CN104437442B - Beta-cyclodextrin-modified gold nanoparticle/silica gel chiral stationary phase and preparation method thereof - Google Patents

Beta-cyclodextrin-modified gold nanoparticle/silica gel chiral stationary phase and preparation method thereof Download PDF

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CN104437442B
CN104437442B CN201410837801.3A CN201410837801A CN104437442B CN 104437442 B CN104437442 B CN 104437442B CN 201410837801 A CN201410837801 A CN 201410837801A CN 104437442 B CN104437442 B CN 104437442B
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beta
silica gel
schardinger dextrin
nanometer particle
golden nanometer
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CN104437442A (en
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陈桐
李媛媛
宋广三
李静
张慧勤
李平
周洪斌
肖震
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COMPREHENSIVE INSPECTION AND QUARANTINE TECHNOLOGY CENTER ZHENJIANG ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU
Ningxia University
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COMPREHENSIVE INSPECTION AND QUARANTINE TECHNOLOGY CENTER ZHENJIANG ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU
Ningxia University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
    • B01D15/3833—Chiral chromatography
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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Abstract

The invention discloses a beta-cyclodextrin-modified gold nanoparticle/silica gel chiral stationary phase and a preparation method thereof. The stationary phase is prepared by the following steps: synthesizing a beta-cyclodextrin derivative with a sulfhydryl group, forming a gold nanoparticle shell on the surface of silica gel by using a sol-gel method, and connecting the beta-cyclodextrin derivative with the sulfhydryl group to the gold nanoparticle surface through an S-H key to form the chiral stationary phase, wherein the silica gel serves as a core, and the beta-cyclodextrin bonded gold nanoparticles are taken as the shell. The process is simple, the prepared separation material is novel in structure, the separation efficiency is high due to the gold nanoparticles, and the method is applied to separation of a chiral compound.

Description

A kind of modified golden nanometer particle/silica gel chiral fixed phase of beta-schardinger dextrin-and its preparation Method
Technical field
The present invention relates to a kind of liquid chromatograph chiral stationary phase and preparation method thereof, specifically, is to provide one kind and prepares Modified golden nanometer particle/silica gel chiral fixed phase of beta-schardinger dextrin-and preparation method thereof.
Background technology
Liquid chromatography is the effective means for splitting enantiomer, and existing market has been developed for polytype chiral fixed Phase.According to the textural classification of fixing phase, can substantially be divided into Pirkle type chiral stationary phases, oversubscription subclass chiral stationary phase is more Saccharide chiral stationary phase, Antibiotic stationary phase, protein-based chiral stationary phase, ligand exchange type is chiral fixed Phase, molecular engram chiral stationary phase, polymer-type chiral stationary phase etc..These fixing phases are all to pass through various chiral selectors The method for applying or being bonded is fixed on stromal surface.
The development for developing into chromatographic stationary phases of nanotechnology brings new opportunity.Due to nano material specific surface area greatly, Mass-transfer efficiency is high, and in separation science field excellent separation selectivity and separation efficiency are shown.At present, large quantities of nano materials (including fullerene, CNT, polymer drops, metal-oxide and Nano silver grain etc.) as a kind of separating medium, It is successfully used in the fields such as chromatography of ions, capillary electrophoresis, capillary electric chromatogram, gas chromatogram, minor effect genes, and table Reveal excellent separation selectivity and separation efficiency.Dun etc. (H.J.Duan, et al, Analytical Chemistry, 76 (2004) 5016-5023) nano zircite LBL self-assembly is made into Stationary Phase for HPLC in Silica Surface, obtain filling out for rule Material pattern, for normal-phase chromatography separation.The fixing phase specific surface area is big, can be with acid and alkali-resistance, and chemical stability is good, and permeability Good, the separating effect and separation selectivity of analyte are greatly improved.Weng etc. (X.X.Weng, et al, Electrophoresis, 27 (2006) 3129-3135) bovine serum albumin bonding is made on the carbon nanotubes chip capillary Electrochromatography fixing phase, rapidly and efficiently separated Tryptophan enantiomer.Moliner-Martinez(Y.M.Martinez,et Al, Electrophoresis, 28 (2007) 2573-2579) with chiral selector to using valid fixation after carbon nano-tube modification Phase, baseline separation clo human relations are special and ephedrine enantiomer.As can be seen here, due to the dimensional effect of nano-particle, by nanometer material Material is incorporated in fixing phase, and the chiral separation ability of fixing phase can be significantly improved.
