CN1289184C - Cyclodextrin linkage silica gel fixed phase, preparing method and use thereof - Google Patents
Cyclodextrin linkage silica gel fixed phase, preparing method and use thereof Download PDFInfo
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Abstract
The present invention relates to a cyclodextrin bonded silica gel fixed phase, a preparation method thereof and an application thereof. The preparation method comprises the following steps of preparing and purifying halogenated propyl bonded silica gel as precursors, making sodium hydride and cyclodextrin react to obtain cyclodextrin sodium salts, and making the cyclodextrin sodium salts and the bonded halogenated propyl react on the surfaces of the silica gel in a solid phase condensation mode to obtain the cyclodextrin bonded silica gel fixed phase. The cyclodextrin bonded silica gel fixed phase prepared with the method has low surface bonding rate, and the short-chain space groups well keep the natural form of the cyclodextrin. The cyclodextrin bonded silica gel fixed phase has better separating selectivity and chiral separation capability than those of natural cyclodextrin bonded fixed phase, and is suitable for separating structural isomers from enantiomer medicines in the application fields of separation science, technique and biologic medicine of high efficiency liquid phase chromatography.
Description
Technical field
The present invention relates to fixedly phase and its production and use of cyclodextrin bonded silica gel chromatograph, function of dominant material synthesis technology on the methodology; Its object belongs to separating medium, is applicable to that high performance liquid chromatography, micro column liquid chromatography and electrochromatography etc. separate science, technical field.
Background technology
High performance liquid chromatography has critical role in modern compartment analysis, be widely used in chemistry, biology, medicine and pharmacology, life science and environmental science, becomes requisite research means.Separation system becomes increasingly complex, particularly the compartment analysis of actual sample is had higher requirement mutually to chromatographic technique especially chromatographic stationary, commercial at present silica gel and modified silica-gel kind are very abundant, are the fixing requirement that can not satisfy compartment analysis mutually of reverse-phase chromatography of representative with octadecyl silane (ODS).Therefore, the development of the chromatographic stationary phase of high selectivity and exploitation are one of core contents of chromatographic field research." the exclusive type " of high selectivity is fixing mutually of a great variety, mainly contains: for satisfying the chiral stationary phase that drug enantiomer separates needs; Adapt to biochemical protein bonded stationary phase of separating; Equate based on crown ether, cyclodextrin, the calixarenes of supermolecule effect molecular imprinting stationary mutually fixing and obligatory type.
Cyclodextrin bonded fixedly as a kind of stable chiral stationary phase, be to prepare with nitrogenous interval base respectively by two Japanology groups the beginning of the eighties the earliest.Subsequently, they have prepared a series of cyclodextrin bonded fixedly phase by different nitrogenous intervals base, and have systematically compared the different interval base to the ground influence of cyclodextrin bonded fixedly phase chromatographic performance.Usefulness such as Fujimur are amino have been prepared cyclodextrin bonded mutually fixing respectively with diaminourea interval base.But just find that subsequently there is the shortcoming of following several respects in nitrogenous interval basic ring dextrin bonded stationary phase: (1) instability is easy to hydrolysis; (2) separation selectivity is influenced by the interval base; (3) in the building-up process, the inevitable partial oxidation of nitrogen and make fixedly phase displaing yellow; (4) the long and complex operation of building-up process.For this reason, Armstrong etc. utilizes 6-10 carbon atom base preparation unazotized β-CD bonded stationary phase and applied for patent at interval first.Also the cyclodextrin bonded fixing of some nonnitrogenous interval base is produced mutually, and its preparation method is subjected to patent protection mostly, wherein many cyclodextrin bonded fixedly phase commercializations.The preparation method of the cyclodextrin bonded fixedly phase of the nonnitrogenous interval base of having reported is few, most often by the KH560 coupling.Our laboratory adopts this interval base to prepare cyclodextrin bonded fixedly phase natural and derivatization, but separation selectivity is not good enough, no chiral separation performance.Armstrong etc. have also prepared cyclodextrin bonded fixedly phase by a series of coupling agent that contains the epoxide function base, and its natural cyclodextrin bonded silica gel fixedly phase enantiomer separation selectivity is not good enough.
Summary of the invention
Problem to be solved by this invention provides a kind of cyclodextrin bonded silica stationary phase and its production and use, this fixedly compare stable, selectivity is high, and the preparation method is simpler.
