of 12ml ethanol and 24ml deionized water, as the core of next step reaction, continues parcel, repeating step 4 times.Having obtained bridged bond in shell has the hud typed material of chirality cyclohexanediamine group, with ethanol and deionized water washing, dries 8h for 80 DEG C.
(4) the hud typed material of chirality obtaining add the above-mentioned reaction of 1g in 200ml Template removal (ethanol-concentrated hydrochloric acid=200: 3 (v/v)) in, stirs 24h under room temperature.G6 sand core funnel filters, and for filter cake, absolute ethyl alcohol, deionized water are fully washed, in 60 DEG C of vacuum drying.
Embodiment 3:
Fig. 1 is the scanning electron microscope (SEM) photograph of the hud typed chromatograph packing material of chirality cyclohexanediamine in embodiment 1
Fig. 2 is the transmission electron microscope picture of the hud typed chromatograph packing material of chirality cyclohexanediamine in embodiment 1
Fig. 3 is that the hud typed chromatograph packing material of chirality cyclohexanediamine of the present invention separates (A) R/S-1,1 '-dinaphthalene-2,2 '-diphenol, (B) R/S-6,6 '-bis-bromo-1,1 '-dinaphthalene-2, the chromatogram of 2 '-diphenol under positive phase system.
Claims (8)
1. a chirality nucleocapsid liquid chromatography stuffing, it is characterized in that, internal layer is atresia silica gel, outer coated by N, the hybrid mesoporous shell that the common hydrolytie polycondensation of N '-bis--[(triethoxy is silica-based) propyl group]-(1R, 2R)-bis--(uride)-cyclohexane and ethyl orthosilicate forms.
2. the preparation method of nucleocapsid liquid chromatography stuffing, is characterized in that, comprises the following steps:
(1) chirality cyclohexanediamine is reacted with isocyanic acid propyl-triethoxysilicane, form two estersil: the N of chirality cyclohexanediamine, N '-bis--[(triethoxy is silica-based) propyl group]-(1R, 2R)-bis--(uride)-cyclohexane (DACH-BS);
(2) get ammoniacal liquor, ethanol and deionized water be mixed and made into A liquid at 150～250: 40～80: 60～120 by volume, by A liquid and ethyl orthosilicate by volume 1～3: 1 under condition of ice bath mix and blend 0.5h～2h, the product obtaining is extremely neutral by deionized water and ethanol washing, 80～100C is dried 8～10h, obtains having the atresia silica gel of spherical morphology;
(3) 1: 1 by volume～5 mix ethanol and deionized water, add 0.1～0.8% (w/v) OTAC, 1～10% (w/v) P123 block copolymer, make B liquid;
(4) 1: 1 by volume～5 mix ethanol and deionized water, get atresia silica gel and add wherein, every 100ml solution adds 1～4g atresia silica gel, and ultrasonic 10～30min, add 28% ammoniacal liquor of above-mentioned cumulative volume 2～10%, stirring at room temperature 15～20min;
(5) B liquid is added step (4) gained solution by 1: 1 by volume～3, stir 30～50min, dropwise add the N mixing, N '-bis--[(triethoxy is silica-based) propyl group]-(1R, 2R)-bis--(uride)-cyclohexane (DACH-BS) and tetraethyl orthosilicate (TEOS), room temperature reaction 1～5h, centrifugal product, obtains the hud typed material of coated one deck chiral hybrid mesoporous silicon glue-line;
(6) material obtaining in step (5) is continued to be scattered in ethanol, deionized water mixed liquor, repeating step (4～5) 2～15 times, obtains the hud typed material of wrapped multiple chiral hybrid mesoporous silicon glue-line;
(7) by ethanol and deionized water, hud typed step (6) gained material is washed to neutral to 60C vacuum drying 8～24h;
(8) within 200: 3 by volume, get ethanol, concentrated hydrochloric acid is mixed into Template removal, every 1g step (7) product at room temperature stirs 24h with 200ml Template removal;
(9) step (8) products therefrom is extremely neutral with deionized water washing, 60C vacuum drying 8～24h, obtains chirality nucleocapsid liquid chromatography stuffing.
3. the preparation method of nucleocapsid liquid chromatography stuffing according to claim 2, is characterized in that, in described step (2), the diameter of atresia silica gel is 1 μ m～5 μ m.
