CN104741102B - A preparing method of a surface organic-inorganic hybrid core-shell type polysaccharide chiral stationary phase - Google Patents
A preparing method of a surface organic-inorganic hybrid core-shell type polysaccharide chiral stationary phase Download PDFInfo
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Abstract
A preparing method of a surface organic-inorganic hybrid core-shell type polysaccharide chiral stationary phase is disclosed. The method adopts a polysaccharide derivative a zone of which contains triethoxysilane and a silane coupling agent as silicon sources, and prepares the chiral stationary phase by alternatively assembling a surfactant and silica sol to surfaces of a silicon ball filler through a layer-by-layer self-assembly technique. The chiral stationary phase prepared by the method is high in separation speed and high in resolution efficiency, expands the using range of a mobile phase solvent, and improves chiral separation capability of the stationary phase.
Description
Technical field
The present invention relates to a kind of preparation method of the hud typed polysaccharide chiral stationary phase of top layer hybrid inorganic-organic, specifically
Say be a kind of polysaccharide derivates that triethoxysilicane is contained with region with silane coupler as silicon source, using sol-gal process and layer
Layer self-assembling technique is prepared for hud typed hybrid inorganic-organic polysaccharide chiral stationary phase, is applied to high performance liquid chromatography enantiomer
Chiral separation field.
Background technology
Medicament research and development is various countries' scientist's study hotspot, and existing chiral chromatogram separates and the development of technology of preparing greatly promotees
Enter chiral new drug development and popularization.The key of chiral chromatogram isolation technics is chiral stationary phase, and polysaccharide derivatives fixing phase is
One of conventional chiral stationary phase, has the features such as easily preservation and separating ranges are wide.Traditional chirality padding is to be with silica gel
Substrate, obtains Aminopropyl silica gel after it is processed, then on Aminopropyl silica gel coat or bonding on polysaccharide derivates.When with chlorine
Imitative, oxolane equal solvent is susceptible to swelling as coating fixing phase during mobile phase.Will using in-situ polymerization or spacerarm method
Polysaccharide derivates bonding is easily reduced polysaccharide derivates high-sequential, thus reducing the chiral separation performance of fixing phase.
Hybrid inorganic-organic materials are a kind of organic components and inorganic component is tied on a molecular scale in the way of covalent bond
The material closing.Organo-functional group is incorporated in material, not only the alkali resistance of reinforcing material, and greatly increases organic content,
And then improve chiral stationary phase load capacity, can be very good to solve swelling problem simultaneously.Di Bin etc. is in Chinese patent
200910213018.9 disclose a kind of routine hybrid ordered mesoporous silica gel chromatograph stationary-phase stuffing and preparation method, will be with ammonia third
Ethyl triethoxy silicane alkane and 1,2- bis-（Triethoxy silicon substrate）Ethane adopts an one-step polycondensation legal system as silicon source.Its fixing phase post
Force down, to toluene, benzene and anthracene, there is preferable separating effect.It is allowed to dragon etc. to disclose in Chinese patent 2012100111495.9
A kind of hybrid chiral fixing phase based on cellulose derivative and preparation method thereof, be cellulose derivative is dissolved after with silane
Coupling agent is reacted, and obtains based on cellulose derivative hydridization fixing phase.But the such fixing phase using above method preparation
Organic content too high, swelling problem still exists.The synthesis of small molecule hybrid chiral stationary phase is easier to, but because of chiral separation
Enantiomer limited, limited by range of application.
Although hybrid inorganic-organic materials have high mechanical performance and stronger acid-proof alkaline, it is difficult to synthesis point
Scattered property is good, uniform particle diameter（3-5μm）And the silicon ball of suitable specific surface area, thus greatly limit hybrid material in high performance liquid chromatography
In application.And polysaccharide derivates are insoluble in water and its alcohol, thus traditional hydrothermal synthesis method cannot prepare the miscellaneous of polysaccharide
Change ball.Wherein, hud typed fixing phase be more common in conventional H PLC separate, the evolving path in hud typed post for the compound shorten thus
Separating rate is fast, the symmetry at peak is good, separation efficiency is high.The shell of the core at its Shi You center and outside assembles, typically
Prepared by LBL self-assembly, template and sol-gal process etc., preparation method comparative maturity.Therefore, by hybrid mesoporous material
Material and hud typed material combine, and prepare a kind of novel organic-inorganic hybrid nucleocapsid using sol-gal process and LBL self-assembly method
The polysaccharide chiral stationary phase of structure.Hybrid inorganic-organic hud typed polysaccharide fixing phase in top layer is domestic at present not yet reports.
Content of the invention
Present invention aim at providing a kind of preparation side of the polysaccharide chiral stationary phase of hybrid inorganic-organic nucleocapsid structure
Method, the chiral stationary phase of preparation has good mechanical performance, anti-Swelling Capacity and Chiral Separation Ability.