Technical scheme provided by the invention is: cyclodextrin bonded silica stationary phase, and its structural formula is:
The present invention also provides the preparation method of above-mentioned cyclodextrin bonded silica stationary phase, and preparation and purifying halopropyl bonded silica gel make the cyclodextrin sodium salt as precursor with sodium hydride and cyclodextrin reaction earlier; Cyclodextrin sodium salt and bonding halopropyl through the solid catalysis condensation reaction, get cyclodextrin bonded silica stationary phase on the silica gel surface.
The present invention can be in silica gel: halopropyl triethoxysilane coupling agent: dry toluene is 10 grams: 10-50 mM: the ratio of 200-500 milliliter, with particle diameter is in silica gel (silica) the adding dry toluene of 2-10 micron, add halopropyl triethoxysilane coupling agent again, add catalyst of triethylamine, be warming up to 110～120 ℃, reaction is 12-36 hour under reflux state, while hot suction filtration, washing, the dry halopropyl bonded silica gel that gets; Sodium hydride and cyclodextrin with mol ratio 1: 0.2～1.0 are reactant, are solvent with anhydrous dimethyl formamide (DMF), and reaction obtained the cyclodextrin sodium salt in 0.5-2 hour under 20-30 ℃ of room temperature; Add 1 gram halopropyl bonded silica gel in the cyclodextrin sodium salt of 0.2～2 mM, stir and be warming up to 80～130 ℃, reaction is 24～56 hours under the nitrogen protection, filter while hot, and washing, oven dry gets cyclodextrin bonded silica stationary phase.Its reaction equation is as follows:
X＝Cl，Br，I
The present invention adopts the solid phase surface continuous catalytic reaction to prepare cyclodextrin bonded fixedly phase.The halopropyl bonded silica gel is a kind of low pole, weak hydrophobic fixedly phase, can also be as the further synthetic bonded stationary phase that contains various functional groups of intermediate.But halopropyl and hydroxyl all are weak nucleophilic groups, the very low even not reaction of the activity of necleophilic reaction between the two.In order to increase its reactivity, the present invention prepares halopropyl bonded silica gel precursor earlier, after filtration, the washing, remove excessive reactant and accessory substance; Reduce complicated operations such as organic intermediate separation and purification; In addition, the bonded amount of halopropyl silica gel prepared by this method can reach 0.1mmol/g, the reaction site of the abundance that provides for follow-up necleophilic reaction.In addition, the cyclodextrin hydroxyl is transformed into sodium salt under the NaH effect, has increased the reactivity of necleophilic reaction greatly.At this moment, improve reaction temperature, bonding halopropyl silica gel can successfully prepare cyclodextrin bonded mutually fixing with the cyclodextrin sodium salt by the solid phase condensation catalytic reaction.The cyclodextrin hydroxyl is transformed into sodium salt under the NaH effect, this has not only increased the reactivity of necleophilic reaction, and the way by filtering, and removes excessive N aH and NaOH accessory substance, prevents the erosion of highly basic to silica matrix, and the permeability of post obviously improves.Cyclodextrin bonded fixedly phase stability height by the ehter bond connection, on fixing phase molecule structural design, adopt three hydrophobic short chains of methylene to connect and to play three-dimensional shielding action to the silica gel surface silanol group, reduce the silanol effect of bonded silica gel, improve the chromatographic peak symmetry; And the hydrophobic short chain of three methylene is not participated in the chromatogram retention behavior, thereby has demonstrated fully the molecule distinguishability of cyclodextrin by the big ring cavity shielding of cyclodextrin.In addition, necleophilic reaction activity between chloropropyl and cyclodextrin sodium salt is not high, again owing to be subjected to sterically hindered the influence, so each cyclodextrin molecular has only a hydroxyl to participate in reaction, the at interval basic coupling ring dextrin of short chain promotes cyclodextrin molecular arrangement and the natural configuration of retaining ring dextrin in order effectively on the silica gel surface, and the cyclodextrin molecular configuration has very strong flexibility, can regulate self configuration according to the size and the shape of guest molecule, thereby reach the optimum Match state of Subjective and Objective, the inclusion ability to function is embodied fully, and the separation selectivity of bonded stationary phase significantly improves.Fixing that the present invention makes is stable mutually, selectivity is high, and synthetic method is simple.