4. the preparation method of nucleocapsid liquid chromatography stuffing according to claim 2, it is characterized in that, centrifugal step (5) gained product is replaced to the atresia silica gel in step (4), repeating step (4) and (5) and other steps are constant, obtain the hud typed material of the coated hybrid mesoporous silica gel of multilayer.
5. the preparation method of nucleocapsid liquid chromatography stuffing according to claim 5, is characterized in that, the coated number of plies of described hybridization mesoporous material is 2～15 layers.
6. according to the preparation method of the arbitrary described nucleocapsid liquid chromatography stuffing of claim 2～5, it is characterized in that, in step (1) and (5), the chirality cyclohexanediamine group of skeleton doping is replaced by chiral binaphthyl diamine groups or chiral binaphthalene diol group.
7. the preparation method of nucleocapsid liquid chromatography stuffing according to claim 2, is characterized in that, in described step (5) and (6), the coated thickness of hybridization mesoporous material is 50～500nm.
8. the preparation method of nucleocapsid liquid chromatography stuffing according to claim 2, wherein alkali is ammoniacal liquor, NaOH or potassium hydroxide; Alcohol is methyl alcohol or ethanol; Surfactant structure is the quaternary ammonium salt shown in following:
Wherein R
1, R
2, R
3and R
4independently be selected from respectively C
1-C
22a kind of in alkyl, and R
1, R
2, R
3and R
4in have one at least for C
12-C
22alkyl; X is halogen; Silane is ethyl orthosilicate, trimethyl methoxy silane, trimethylethoxysilane or tetramethoxy-silicane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109414681A (en) * | 2016-03-06 | 2019-03-01 | 沃特世科技公司 | The hybrid material comprising porous surface core and adjacent material for chromatographic isolation |
| CN113680338A (en) * | 2021-08-26 | 2021-11-23 | 天津津颐生物科技有限公司 | Novel chromatographic material and preparation method thereof |
| CN115058065A (en) * | 2022-06-30 | 2022-09-16 | 万华化学集团股份有限公司 | Modified filler with light-oxygen degradation agent slow release effect, preparation method and degradation rate controllable PBAT mulching film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717513A (en) * | 2009-11-10 | 2010-06-02 | 中国药科大学 | Hybrid ordered mesoporous silica gel chromatograph stationary-phase stuffing and preparation method thereof |
| CN102241823A (en) * | 2011-04-29 | 2011-11-16 | 中国药科大学 | Binaphthylamine derivative hybrid mesoporous silica gel chiral stationary phase |
-
2013
- 2013-05-09 CN CN201310167942.4A patent/CN104138751A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717513A (en) * | 2009-11-10 | 2010-06-02 | 中国药科大学 | Hybrid ordered mesoporous silica gel chromatograph stationary-phase stuffing and preparation method thereof |
| CN102241823A (en) * | 2011-04-29 | 2011-11-16 | 中国药科大学 | Binaphthylamine derivative hybrid mesoporous silica gel chiral stationary phase |
Non-Patent Citations (2)
| Title |
|---|
| GUIRU ZHU ET AL: "Chiral mesoporous organosilica spheres: Synthesis and chiral separation capacity", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| JESSE O.OMAMOGHO ET AL.: "Structural variation of solid core and thickness of porous shell of 1.7μm core–shell silica particles on chromatographic performance: Narrow bore columns", 《JOURNAL OF CHROMATOGRAPHY A》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109414681A (en) * | 2016-03-06 | 2019-03-01 | 沃特世科技公司 | The hybrid material comprising porous surface core and adjacent material for chromatographic isolation |
| US11642653B2 (en) | 2016-03-06 | 2023-05-09 | Waters Technologies Corporation | Hybrid material for chromatographic separations comprising a superficially porous core and a surrounding material |
| CN113680338A (en) * | 2021-08-26 | 2021-11-23 | 天津津颐生物科技有限公司 | Novel chromatographic material and preparation method thereof |
| CN115058065A (en) * | 2022-06-30 | 2022-09-16 | 万华化学集团股份有限公司 | Modified filler with light-oxygen degradation agent slow release effect, preparation method and degradation rate controllable PBAT mulching film |
| CN115058065B (en) * | 2022-06-30 | 2023-07-11 | 万华化学集团股份有限公司 | Modified filler with photooxidation degradation agent slow release effect, preparation method and PBAT (Poly Butylene terephthalate) mulch film with controllable degradation rate |
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