Even so, the species at present nano material being introduced into Stationary Phase for HPLC is also very limited, therefore, to such handss Property fixing phase preparation and have great importance with applied research, new path will be opened up to develop new chiral stationary phase.
The content of the invention
In view of above-mentioned, the purpose of the present invention aims to provide the Jenner being modified for a kind of detached beta-schardinger dextrin-of liquid chromatograph Rice corpuscles/silica gel chiral fixed phase and preparation method thereof.This is a kind of new separation material, and this material structure is novel, point From efficiency high, separation selectivity is good, and its preparation method is simple and reliable, can be used for chiral separation.
To realize the goal of the invention of the present invention, the technical scheme that the present invention is provided is a kind of modified gold nano of beta-schardinger dextrin- Particle/silica gel chiral fixed phase, its general structure is：
Wherein, ●-gold nano grain is represented,- represent beta-schardinger dextrin-.
Another technical scheme that the present invention is provided is to prepare the modified golden nanometer particle/silica gel chiral fixed phase of beta-schardinger dextrin- Preparation method, comprise the steps：
1) preparation of beta-schardinger dextrin-derived from mercapto groups
Beta-schardinger dextrin-and concentration are sufficiently mixed for 2～4mol/L sodium hydrate aqueous solutions, sodium hydroxide concentration is β-ring The 35～45% of dextrin quality, are then added dropwise over mixed liquor, paratoluensulfonyl chloride and beta-schardinger dextrin-matter by paratoluensulfonyl chloride Amount is than being 1:4～8,4-8 hours are reacted under ice bath, then filter, pH is adjusted to neutrality, recrystallization, it is dried, obtain final product benzoyl The beta-schardinger dextrin-of change；
It is 1 by mass ratio:1～1.5 benzoylated beta-schardinger dextrin-is dissolved in the mixed liquor of methanol/water with derivative reagent In, the volume ratio of methanol/water is 4:1, methanol/water solution needed for per gram of benzoylated beta-schardinger dextrin-is 50～80mL, is reacted 40～60 hours, sucking filtration, with gained solid after 10% sodium hydrate aqueous solution dissolving sucking filtration, was stirred 5～7 hours at 50 DEG C, PH is adjusted to 2 or so, trichloro ethylene is eventually adding；It is 2～5mL that every gram of derivative reagent adds the amount of trichloro ethylene, stirring 24～ 36 hours, sucking filtration, recrystallization obtained final product beta-schardinger dextrin-derived from mercapto groups.
2) preparation of alkylamino silica gel
By 3～10 μm of colloidal silica dispersions of diameter in dry toluene, amino silane is added, under nitrogen protection, be stirred at reflux 12-24 hours, then filter, and successively with dichloromethane, acetone, methanol washing is dried, and obtains final product alkylamino silica gel；Wherein, every gram of silicon Dry toluene dosage needed for glue is 10～50mL, and amino silane dosage needed for every gram of silica gel is 0.5～1.5mL.
3) formation of the golden nanometer particle in Silica Surface
Alkylamino silica gel is dispersed in 0.01～0.05% aqueous solution of chloraurate, boiling is heated to, is then quickly added into 0.5～2% reducing agent aqueous solution, after 10～40min of reaction room temperature is cooled to；This process repeats 2～3 times and obtains final product Jenner's grain of rice The silica gel that attached bag is covered；Wherein, aqueous solution of chloraurate dosage needed for every gram of alkylamino silica gel is 20～50mL, needed for every gram of gold chloride also Former agent dose is 2～5g.