For achieving the above object, the present invention adopts embodiments below：
The present invention be broadly divided into the preparation of polysaccharide derivates, silicon ball acid-base pretreatment, surfactant assembling, hybrid silicon molten
Glue preparation and colloidal sol assemble five steps.The preparation of polysaccharide derivates refers to the 2- in polysaccharide, 3- and 6- position derives various respectively
Functional group, prepares a series of polysaccharide derivates.Silicon ball pretreatment is that silicon ball priority is immersed in ammonia and hydrochloric acid composition
Carry out acid-alkali treatment in mixed liquor, be vacuum dried silicon ball；Again the silica gel of acid-alkali treatment is immersed in the water containing surfactant
In solution, ultrasonator carries out surfactant assembling.Hydridization Ludox preparation process is will to contain triethoxysilicane
Polysaccharide derivates and silylating reagent in acid condition hybrid inorganic-organic Ludox is prepared by sol-gal process.Molten
Glue assembling process is that the silica gel assembling surfactant immerses in hydridization Ludox, is assembled into Ludox by adsorption
Silicon ball surface.Through the alternately assembling of multiple surfactant and hydridization Ludox, prepare hybrid inorganic-organic of the present invention
The polysaccharide chiral stationary phase of nucleocapsid structure.
A kind of preparation method of the hud typed polysaccharide chiral stationary phase of top layer hybrid inorganic-organic is it is characterised in that step is：
1）The preparation of polysaccharide derivates：The Microcrystalline Cellulose being dried is dissolved in anhydrous pyridine, adds triphenylchloromethane
Protection cellulose 6- position hydroxyl, 80-90 DEG C of reaction, add 3,5- dimethylphenyl isocyanate, continue reaction, solution is poured into
In methanol, the cellulose derivative Precipitation of 6- position triphenyl methane protection, buchner funnel sucking filtration, methanol washs；Then will
This derivant deprotects in the methanol solution interior edema solution containing a small amount of hydrochloric acid, sucking filtration, and methanol washs, and obtains 6- hydroxyl -2,3- bis-
(3,5- dimethylphenylcarbamate) cellulose；6- hydroxylated cellulose derivant is dissolved in N, N '-dimethyl acetylamide
（DMAC）, anhydrous Lithium chloride and pyridine mixed liquor in, add 3- (triethoxysilicane) propylisocyanate, 80-90 DEG C of reaction,
Add 3, the 5- dimethylphenyl isocyanate reaction of 1.5 times of cellulose moles, pour in methanol, cellulose derivative is sunk
Precipitation goes out, sucking filtration, and methanol washs, 60 DEG C of vacuum drying, obtains the triethoxy silicon substrate third containing different content for the cellulose 6- position
Base -2,3- two (3,5- Dichlorobenzene base carbamate) cellulose derivative；
2）Silicon ball pretreatment：After silicon ball is cleaned with distilled water, successively immerse and be made up of distilled water, ammonia, hydrogen peroxide
Mixed liquor and the mixed liquor being made up of distilled water, concentrated hydrochloric acid, hydrogen peroxide, be standing and soak for, with dehydrated alcohol and distillation washing
Wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying；
3）Surfactant assembles：The dring silicon bead that acid-alkali treatment is crossed is immersed in cetyl ammonium bromide
(CTAB), in surfactant solution, supersound process, washing with alcohol silicon ball, 60 DEG C of vacuum drying are carried out；
4）Prepared by hydridization Ludox：By step 1）Preparation cellulose derivative is dissolved in N, N '-dimethylformamide（DMF）
In, add silane reagent, ethanol, surfactant and acid catalyst, room temperature reaction, prepare hybrid inorganic-organic silicon
Colloidal sol；
5）Colloidal sol assembles：Step 2）Handled silicon ball is added in hybrid inorganic-organic Ludox, assembles 0.5-3h,
Standing 0.5-1h, ethanol centrifuge washing, 60 DEG C of vacuum drying；
6）Repeat step 3）To 5）Process, alternately assembles for several times, silicon ball is added in ethanol, and stirring is filtered, 60 DEG C of vacuum
It is dried, prepare the Cellulose chiral stationaryphase of hybrid inorganic-organic nucleocapsid structure.