Cyclodextrin bonded silica stationary of the present invention can be used as high performance liquid chromatography, micro column liquid chromatography or capillary electric chromatogram separating filler mutually, be used for separating luxuriant and rich with fragrance and octadecyl silane reverse-phase chromatographies commonly used such as anthracene, neighbour-terphenyl and anthracene, ethylbenzene and naphthalene, alpha-Naphthol and betanaphthol, alpha-naphthylamine and beta-naphthylamine fixedly phase (ODS) material that is difficult to separate to reaching amine environmental contaminants or dansyl amino acid enantiomer.
Description of drawings
Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5 be respectively cyclodextrin bonded silica stationary of the present invention mutually as the high performance liquid chromatography separating filler separate phenanthrene and anthracene material to, neighbour-terphenyl and anthracene material to, ethylbenzene and naphthalene material to, alpha-Naphthol and betanaphthol material to, alpha-naphthylamine and beta-naphthylamine material right separate spectrogram;
Fig. 6, Fig. 7 are respectively cyclodextrin bonded silica stationary of the present invention is separated the amine environmental contaminants mutually with the ODS post as the high performance liquid chromatography separating filler separation spectrogram;
Fig. 8, Fig. 9, Figure 10 are respectively cyclodextrin bonded silica stationary of the present invention and separate red sulfonylation phenylamino acid (Dns-Phe.), red sulfonylation figured silk fabrics amino acid (Dns-Val.), the positive figured silk fabrics amino acid of red sulfonylation (Dns-Nor.) Separation of Enantiomers spectrogram as the high performance liquid chromatography separating filler mutually.
The specific embodiment
1. the preparation of cyclodextrin bonded silica stationary phase
1.1 the preparation of halopropyl bonded silica gel
In silica gel: coupling agent: dry toluene is the ratio of 1g: 5mmoL: 50ml, in the 250ml three-neck flask, add 150ml and newly steam dry toluene (dry toluene with sodium metal reflux the preparation that dewaters), add activation silica particles (particle diameter 5 μ m fast, Kromasil, Sweden), add halopropyl triethoxysilane coupling agent again.Under drying nitrogen (nitrogen is in advance through the concentrated sulfuric acid and calcium chloride drying) protection, the magnetic agitation; drip 3 (about 0.1ml) and newly steam triethylamine; oil bath is warming up to 110～120 ℃ rapidly; reaction 24 hours (the condenser pipe upper end adds the drying tube of anhydrous calcium chloride) under reflux state; use G-4 sand core funnel suction filtration while hot, solid with toluene, acetone, methyl alcohol, water, acetone washing, gets halopropyl bonded silica gel (CPS) successively; vacuum drying (100 ℃) 8 hours is stored in the drier standby.
The specific embodiment
1. the preparation of cyclodextrin bonded silica stationary phase
1.1 preparation activated silica gel
(particle diameter 5 μ m, Kromasil, Sweden) is suspended in the hydrochloric acid of 6 mol with silica gel, and silica gel quality and hydrochloric acid volume ratio are 1g: 15～20ml.Stir down and refluxed 24 hours, filter with the G-4 sand core funnel while hot, solid is extremely neutral with secondary water washing repeatedly, and, disperse 160 ℃ of bakings more than 10 hours in baking oven again with acetone washing three times prior to drying under the infrared lamp to silica gel, taking-up places drier to be chilled to room temperature, change it over to vacuum drying rifle rapidly, the water-bath heating, vacuum drying made activated silica gel more than 16 hours.
1.2 the preparation of halopropyl bonded silica gel
In silica gel: coupling agent: dry toluene is the ratio of 1g: 5mmoL: 50ml, in the 250ml three-neck flask, add 150ml and newly steam dry toluene (dry toluene with sodium metal reflux the preparation that dewaters), add above-mentioned activated silica gel fast, add halopropyl triethoxysilane coupling agent again.Under drying nitrogen (nitrogen is in advance through the concentrated sulfuric acid and calcium chloride drying) protection, the magnetic agitation; drip 3 (about 0.1ml) and newly steam triethylamine; oil bath is warming up to 110～120 ℃ rapidly; reaction 24 hours (the condenser pipe upper end adds the drying tube of anhydrous calcium chloride) under reflux state; use G-4 sand core funnel suction filtration while hot, solid with toluene, acetone, methyl alcohol, water, acetone washing, gets halopropyl bonded silica gel (CPS) successively; vacuum drying (100 ℃) 8 hours is stored in the drier standby.