4) the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-
The colloidal silica dispersion that golden nanometer particle is coated is subsequently adding mass concentration for 0.2- in DMF The DMF solution of beta-schardinger dextrin-derived from 1.0% mercapto groups, reacts 24-48 hours, filters, successively with N, Dinethylformamide, ultra-pure water cleaning, are dried, and obtain final product the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-；It is wherein every DMF dosage needed for the silica gel of gram golden nanometer particle cladding is 10-30mL, every gram of golden nanometer particle cladding Beta-schardinger dextrin-dosage derived from mercapto groups needed for silica gel is 0.5-1.0g.
The consumption of corresponding 10% sodium hydrate aqueous solution of every gram of derivative reagent is 20-40mL.The derivative reagent is sulfur Urea.
The amino silane is aminopropyl trimethoxysilane or aminopropyl triethoxysilane.
The silica gel is spherical silica gel, and aperture is 10～50nm, and specific surface area is 300-500m2/g。
The reducing agent is trisodium citrate.Described golden nanometer particle is spherical, and particle diameter is 10-50nm.
The invention has the advantages that：
1. structure is novel.With silica gel as core, golden nanometer particle is shell to the fixing phase of present invention synthesis, and beta-schardinger dextrin-is function Group.Due to the dimensional effect of nanoparticle, therefore the chiral separation ability of fixing phase can be significantly increased.
2. simple, applied range is prepared.Products material wide material sources of the present invention, reaction condition are gentle, cost is relatively low；Gu Determine that phase preparation process is simple and reliable, the separation of various chiral materials is widely used in, with certain practical value.
Description of the drawings
Fig. 1, gold nano grain transmission electron microscope picture.
Fig. 2, the transmission electron microscope picture of silica gel.
Fig. 3, the transmission electron microscope picture of the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-.
Fig. 4, using the chromatographic fractionation figure of obtained fixed a pair of the flavanone enantiomer that are separated.
Fig. 5, using the chromatographic fractionation figure of obtained fixed a pair of the bupivacaine enantiomer that are separated.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute State method and be conventional method if no special instructions.The raw material can be obtained if no special instructions from open commercial sources.
The method for preparing the modified golden nanometer particle/silica gel chiral fixed phase of beta-schardinger dextrin-of the present invention, including following step Suddenly：1) preparation of beta-schardinger dextrin-derived from mercapto groups
Beta-schardinger dextrin-and concentration are sufficiently mixed for 2～4mol/L sodium hydrate aqueous solutions, sodium hydrate aqueous solution consumption For the 35～45% of beta-schardinger dextrin-quality, then paratoluensulfonyl chloride is added dropwise over into mixed liquor, paratoluensulfonyl chloride and β-ring Dextrin mass ratio is 1:4～8,4-8 hours are reacted under ice bath, then filter, pH is adjusted to neutrality, recrystallization, it is dried, obtain final product Benzoylated beta-schardinger dextrin-；
It is 1 by mass ratio:1～1.5 benzoylated beta-schardinger dextrin-is dissolved in the mixed liquor of methanol/water with derivative reagent In, the volume ratio of methanol/water is 4:1, methanol/water solution needed for per gram of benzoylated beta-schardinger dextrin-is 50～80mL, is reacted 40～60 hours, sucking filtration, with gained solid after 10% sodium hydrate aqueous solution dissolving sucking filtration, was stirred 5～7 hours at 50 DEG C, PH is adjusted to 2 or so, trichloro ethylene is eventually adding；It is 2～5mL that every gram of derivative reagent adds the amount of trichloro ethylene, stirring 24～ 36 hours, sucking filtration, recrystallization obtained final product beta-schardinger dextrin-derived from mercapto groups.The derivative reagent is thiourea；Every gram of derivative reagent Corresponding 10% sodium hydroxide concentration is 20-40mL.
2) preparation of alkylamino silica gel
By 3～10 μm of colloidal silica dispersions of diameter in dry toluene, amino silane is added, under nitrogen protection, be stirred at reflux 12-24 hours, then filter, and successively with dichloromethane, acetone, methanol washing is dried, and obtains final product alkylamino silica gel；Wherein, every gram of silicon Dry toluene dosage needed for glue is 10～50mL, and amino silane dosage needed for every gram of silica gel is 0.5～1.5mL.