Step 1 of the present invention）Described polysaccharide derivates include Microcrystalline Cellulose, amylose, amylopectin, nanofiber
Element, nanometer amylose and nanometer amylopectin；The proportionate relationship that 6 hydroxyl protections of polysaccharide derivates react agents useful for same is,
Polysaccharide derivates：Pyridine：Triphenylchloromethane：Phenyl isocyanate derivant：Methanol=1g:50mL:3.5g:5mL:400mL；
The proportionate relationship of 6 protective reaction agents useful for same of polysaccharide derivates is, polysaccharide derivates：Hydrochloric acid：Methanol=1g：3mL：
400mL；The proportionate relationship of polysaccharide 6- position hydroxyl derivatization reaction agents useful for same is, polysaccharide derivates：DMAC：Lithium chloride：Pyridine：First
Alcohol=1g: 20mL: 1.5g:60mL:400mL, adds the 3- of 6 hydroxyl moles 2-99.9% of polysaccharide derivates（Three ethoxy silicon
Base）Propylisocyanate, carries out regioselectivity derivatization reaction, 3- on polysaccharide 6- position to the 6- position of polysaccharide（Three ethoxy silicon substrates）
The substitution value of propyl group is 2-99.9%, then again to polysaccharide 6- position residual hydroxyl and phenyl isocyanate derivatives reaction.
Step 1 of the present invention）Described phenyl isocyanate derivant used include 3,5- dimethylphenyl isocyanate, 3,
5- difluorophenyl isocyanate and 3,5- dichlorophenyl isocyanate.
Step 2 of the present invention）Described silicon ball particle diameter is 100-1000 angstrom in 5-20 micron, aperture；Distilled water and peroxidating
The volume ratio of hydrogen mixed liquor is 15mL:1mL, alkaline mixed solution adjusts pH=7-8 by ammonia；Acid mixed solution is adjusted by concentrated hydrochloric acid
pH=2-4；Silicon ball quality is 1g with the volume ratio of mixed liquor: 15-20mL.
Step 3 of the present invention）With 4）Described surfactant is cetyl trimethylammonium bromide, trimethyl
Ammonium chloride or octadecyl trimethyl ammonium chloride；Step 3）The concentration of surfactant used is 0.025mol/L, silicon ball quality
Volume ratio with surfactant is 1g: 20mL.
Step 4 of the present invention）Described dissolving polysaccharide derivates solvent for use can be selected for oxolane, pyridine, DMF, acetone,
DMAC or dimethyl sulfoxide.Silane reagent used is tetraethyl orthosilicate, 1,2- is double（Triethoxysilicane）Ethane, double three siloxy first
Base silane or (triethoxy silicon substrate) hexamethylene；Acid catalyst used is hydrochloric acid, one kind of sulphuric acid, phosphoric acid or nitric acid or two
Kind；The proportionate relationship of agents useful for same is, polysaccharide derivates：Dissolving polysaccharide derivates solvent：Silane reagent：Water：Ethanol：Live in surface
Property agent：Acid catalyst=0.05-0.40 g: 25-45 mL: 1-10 mL: 2 mL: 0.1 g: 0.25mL.
Step 5 of the present invention）Described silicon ball quality is 1g with the volume ratio of hybrid inorganic-organic Ludox:10-20mL.
Step 6 of the present invention）Described assembling number of times is 2-8 time, adds the quality of silicon ball to be 1g with the volume ratio of ethanol:
150mL.
The present invention has advantages below：
The present invention utilizes layer-by-layer and sol-gal process, is prepared for top layer hybrid inorganic-organic hud typed
Polysaccharide chiral stationary phase.The nucleocapsid chiral stationary phase of present invention preparation has that preparation process is simple, the load capacity of polysaccharide derivates
Controlled and the features such as mechanical strength is good, and also there are good chipal compounds split performance.Positive condition can adopt
Improve chromatographic column chiral separation performance containing chloroform, dichloromethane, oxolane equal solvent as Mobile Phase Additives.Anti-phase
Under the conditions of can also carry out the fractionation of enantiomer using acetonitrile, chloroform, methanol, oxolane polar solvent.Molten using polarity
Mobile phase is done in agent, enhances the solvent range of chiral stationary phase, and remains in that preferable swelling resistance performance.
Prepared by the present invention, nucleocapsid chiral stationary phase can be widely applied to pharmacy, Natural Medicine Chemistry, chemosynthesis, biology
And the separation analysis of chipal compounds and industrially prepared in the field product such as biochemistry.
Brief description
Fig. 1 is the scanning electron microscope (SEM) photograph of case study on implementation 6 of the present invention.
Fig. 2 is that the positive condition of case study on implementation 2 of the present invention separates 1- mandelonitrile chromatogram.
Fig. 3 is that the antiphasic condition of case study on implementation 6 of the present invention separates 1- phenethanol chromatogram.