1.3 the preparation of cyclodextrin sodium salt
Take by weighing the pre-dry cyclodextrin of 3mmol in the 250ml flask, add 150ml and newly steam dry DMF, load onto nitrogen ingress pipe and calcium chloride tube, feed nitrogen, add 2.1mmol sodium hydride powder (perishable in the air) rapidly, stirring at room 0.5～2 hour is filtered to remove excessive N aH and NaOH accessory substance, gets the cyclodextrin sodium salt filtering liquid.
1.4 the preparation of the silica gel bonded phase of cyclodextrin
The 1.2 halopropyl bonded silica gels that prepare are added in the above-mentioned cyclodextrin sodium salt solution rapidly, stir and be warming up to 80～130 ℃, nitrogen protection was reacted 24～56 hours down.Stop heating, filter with the G-4 sand core funnel while hot, use DMF, acetone, methyl alcohol, redistilled water, acetone washed twice successively, infrared lamp is oven dry, fixedly phase crude product down.
1.5 flotation
Get a 50mL beaker, add 30mL and analyze pure methyl alcohol, add fixedly phase crude product again, ultrasonic wave was handled 5 minutes, left standstill the tipping supernatant liquor about 2 hours, add 30ml methyl alcohol and ultrasonic again,, check flotation effect upper strata liquid microexamination, adjust flotation number of times and methanol usage, general flotation 3～4 times is filtered, with the acetone washing, oven dry (100 ℃) gets cyclodextrin bonded silica stationary phase, behind dry 48 hours of the vacuum gun, be used for elementary analysis and correlation analysis.
1.3 the preparation of the silica gel bonded phase of cyclodextrin
2. bonding concentration
Fixing phase surface cyclodextrin concentration: α=W/M (μ molg
-1)
W is fixing phase surface cyclodextrin weight (g), and M is the cyclodextrin molal weight, and α is fixing phase surface cyclodextrin concentration (μ molg
-1).
With the beta-schardinger dextrin-is example, α: 10-20 μ molg
-1
3. adopting chloropropyl triethoxysilane is that coupling agent and beta-schardinger dextrin-are raw material, and Kromasil 5 μ m spherical silica gels are matrix, the silica gel bonded fixedly phase of preparation cyclodextrin example
By 1.1 to 1.5 steps prepare beta-schardinger dextrin-bonded stationary phase (β-CD-BS), this fixedly phase bonding cyclodextrin concentration be: 13 μ molg
-1(according to carbon element content, see Table 1, wherein CPS is
BondingChloropropyl silica gel).
The raw material rate of charge, activated silica gel (g): coupling agent (mmol): beta-schardinger dextrin-(mmol): sodium hydride (mmol)=1: 5: 1.0: 0.7.
Activated silica gel (g): dry toluene (ml): beta-schardinger dextrin-(mmol): DMF (ml)=1: 50: 1: 50
The cyclodextrin bonded phase bonding of table 1. concentration
| The bonding phase | C(％) | H(％) | Bonding concentration μ molg -1 |
| β-CD-BS CPS | 3.89 3.35 | 1.18 0.72 | 13 104 |
As stated above, the present invention can replace beta-schardinger dextrin-to prepare α or gamma-cyclodextrin bonded stationary phase with α or gamma-cyclodextrin.
Practical example:
By homogenate method filling stainless steel performance liquid chromatographic column (150mm * 4.6mm (i.d.)).With methanol-water or methyl alcohol-buffer solution is the phase that flows, investigated difficult retention behavior and the separating power of material to solutes such as, disubstituted benzenes position isomer, phenyl amines environmental contaminants and red sulphonyl derivatization amino acid enantiomers of dividing of fixing relative PAHs, ODS, all kinds of solutes are well separated.Below we are example with the difficult material that divides of ODS to, amine environmental contaminants and dansyl amino acid Separation of Enantiomers, this fixedly advantage of phase is described.
The right separation of difficult separate substance is the difficult point and the emphasis of chromatographic isolation always.The ODS post is widely used in daily compartment analysis as the reverse-phase chromatographic column of routine.Yet separation selectivity is very poor between the minimum material of hydrophobic difference.We have selected 5 pairs of difficult separate substances to investigating the separation selectivity of β-CD-BS.Table 2 has provided mask data, as can be known from the table data, though the reservation of solute on ODS is very strong, but separation selectivity is very poor, and on β-CD-BS, regulates the ratio of methanol-water in flowing mutually, solute demonstrates good separation selectivity on fixing mutually, 5 pairs of solutes obtain quick baseline separation.Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5 be respectively luxuriant and rich with fragrance (a) and anthracene (b) material to, adjacent-three (c) and anthracene (d) material to, ethylbenzene (e) and naphthalene (f) material to, alpha-Naphthol (g) and betanaphthol (h) material to, alpha-naphthylamine (i) and beta-naphthylamine (j) material to separating spectrogram, mobile phase condition is consistent with table 2.