3) formation of the golden nanometer particle in Silica Surface
Alkylamino silica gel is dispersed in 0.01～0.05% aqueous solution of chloraurate, boiling is heated to, is then quickly added into 0.5～2% reducing agent aqueous solution, after 10～40min of reaction room temperature is cooled to；This process repeats 2～3 times and obtains final product Jenner's grain of rice The silica gel that attached bag is covered；Wherein, aqueous solution of chloraurate dosage needed for every gram of alkylamino silica gel is 20～50mL, needed for every gram of gold chloride also Former agent dose is 2～5g；The reducing agent is trisodium citrate.
4) the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-
The colloidal silica dispersion that golden nanometer particle is coated is subsequently adding mass concentration for 0.2- in DMF The DMF solution of beta-schardinger dextrin-derived from 1.0% mercapto groups, reacts 24-48 hours, filters, successively with N, Dinethylformamide, ultra-pure water cleaning, are dried, and obtain final product the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-；It is wherein every DMF dosage needed for the silica gel of gram golden nanometer particle cladding is 10-30mL, every gram of golden nanometer particle cladding Beta-schardinger dextrin-dosage derived from mercapto groups needed for silica gel is 0.5-1.0g.
For above-mentioned preparation method, embodiment is set forth below and is specifically described.
Embodiment 1
1). the preparation of beta-schardinger dextrin-derived from mercapto groups
30.0g beta-schardinger dextrin -s are added into the sodium hydrate aqueous solution of 150mL 2.0mol/L, is sufficiently stirred for, then by 6.0g Paratoluensulfonyl chloride is added dropwise over mixed liquor, reacts 6 hours under ice bath, then filters, and with salt acid for adjusting pH to neutrality, uses water Recrystallization, is dried, and obtains final product benzoylated beta-schardinger dextrin-；
The benzoylated beta-schardinger dextrin -s of 5.0g and 6.0g thiourea are dissolved in into 250mL methanol/water, and (volume ratio is 4:1) mixed In closing liquid, react 50 hours, sucking filtration, with the sodium hydrate aqueous solution dissolving sucking filtration gained solid of 180mL 10%, at 50 DEG C Stirring 6 hours, with salt acid for adjusting pH to 2 or so, is eventually adding 18mL trichloro ethylenes, stirs 30 hours, and sucking filtration is tied again with pure water Crystalline substance, obtains final product beta-schardinger dextrin-derived from mercapto groups.
2). the preparation of alkylamino silica gel
Silica gel is spherical silica gel, a diameter of 5 μm, and aperture is 10nm, specific surface area 380m2/g.By 3g colloidal silica dispersions in In 30mL dry toluenes, 2.5mL aminopropyl trimethoxysilanes are added, under nitrogen protection, be stirred at reflux 24 hours.Then use Sintered filter funnel is filtered, and successively with dichloromethane, acetone, methanol washing is placed in vacuum drying oven in 60 DEG C of dryings 12 hours, Obtain final product alkylamino silica gel.
3). formation of the golden nanometer particle in Silica Surface
3g alkylamino silica gels are dispersed in the aqueous solution of chloraurate of 100mL 0.03%, boiling is heated to, are then quickly added Enter 1.5% trisodium citrate aqueous solution 6mL, after reaction 20min room temperature is cooled to.This process is repeated 3 times and obtains final product Jenner's grain of rice The silica gel that attached bag is covered.
4). the synthesis of the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-
The colloidal silica dispersion that 3g golden nanometer particles are coated is subsequently adding quality dense in 50mL DMFs The DMF solution 200mL of the beta-schardinger dextrin-derived from 1.0% mercapto groups is spent, is reacted 36 hours, filtered, used DMF, ultra-pure water cleaning, are dried, and obtain final product the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-.