Specific embodiment
Embodiment 1 top layer hybrid inorganic-organic hud typed Microcrystalline Cellulose chiral stationary phase preparation method, is embodied as walking
Suddenly as follows：
1）6- contains position on a small quantity（3-（Triethoxy silicon substrate））The preparation of propyl group microcrystalline cellulose derivative
The Microcrystalline Cellulose that 1g is dried is dissolved in 50mL anhydrous pyridine, adds 3.5g triphenylchloromethane protection cellulose
6 hydroxyls, 80-90 DEG C of reaction 24h, add 3,5- difluorophenyl isocyanate 5mL, continue reaction 24h, solution is poured into
In 400mL methanol, the cellulose derivative Precipitation of 6- position triphenyl methane protection, buchner funnel sucking filtration, methanol washs.So
Afterwards this derivant of 1 g is deprotected in 400mL methanol (3mL concentrated hydrochloric acid) solution interior edema solution, buchner funnel sucking filtration, methanol washs,
Obtain 6- hydroxyl -2,3- two (3,5- Difluorophenylamino formic acid esters) cellulose.6- hydroxylated cellulose derivant 1g is dissolved in
In the mixed liquor of 20 mLDMAC, 1.5g anhydrous Lithium chlorides and 60mL pyridine, add 1.35g3- (triethoxysilicane) propyl group isocyanide
Acid esters (the 30% of cellulose 6- position hydroxyl moles).80-90 DEG C of reaction 16h, adds 1.36g3,5- difluorophenyl Carbimide.
Ester（1.5 times of cellulose moles）Reaction 24h, pours in 400mL methanol, cellulose derivative Precipitation, and buchner funnel is taken out
Filter, methanol washs, 60 DEG C of vacuum drying 8h, obtains triethoxy silicon substrate propyl group -2 that cellulose 6- position is containing 30%, and 3,6- tri-
(3,5- Difluorophenylamino formic acid esters) cellulose derivative.
2）Silicon ball pretreatment.By 1g20 micron silicon ball（1000 angstroms of aperture）After being cleaned with distilled water, immersion is distilled by 15mL
Water, the mixed liquor of 1mL hydrogen peroxide composition, ammonia adjusts pH=7-8, is standing and soak for 24h, and G4 sand core funnel filters, and uses anhydrous second
Alcohol and distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h；Again silicon ball is immersed 15mL distilled water, 1mL
The mixed liquor of hydrogen peroxide composition, concentrated hydrochloric acid adjusts pH=2-4, is standing and soak for 24h, and G4 sand core funnel filters, with dehydrated alcohol and
Distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h.
3）Surfactant assembles.The 1g that acid-alkali treatment is crossed is dried the dodecyl front three that silicon ball is immersed in 20mL
Ammonium chloride solution（Concentration is 0.025mol/L）In, carry out ultrasonic 40-50min, washing with alcohol silicon ball, 60 DEG C of vacuum drying
8h.
4）Prepared by hydridization Ludox.By 0.1g step 1）Cellulose derivative is dissolved in 35mL acetone for preparation, adds 4mL
(triethoxy silicon substrate) hexamethylene, 2mL ethanol, 0.1g surfactant and 0.25mL acid catalyst.Room temperature reaction 9 h, preparation
Obtain hybrid inorganic-organic Ludox.
5）Colloidal sol assembles.1g step 2）Handled silicon ball is added in 12mL hybrid inorganic-organic Ludox, assembling
2h, stands 1 h, ethanol centrifuge washing, 60 DEG C of vacuum drying 8h.
6）Repeat step 3-5 process, alternately assembles 5 times, and 1g silicon ball is added in 150mL ethanol, 50 DEG C of stirring 6h, G4 sand
Core funnel filters, 60 DEG C of vacuum drying 8h.Prepare the hud typed Cellulose chiral stationaryphase of top layer hybrid inorganic-organic.
The hud typed Amylose Chiral Stationary Phase preparation method of embodiment 2 top layer hybrid inorganic-organic, specific implementation step
As follows：
1）6- contains position a small amount of 3-（Triethoxy silicon substrate）Prepared by propyl group straight chain starch derivative
The amylose that 1g is dried is dissolved in 50mL anhydrous pyridine, adds 3.5g triphenylchloromethane protection amylose
6 hydroxyls, 80-90 DEG C of reaction 24h, add 3,5- dimethylphenyl isocyanate 5mL, continue reaction 24h, solution is poured into
In 400mL methanol, the straight chain starch derivative Precipitation of 6- position triphenyl methane protection, buchner funnel sucking filtration, methanol washs.
Then this derivant of 1 g is deprotected in 400mL methanol (3mL concentrated hydrochloric acid) solution interior edema solution, buchner funnel sucking filtration, methanol is washed
Wash, obtain 6- hydroxyl -2,3- bis- (3,5- dimethylphenylcarbamate) amylose.6- hydroxyl amylose is derived
Thing 1g is dissolved in 20 mLDMAC, 1.5g anhydrous Lithium chlorides and the mixed liquor of 60mL pyridine, adds 0.45g3- (triethoxy
Silicon) propylisocyanate (the 10% of amylose 6- position hydroxyl moles).80-90 DEG C of reaction 16h, adds 1.36g3,5- bis-
Methylphenyl isocyanate（1.5 times of amylose moles）Reaction 24h, pours in 400mL methanol, and straight chain starch derivative sinks
Precipitation goes out, buchner funnel sucking filtration, and methanol washs, 60 DEG C of vacuum drying 8h, obtains the triethoxy that amylose 6 is containing 10%
Silicon substrate propyl group -2,3,6- three (3,5- dimethylphenylcarbamate) straight chain starch derivative.