Table 2 solute is to capacity factor measure on β-CD-BS and ODS respectively (k ') and selectivity factor (α)
Material is right: the luxuriant and rich with fragrance b. anthracene of 1.a.; 2.c. neighbour-terphenyl d. anthracene; 3.e. ethylbenzene f. naphthalene; 4.g. alpha-Naphthol h. betanaphthol; 5.i. alpha-naphthylamine j. beta-naphthylamine.
Phase: β-CD-BS flows: methanol-water, 1 and 2: 55: 45; 3,4 and 5: 40: 60ODS: methanol-water, 1 and 5: 65: 35; 4: 80: 20; Second eyeball-water, 2: 80: 20; 3: 65: 35 relevant ODS to solute to the data of 1-3 from document.
Methanol-water is under 30: 70 the mobile phase condition, the quick baseline separation of β-CD-BS 6 kinds of amine environmental contaminants, post is imitated high, chromatographic peak is symmetry sharply, effectively avoided the conditions of streaking (see figure 6) of ODS post to alkali solute, chromatographic peak is followed successively by in the separation graph: 6. 9.-chloroaniline of amino-pyrimidine 7. aniline 8.N-methylanilines 10.N, accelerine 11. p-Nitranilines.Regulating the methanol-water ratio is 70: 30, obtain under the close condition of retention of solute with β-CD-BS, and the separation spectrogram (Fig. 7) on ODS, solute is consistent with Fig. 6, but peak sequence and Fig. 6 are variant, are followed successively by: 6,11,7,9,8,10.Relatively two spectrograms find that solute obviously is better than ODS at the separation selectivity of β-CD-BS, and peak sequence is inconsistent.As seen, adopt three carbon atom short chains nonnitrogenous cyclodextrin bonded fixing silicon hydroxyl that effectively shielded mutually of base preparation at interval, thereby eliminated the non-specific adsorption of silicon hydroxyl well to alkali solute, improved peak and post and imitated, and the cyclic dextrin clathrate effect improves the solute separation selectivity greatly.
In addition, through optimizing the phase condition that flows, 3 pairs of dansyl amino acid enantiomers are separated preferably, and its separation all is better than the bibliographical information value, and data are as shown in table 3.Fig. 8, Fig. 9, Figure 10 are respectively the separation spectrogram of red sulfonylation phenylamino acid (Dns-Phe.), red sulfonylation figured silk fabrics amino acid (Dns-Val.), the positive figured silk fabrics amino acid of red sulfonylation (Dns-Nor.), and the peak sequence of optical isomer all is that the L-configuration is prior to its corresponding D-form among the figure; The phase condition that flows is consistent with table 3.In addition, although bonded amount well below this laboratory originally by KH560 as the at interval cyclodextrin of base and the β-CD bonded stationary phase (reaching 0.22mmol/g) of L-Tyrosine derivatization, the chiral resolution ability is better than above fixedly phase.The chiral Recognition ability of β-CD-BS may be owing to the reason of following several respects: one, because the reactivity between chloropropyl and the β-CD sodium salt is limited, and be subjected to the short chain influence of base at interval, that reacts is sterically hindered bigger, thereby, in the immobilization process of β-CD, have only a hydroxyl to be connected the flexibility that the silica gel surface has guaranteed that the cyclodextrin conformation is adjusted, help to have kept its natural configuration with the chloropropyl reaction.Two, three the hydrophobic interval of methylene short chain bases are shielded by the big ring cavity of β-CD, do not participate in retention process, thereby have demonstrated fully the chiral Recognition ability of β-CD.Three, bonded amount is low, and cyclodextrin is arranged in order on silica gel surface and mutual extrusion not, has guaranteed the stability of its natural configuration and has helped to strengthen synergy between β-CD, strengthens the chiral Recognition ability.