Embodiment 2
1). the preparation of beta-schardinger dextrin-derived from mercapto groups
72g beta-schardinger dextrin -s are added into the sodium hydrate aqueous solution of 200mL 4.0mol/L, is sufficiently stirred for, then by 9.0g pair Toluene sulfochloride is added dropwise over mixed liquor, reacts 8 hours under ice bath, then filters, and with salt acid for adjusting pH to neutrality, uses water weight Crystallization, is dried, and obtains final product benzoylated beta-schardinger dextrin-；
The benzoylated beta-schardinger dextrin -s of 8.0g and 12.0g thiourea are dissolved in into 640mL methanol/water, and (volume ratio is 4:1) In mixed liquor, react 60 hours, sucking filtration, with the sodium hydrate aqueous solution dissolving sucking filtration gained solid of 480mL 10%, at 50 DEG C Lower stirring 7 hours, with salt acid for adjusting pH to 2 or so, is eventually adding 60mL trichloro ethylenes, stirs 36 hours, and sucking filtration uses pure water weight Crystallization, obtains final product beta-schardinger dextrin-derived from mercapto groups.
2). the preparation of alkylamino silica gel
Silica gel is spherical silica gel, a diameter of 10 μm, and aperture is 50nm, specific surface area 300m2/g.By 4g colloidal silica dispersions in In 200mL dry toluenes, 6mL aminopropyl trimethoxysilanes are added, under nitrogen protection, be stirred at reflux 24 hours.Then use Sintered filter funnel is filtered, and successively with dichloromethane, acetone, methanol washing is placed in vacuum drying oven in 60 DEG C of dryings 12 hours, Obtain final product alkylamino silica gel.
3). formation of the golden nanometer particle in Silica Surface
4g alkylamino silica gels are dispersed in the aqueous solution of chloraurate of 200mL 0.05%, boiling is heated to, are then quickly added Enter 2% trisodium citrate aqueous solution 25mL, after reaction 40min room temperature is cooled to.This process is repeated 3 times and obtains final product golden nanometer particle The silica gel of cladding.
4). the synthesis of the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-
The colloidal silica dispersion that 2g golden nanometer particles are coated is subsequently adding quality dense in 60mL DMFs The DMF solution 180mL of the beta-schardinger dextrin-derived from 0.6% mercapto groups is spent, is reacted 24 hours, filtered, according to Secondary DMF, ultra-pure water are cleaned one time, are dried, and obtain final product the modified golden nanometer particle/silica gel solid of beta-schardinger dextrin- Determine phase.
Embodiment 3
1). the preparation of beta-schardinger dextrin-derived from mercapto groups
30.0g beta-schardinger dextrin -s are added into the sodium hydrate aqueous solution of 90mL 3.0mol/L, is sufficiently stirred for, then by 7.5g Paratoluensulfonyl chloride is added dropwise over mixed liquor, reacts 4 hours under ice bath, then filters, and with salt acid for adjusting pH to neutrality, uses water Recrystallization, is dried, and obtains final product benzoylated beta-schardinger dextrin-；
The benzoylated beta-schardinger dextrin -s of 4.0g and 4.0g thiourea are dissolved in into 260mL methanol/water, and (volume ratio is 4:1) mixed In closing liquid, react 40 hours, sucking filtration, with the sodium hydrate aqueous solution dissolving sucking filtration gained solid of 80mL 10%, stir at 50 DEG C Mix 5 hours, with salt acid for adjusting pH to 2 or so, be eventually adding 8mL trichloro ethylenes, stir 24 hours, sucking filtration uses pure water recrystallization, Obtain final product beta-schardinger dextrin-derived from mercapto groups.
2). the preparation of alkylamino silica gel
Silica gel is spherical silica gel, a diameter of 3 μm, and aperture is 30nm, specific surface area 500m2/g.By 4g colloidal silica dispersions in In 100mL dry toluenes, 2mL aminopropyl triethoxysilanes are added, under nitrogen protection, be stirred at reflux 24 hours.Then use Sintered filter funnel is filtered, and successively with dichloromethane, acetone, methanol is washed one time, is placed in vacuum drying oven in 60 DEG C of dryings 12 Hour, obtain final product alkylamino silica gel.
3). formation of the golden nanometer particle in Silica Surface
4g alkylamino silica gels are dispersed in the aqueous solution of chloraurate of 80mL 0.01%, boiling is heated to, are then quickly added into 0.5% trisodium citrate aqueous solution 3.2mL, after reaction 15min room temperature is cooled to.This process is repeated 3 times and obtains final product Jenner's grain of rice The silica gel that attached bag is covered.