2）Silicon ball pretreatment.By 1g7 micron silicon ball（500 angstroms of aperture）After being cleaned with distilled water, immersion by 15mL distilled water,
The mixed liquor of 1mL hydrogen peroxide composition, ammonia adjusts pH=7-8, is standing and soak for 24h, and G4 sand core funnel filters, and uses dehydrated alcohol
With distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h；Again silicon ball is immersed 15mL distilled water, 1mL mistake
The mixed liquor of hydrogen oxide composition, concentrated hydrochloric acid adjusts pH=2-4, is standing and soak for 24h, and G4 sand core funnel filters, with dehydrated alcohol and steaming
Distilled water washs silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h.
3）Surfactant assembles.The 1g that acid-alkali treatment is crossed is dried the dodecyl front three that silicon ball is immersed in 20mL
Ammonium chloride solution（Concentration is 0.025mol/L）In, carry out ultrasonic 40-50min, washing with alcohol silicon ball, 60 DEG C of vacuum drying
8h.
4）Prepared by hydridization Ludox.By 0.1g step 1）Prepare straight chain starch derivative to be dissolved in 30mL oxolane, then
Add the double three silica butyldimethylsilyl of 3mL, 2mL ethanol, 0.1g surfactant and 0.25mL sulfuric acid catalyst.Room temperature reaction 9
H, prepares hybrid inorganic-organic Ludox.
5）Colloidal sol assembles.1g step 2）Handled silicon ball is added in 15mL hybrid inorganic-organic Ludox, assembling
1h, stands 0.5 h, ethanol centrifuge washing, 60 DEG C of vacuum drying 8h.
6）Repeat step 3-5 process, alternately assembles 6 times, and 1g silicon ball is added in 150mL ethanol, 50 DEG C of stirring 6h, G4 sand
Core funnel filters, 60 DEG C of vacuum drying 8h.Prepare the hud typed Amylose Chiral Stationary Phase of top layer hybrid inorganic-organic.
Embodiment 3 top layer hybrid inorganic-organic hud typed amylopectin chiral stationary phase preparation method, specific implementation step
As follows：
1）6- contains position on a small quantity（3-（Triethoxy silicon substrate）The preparation of propyl group branches starch derivatives
The amylopectin that 1g is dried is dissolved in 50mL anhydrous pyridine, adds 3.5g triphenylchloromethane protection amylopectin
6 hydroxyls, 80-90 DEG C of reaction 24h, add 3,5- dichlorophenyl isocyanate 5mL, continue reaction 24h, solution is poured into
In 400mL methanol, the amylin derivative Precipitation of 6- position triphenyl methane protection, buchner funnel sucking filtration, methanol washs.
Then this derivant of 1 g is deprotected in 400mL methanol (3mL concentrated hydrochloric acid) solution interior edema solution, buchner funnel sucking filtration, methanol is washed
Wash, obtain 6- hydroxyl -2,3- bis- (3,5- Dichlorobenzene base carbamate) amylopectin.By 6- hydroxyl amylin derivative
1g is dissolved in 20 mLDMAC, 1.5g anhydrous Lithium chlorides and the mixed liquor of 60mL pyridine, adds 0.9g3- (triethoxysilicane) third
Based isocyanate (the 20% of amylopectin 6- position hydroxyl moles).80-90 DEG C of reaction 16h, adds 1.36g3,5- dichloro-benzenes
Based isocyanate（1.5 times of amylopectin sugar unit moles）Reaction 24h, pours in 400mL methanol, and amylin derivative sinks
Precipitation goes out, buchner funnel sucking filtration, and methanol washs, 60 DEG C of vacuum drying 8h, obtains the triethoxy that amylopectin 6 is containing 20%
Silicon substrate propyl group -2,3,6- three (3,5- Dichlorobenzene base carbamate) amylin derivative.
2）Silicon ball pretreatment.By 1g10 micron silicon ball（800 angstroms of aperture）After being cleaned with distilled water, immersion is distilled by 15mL
Water, the mixed liquor of 1mL hydrogen peroxide composition, ammonia adjusts pH=7-8, is standing and soak for 24h, and G4 sand core funnel filters, and uses anhydrous second
Alcohol and distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h；Again silicon ball is immersed 15mL distilled water, 1mL
The mixed liquor of hydrogen peroxide composition, concentrated hydrochloric acid adjusts pH=2-4, is standing and soak for 24h, and G4 sand core funnel filters, with dehydrated alcohol and
Distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h.