Table 3 dansyl amino acid is respectively at β-CD-BS and Alpha-Methyl-Aminobenzoate-β-CD
Mask data on the bonded stationary phase
| Solute | β-CD-BS | α-methyl-benzylamine-β-CD | ||
| Dns-Phe. Dns-Val. Dns-Nor. | k 1’ | α | R s | R a s |
| 6.36 4.21 3.52 | 1.10 1.12 1.08 | 1.13 1.25 0.89 | 0.80 1.10 0.74 | |
Phase: β-CD-BS flows: methyl alcohol-buffer solution (triethylamine (0.01%)-acetate) (1) Dns-Phe.60:40 (pH4.05); (2) Dns-Nor.50:50 (pH5.02); (3) Dns-Val.60:40 (pH5.02)
A. data are from document.
α or gamma-cyclodextrin bonded stationary phase by the method for the invention preparation have the similar chromatographic performance of beta-schardinger dextrin-bonding bonded stationary phase, and above solute are had similar separation selectivity.
Claims (5)
1. cyclodextrin bonded silica stationary phase, its structural formula is:
2. the preparation method of the described cyclodextrin bonded silica stationary phase of claim 1, it is characterized in that: in silica gel: halopropyl triethoxysilane coupling agent: dry toluene is 10 grams: 10-50 mM: the ratio of 200-500 milliliter, with particle diameter is in the silica gel adding dry toluene of 2-10 micron, add halopropyl triethoxysilane coupling agent again, add catalyst of triethylamine, be warming up to 110～120 ℃, reaction is 12-36 hour under reflux state, suction filtration while hot, washing, the dry halopropyl bonded silica gel that gets; Sodium hydride and cyclodextrin with mol ratio 1: 0.2～1.0 are reactant, are solvent with the anhydrous dimethyl formamide, and reaction obtained the cyclodextrin sodium salt in 0.5-2 hour under 20-30 ℃ of room temperature; Add 1 gram halopropyl bonded silica gel in the cyclodextrin sodium salt of 0.2～2 mM, stir and be warming up to 80～130 ℃, reaction is 24～56 hours under the nitrogen protection, filter while hot, and washing, oven dry gets cyclodextrin bonded silica stationary phase.
3. the purposes of the described cyclodextrin bonded silica stationary phase of claim 1 is used as high performance liquid chromatography, micro column liquid chromatography or capillary electric chromatogram separating filler.
4. purposes according to claim 3 is characterized in that: above-mentioned cyclodextrin bonded silica stationary is used as high performance liquid chromatography separating filler enantiomer separation mutually.
5. purposes according to claim 3; it is characterized in that: with above-mentioned cyclodextrin bonded silica stationary mutually as the high performance liquid chromatography separating filler, separate luxuriant and rich with fragrance and the anthracene material to, neighbour-terphenyl and anthracene material to, ethylbenzene and naphthalene material to, alpha-Naphthol and betanaphthol material to, alpha-naphthylamine and beta-naphthylamine material to, amine environmental contaminants or dansyl amino acid enantiomer.
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| CN1864852B (en) * | 2006-04-19 | 2012-01-11 | 南昌大学 | A method for preparing chromatogram stationery phase of rhein bonded silica gel |
| 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 |
| CN101537345B (en) * | 2009-03-24 | 2010-12-29 | 苏州汇通色谱分离纯化有限公司 | Preparation method of modified cyclodextrin chiral hybrid monolithic chromatogram stationary phase |
| CN103623796A (en) * | 2012-08-28 | 2014-03-12 | 翁文 | Preparation method of cyclodextrin/human serum albumin composite chiral immobile phase |
| CN104119459A (en) * | 2014-03-03 | 2014-10-29 | 南昌大学 | Preparation method of cyclodextrin hybrid alkyl skeleton chiral stationary phase |
| CN104209105B (en) * | 2014-08-12 | 2016-05-11 | 高立娣 | The preparation method of mesoporous tungsten oxide and poly-beta-schardinger dextrin-framework integral separation medium |
| CN109513431A (en) * | 2017-09-19 | 2019-03-26 | 中国科学院大连化学物理研究所 | The nucleocapsid silica gel chiral resolution material of bonding beta-cyclodextrin and its preparation and application |
| CN111012916B (en) * | 2018-10-09 | 2021-10-01 | 厦门大学 | Surface-modified sponge spicule and preparation method and application thereof |
| CN111330557B (en) * | 2020-01-17 | 2022-11-18 | 中山职业技术学院 | Chiral stationary phase, preparation thereof and application thereof in chiral drug resolution |
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