4). the synthesis of the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-
The colloidal silica dispersion that 2g golden nanometer particles are coated is subsequently adding quality dense in 40mL DMFs The DMF solution 200mL of the beta-schardinger dextrin-derived from 0.5% mercapto groups is spent, is reacted 24 hours, filtered, according to Secondary DMF, ultra-pure water are cleaned one time, are dried, and obtain final product the modified golden nanometer particle/silica gel solid of beta-schardinger dextrin- Determine phase.
The structural confirmation result of the modified golden nanometer particle/silica gel solid phase of the beta-schardinger dextrin-of above-mentioned preparation is as follows：Fig. 1 Clearly show the overall pattern and particle size of gold nano grain.Gold nano grain is elliposoidal, and particle size distribution is more equal Even, about in 8～15nm or so, dispersibility is relatively good, agglomeration does not occur.Fig. 2 and Fig. 3 indicate silica gel and parcel gold Surface topography after nano-particle, as seen from Figure 2, Silica Surface smoother；But after having wrapped up gold nano grain, in Fig. 3 Silica gel edge significantly built up many nano-particle, the gold nano grain layer for showing Silica Surface has been formed.
Table 1 is the elementary analysiss table of golden nanometer particle/silica gel solid phase that beta-schardinger dextrin-is modified, from elementary analysiss in table 1 As a result it can also be seen that the carbon content of silica gel increases after aminopropyl trimethoxysilane modification, aminopropyl trimethoxysilane is shown Successfully it is modified in Silica Surface.And the fixing phase for being bonded beta-schardinger dextrin-finds the content of sulfur from scratch, this should be Introduce the result after thiourea, therefore these golden nanometer particle/silica gel solid phase successes for showing that beta-schardinger dextrin-is modified for being aware that Be produced；
Table 1, the elementary analysiss table of the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-.
Embodiment 4
Golden nanometer particle/the silica gel solid phase being modified with resulting beta-schardinger dextrin-, homogenate method is filled in long 150mm, interior Footpath is in the rustless steel pillar of 4.6mm, the chromatographic column for obtaining is used for analytical separation sample.
Application examples 1
With the chromatographic column prepared by embodiment 4, a pair of flavanone enantiomer have been separated.Fig. 4 is its chromatographic isolation result.Color Spectral condition is:Acetonitrile/acetic acid-triethylamine (1%) solution (1% triethylamine aqueous solution Deca vinegar acid for adjusting pH is 5.04) (30/ 70, v/v), isocratic elution；Flow velocity is 1.0mL/min；Detection wavelength 254nm.
Application examples 2
With the chromatographic column prepared by embodiment 4, a pair of bupivacaine enantiomer have been separated.Fig. 5 is its chromatographic isolation result. Chromatographic condition is:(1% triethylamine aqueous solution Deca vinegar acid for adjusting pH is methanol/acetic acid-triethylamine (1%) aqueous solution 4.98), (25/75, v/v), isocratic elution；Flow velocity is 1.0mL/min；Detection wavelength 215nm.
Fig. 4 and Fig. 5 explanations, the modified golden nanometer particle/silica gel solid phase of the beta-schardinger dextrin-that the present invention is provided, for chirality The separation of material, with very strong fractionation ability.
Above-mentioned fact Example is merely to clearly illustrate example of the present invention, and be not the embodiment party to the present invention The restriction of formula, cannot be illustrated here to all of embodiment.It is every to belong to what technical scheme was amplified out It is obvious to change or change the row still in protection scope of the present invention.