3）Surfactant assembles.The 1g that acid-alkali treatment is crossed is dried the octadecyl front three that silicon ball is immersed in 20mL
Ammonium chloride solution（Concentration is 0.025mol/L）In, carry out ultrasonic 40-50min, washing with alcohol silicon ball, 60 DEG C of vacuum drying
8h.
4）Prepared by hydridization Ludox.By 0.2g step 1）Prepare amylin derivative to be dissolved in 35mL acetone, add
6mL1,2- is double（Triethoxy silicon substrate）Ethane, 2mL ethanol, 0.1g surfactant and 0.25mL acid catalyst.Room temperature reaction 9
H, prepares hybrid inorganic-organic Ludox.
5）Colloidal sol assembles.1g step 2）Handled silicon ball is added in 18mL hybrid inorganic-organic Ludox, assembling
1h, stands 1 h, ethanol centrifuge washing, 60 DEG C of vacuum drying 8h.
6）Repeat step 3-5 process, alternately assembles 5 times, and 1g silicon ball is added in 150mL ethanol, 50 DEG C of stirrings 6 h, G4
Sand core funnel filters, 60 DEG C of vacuum drying 8h.Prepare the hud typed amylopectin of top layer hybrid inorganic-organic chiral fixing
Phase.
Embodiment 4 top layer hybrid inorganic-organic core-shell type nano Cellulose chiral stationaryphase preparation method, is embodied as walking
Suddenly as follows：
1）6- contains 3- in position（Triethoxy silicon substrate）Prepared by propyl group nano-cellulose derivant
The nano-cellulose that 1g is dried is dissolved in 50mL anhydrous pyridine, adds 3.5g triphenylchloromethane protection Nanowire
Plain 6 hydroxyls of dimension, 80-90 DEG C of reaction 24h, add 3,5- dimethylphenyl isocyanate 5mL, continue reaction 24h, solution is fallen
Enter in 400mL methanol, the nano-cellulose derivant Precipitation of 6- position triphenyl methane protection, buchner funnel sucking filtration, methanol
Washing.Then this derivant of 1g is deprotected in 400mL methanol (3mL concentrated hydrochloric acid) solution interior edema solution, buchner funnel sucking filtration, methanol
Washing, obtains 6- hydroxyl -2,3- bis- (3,5- dimethylphenylcarbamate) nano-cellulose.By 6- hydroxyl nanofiber
Plain derivant 1g is dissolved in 20 mLDMAC, 1.5g anhydrous Lithium chlorides and the mixed liquor of 60mL pyridine, adds 0.09g3- (three second
Epoxide silicon) propylisocyanate (the 2% of nano-cellulose 6- position hydroxyl moles).80-90 DEG C of reaction 16h, adds
1.36g3,5- dimethylphenyl isocyanate（1.5 times of nano-cellulose moles）Reaction 24h, pours in 400mL methanol, receives
Rice cellulose derivative Precipitation, buchner funnel sucking filtration, methanol washs, 60 DEG C of vacuum drying 8h, obtains nano-cellulose 6
Containing 2% triethoxy silicon substrate propyl group -2,3,6- three (3,5- dimethylphenylcarbamate) nano-cellulose derivant.
2）Silicon ball pretreatment.By 1g5 micron silicon ball（100 angstroms of aperture）After being cleaned with distilled water, immersion by 15mL distilled water,
The mixed liquor of 1mL hydrogen peroxide composition, ammonia adjusts pH=7-8, is standing and soak for 24h, and G4 sand core funnel filters, and uses dehydrated alcohol
With distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h；Again silicon ball is immersed 15mL distilled water, 1mL mistake
The mixed liquor of hydrogen oxide composition, concentrated hydrochloric acid adjusts pH=2-4, is standing and soak for 24h, and G4 sand core funnel filters, with dehydrated alcohol and steaming
Distilled water washs silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h.
3）Surfactant assembles.The 1g that acid-alkali treatment is crossed is dried the CTAB solution that silicon ball is immersed in 20mL（Dense
Spend for 0.025mol/L）In, carry out ultrasonic 40-50min, washing with alcohol silicon ball, 60 DEG C of vacuum drying 8h.
4）Prepared by hydridization Ludox.By 0.05g step 1）Prepare nano-cellulose derivant to be dissolved in 25mLDMF, then plus
Enter 1mL tetraethyl orthosilicate, 2mL ethanol, 0.1g surfactant and 0.25mL hydrochloric acid catalyst.Room temperature reaction 9h, prepares
Hybrid inorganic-organic Ludox.
5）Colloidal sol assembles.1g step 2）Handled silicon ball is added in 20mL hybrid inorganic-organic Ludox, assembling
0.5h, stands 0.5 h, ethanol centrifuge washing, 60 DEG C of vacuum drying 8h.
6）Repeat step 3-5 process, alternately assembles 2 times, and 1g silicon ball is added in 150mL ethanol, 50 DEG C of stirring 6h, G4 sand
Core funnel filters, 60 DEG C of vacuum drying 8h.Prepare top layer hybrid inorganic-organic core-shell type nano cellulose chiral to fix
Phase.
Embodiment 5 top layer hybrid inorganic-organic core-shell type nano Cellulose chiral stationaryphase preparation method, is embodied as walking
Suddenly as follows：
1）6- contains 3- in position（Triethoxy silicon substrate）Prepared by propyl group nano-cellulose derivant
The nano-cellulose that 1g is dried is dissolved in 50mL anhydrous pyridine, adds 3.5g triphenylchloromethane protection Nanowire
Dimension plain 6- position hydroxyl, 80-90 DEG C of reaction 24h, add 3,5- difluorophenyl isocyanate 5mL, continue reaction 24h, solution is fallen
Enter in 400mL methanol, the nano-cellulose derivant Precipitation of 6- position triphenyl methane protection, buchner funnel sucking filtration, methanol
Washing.Then this derivant of 1g is deprotected in 400mL methanol (3mL concentrated hydrochloric acid) solution interior edema solution, buchner funnel sucking filtration, methanol
Washing, obtains 6- hydroxyl -2,3- bis- (3,5- Difluorophenylamino formic acid esters) nano-cellulose.By 6- hydroxyl nano-cellulose
Derivant 1g is dissolved in 20 mLDMAC, 1.5g anhydrous Lithium chlorides and the mixed liquor of 60mL pyridine, adds 2.25g3- (three ethoxies
Base silicon) propylisocyanate (the 50% of nano-cellulose 6- position hydroxyl moles).80-90 DEG C of reaction 16h, adds 1.36g3,
5- difluorophenyl isocyanate（1.5 times of nano-cellulose sugar unit moles）Reaction 24h, pours in 400mL methanol, Nanowire
The plain derivant Precipitation of dimension, buchner funnel sucking filtration, methanol washs, 60 DEG C of vacuum drying 8h, obtains nano-cellulose 6- position and contains
There is 50% triethoxy silicon substrate propyl group -2,3,6- three (3,5- Difluorophenylamino formic acid esters) nano-cellulose derivant.
2）Silicon ball pretreatment.By 1g5 micron silicon ball（120 angstroms of aperture）After being cleaned with distilled water, immersion by 15mL distilled water,
The mixed liquor of 1mL hydrogen peroxide composition, ammonia adjusts pH=7-8, is standing and soak for 24h, and G4 sand core funnel filters, and uses dehydrated alcohol
With distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h；Again silicon ball is immersed 15mL distilled water, 1mL mistake
The mixed liquor of hydrogen oxide composition, concentrated hydrochloric acid adjusts pH=2-4, is standing and soak for 24h, and G4 sand core funnel filters, with dehydrated alcohol and steaming
Distilled water washs silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h.
3）Surfactant assembles.The 1g that acid-alkali treatment is crossed is dried the octadecyl front three that silicon ball is immersed in 20mL
Ammonium chloride solution（Concentration is 0.025mol/L）In, carry out ultrasonic 40-50min, washing with alcohol silicon ball, 60 DEG C of vacuum drying
8h.
4）Prepared by hydridization Ludox.By 0.4g step 1）Prepare nano-cellulose derivant to be dissolved in 35mL acetone, then plus
Enter the double three silica butyldimethylsilyl of 7mL, 2mL ethanol, 0.1g surfactant and 0.25mL acid catalyst.Room temperature reaction 9 h, system
Standby obtain hybrid inorganic-organic Ludox.
5）Colloidal sol assembles.1g step 2）Handled silicon ball is added in 15mL hybrid inorganic-organic Ludox, assembling
2h, stands 1h, ethanol centrifuge washing, 60 DEG C of vacuum drying 8h.
6）Repeat step 3-5 process, alternately assembles 6 times, and 1g silicon ball is added in 150mL ethanol, 50 DEG C of stirring 6h, G4 sand
Core funnel filters, 60 DEG C of vacuum drying 8h.Prepare top layer hybrid inorganic-organic core-shell type nano cellulose chiral to fix
Phase.