Claims (6)

1. a kind of preparation method of the modified golden nanometer particle/silica gel chiral fixed phase of beta-schardinger dextrin-, the beta-schardinger dextrin-is modified Golden nanometer particle/silica gel chiral fixed phase general structure be：
Wherein, ●-gold nano grain is represented,- represent beta-schardinger dextrin-；Its preparation method comprises the steps：
1) preparation of beta-schardinger dextrin-derived from mercapto groups
Beta-schardinger dextrin-and concentration are sufficiently mixed for 2～4mol/L sodium hydrate aqueous solutions, the sodium hydroxide concentration is β-ring The 35～45% of dextrin quality, are then added dropwise over mixed liquor, paratoluensulfonyl chloride and beta-schardinger dextrin-matter by paratoluensulfonyl chloride Amount is than being 1:4～8,4-8 hours are reacted under ice bath, then filter, pH is adjusted to neutrality, recrystallization, it is dried, obtain final product to toluene The beta-schardinger dextrin-of sulfonylation；
It is 1 by mass ratio:The beta-schardinger dextrin-of 1～1.5 tosylation is dissolved in the mixing of methanol/water with derivative reagent In liquid, the volume ratio of methanol/water is 4:1, methanol/water solution needed for the beta-schardinger dextrin-of every gram of tosylation be 50～ 80mL, reacts 40～60 hours, sucking filtration, with gained solid after 10% sodium hydrate aqueous solution dissolving sucking filtration, at 50 DEG C 5 is stirred ～7 hours, pH is adjusted to 2, be eventually adding trichloro ethylene；It is 2～5mL that every gram of derivative reagent adds the amount of trichloro ethylene, is stirred 24～36 hours, sucking filtration, recrystallization obtained final product beta-schardinger dextrin-derived from mercapto groups；The derivative reagent is thiourea；
2) preparation of alkylamino silica gel
By 3～10 μm of colloidal silica dispersions of diameter in dry toluene, amino silane is added, under nitrogen protection, be stirred at reflux 12-24 Hour, then filter, successively with dichloromethane, acetone, methanol washing is dried, and obtains final product alkylamino silica gel；Wherein, every gram of silica gel institute Dry toluene dosage is needed to be 10～50mL, amino silane dosage needed for every gram of silica gel is 0.5～1.5mL；
3) formation of the golden nanometer particle in Silica Surface
Alkylamino silica gel is dispersed in 0.01～0.05% aqueous solution of chloraurate, boiling is heated to, it is then quickly added into 0.5～ 2% reducing agent aqueous solution, after 10～40min of reaction room temperature is cooled to；This process repeats 2～3 times and obtains final product golden nanometer particle bag The silica gel for covering；Wherein, aqueous solution of chloraurate dosage needed for every gram of alkylamino silica gel be 20～50mL, reducing agent needed for every gram of gold chloride Dosage is 2～5g；
4) the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-
The colloidal silica dispersion that golden nanometer particle is coated is subsequently adding mass concentration for 0.2- in DMF The DMF solution of beta-schardinger dextrin-derived from 1.0% mercapto groups, reacts 24-48 hours, filters, successively with N, Dinethylformamide, ultra-pure water cleaning, are dried, and obtain final product the modified golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-；It is wherein every DMF dosage needed for the silica gel of gram golden nanometer particle cladding is 10-30mL, every gram of golden nanometer particle cladding Beta-schardinger dextrin-dosage derived from mercapto groups needed for silica gel is 0.5-1.0g.
2. the preparation method of the modified golden nanometer particle/silica gel chiral fixed phase of a kind of beta-schardinger dextrin-according to claim 1, It is characterized in that the step 1) in every gram of derivative reagent corresponding 10% sodium hydrate aqueous solution consumption be 20-40mL.
3. the preparation method of the modified golden nanometer particle/silica gel chiral fixed phase of a kind of beta-schardinger dextrin-according to claim 1, It is characterized in that the step 2) amino silane is aminopropyl trimethoxysilane or aminopropyl triethoxysilane.
4. the preparation method of the modified golden nanometer particle/silica gel chiral fixed phase of a kind of beta-schardinger dextrin-according to claim 1, It is characterized in that the step 2) used by silica gel be spherical silica gel, aperture is 10-50nm, and specific surface area is 300-500m2/g。
5. the preparation method of the modified golden nanometer particle/silica gel chiral fixed phase of a kind of beta-schardinger dextrin-according to claim 1, It is characterized in that the step 3) reducing agent be trisodium citrate.
6. the preparation side of the modified golden nanometer particle/silica gel chiral fixed phase of a kind of beta-schardinger dextrin-according to claim 1 Method, it is characterised in that the step 3) in the golden nanometer particle for spherical, particle diameter is 10-50nm.
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