The hud typed Amylose Chiral Stationary Phase preparation method of embodiment 6 top layer hybrid inorganic-organic, specific implementation step
As follows：
1）6- contains 3- in position（Triethoxy silicon substrate）Prepared by propyl group straight chain starch derivative
The amylose that 1g is dried is dissolved in 50mL anhydrous pyridine, adds 3.5g triphenylchloromethane protection amylose
6- position hydroxyl, 80-90 DEG C of reaction 24h, add 3,5- dichlorophenyl isocyanate 5mL, continue reaction 24h, solution is poured into
In 400mL methanol, the straight chain starch derivative Precipitation of 6- position triphenyl methane protection, buchner funnel sucking filtration, methanol washs.
Then this derivant of 1 g is deprotected in 400mL methanol (3mL concentrated hydrochloric acid) solution interior edema solution, buchner funnel sucking filtration, methanol is washed
Wash, obtain 6- hydroxyl -2,3- bis- (3,5- Dichlorobenzene base carbamate) amylose.By 6- hydroxyl straight chain starch derivative
1g is dissolved in 20 mLDMAC, 1.5g anhydrous Lithium chlorides and the mixed liquor of 60mL pyridine, adds 3.15g3- (triethoxysilicane)
Propylisocyanate (the 70% of amylose 6- position hydroxyl moles).80-90 DEG C of reaction 16h, adds 0.46g3,5- dichloro
Phenyl isocyanate（0.5 times of amylose sugar unit mole）Reaction 24h, pours in 400mL methanol, straight chain starch derivative
Precipitation, buchner funnel sucking filtration, methanol washs, 60 DEG C of vacuum drying 8h, obtains three ethoxies that amylose 6 is containing 70%
Base silicon substrate propyl group -2,3,6- three (3,5- Dichlorobenzene base carbamate) straight chain starch derivative.
2）Silicon ball pretreatment.By 1g5 micron silicon ball（100 angstroms of aperture）After being cleaned with distilled water, immersion by 15mL distilled water,
The mixed liquor of 1mL hydrogen peroxide composition, ammonia adjusts pH=7-8, is standing and soak for 24h, and G4 sand core funnel filters, and uses dehydrated alcohol
With distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h；Again silicon ball is immersed 15mL distilled water, 1mL mistake
The mixed liquor of hydrogen oxide composition, concentrated hydrochloric acid adjusts pH=2-4, is standing and soak for 24h, and G4 sand core funnel filters, with dehydrated alcohol and steaming
Distilled water washs silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h.
3）Surfactant assembles.The 1g that acid-alkali treatment is crossed is dried the cetyl front three that silicon ball is immersed in 20mL
Base ammonium bromide solution（Concentration is 0.025mol/L）In, carry out ultrasonic 40-50min, washing with alcohol silicon ball, 60 DEG C of vacuum drying
8h.
4）Prepared by hydridization Ludox.By 0.2g step 1）Prepare straight chain starch derivative to be dissolved in 35mL pyridine, add
5mL1,2- is double（Triethoxysilicane）Ethane, 2mL ethanol, 0.1g surfactant and 0.25mL hydrochloric acid.Room temperature reaction 9 h, preparation
Obtain hybrid inorganic-organic Ludox.
5）Colloidal sol assembles.1g step 2）Handled silicon ball is added in 15mL hybrid inorganic-organic Ludox, assembling
2h, stands 1h, ethanol centrifuge washing, 60 DEG C of vacuum drying 8h.
6）Repeat step 3-5 process, alternately assembles 7 times, and 1g silicon ball is added in 150mL ethanol, 50 DEG C of stirring 6h, G4 sand
Core funnel filters, 60 DEG C of vacuum drying 8h.Prepare the hud typed Amylose Chiral Stationary Phase of top layer hybrid inorganic-organic.
Embodiment 7 top layer hybrid inorganic-organic core-shell type nano Amylose Chiral Stationary Phase preparation method, is embodied as
Step is as follows：
1）6- contains position on a small quantity（3-（Triethoxy silicon substrate））The preparation of propyl group nanometer straight chain starch derivative
The nanometer amylose that 1g is dried is dissolved in 50mL anhydrous pyridine, adds 3.5g triphenylchloromethane protection nanometer
Amylose 6- position hydroxyl, 80-90 DEG C of reaction 24h, add 3,5- dichlorophenyl isocyanate 5mL, continue reaction 24h, will be molten
Liquid is poured in 400mL methanol, the nanometer straight chain starch derivative Precipitation of 6- position triphenyl methane protection, and buchner funnel is taken out
Filter, methanol washs.Then this derivant of 1 g is deprotected in 400mL methanol (3mL concentrated hydrochloric acid) solution interior edema solution, buchner funnel
Sucking filtration, methanol washs, and obtains 6- hydroxyl -2,3- bis- (3,5- Dichlorobenzene base carbamate) nanometer amylose.By 6- hydroxyl
Nanometer straight chain starch derivative 1g is dissolved in 20mLDMAC, 1.5g anhydrous Lithium chloride and the mixed liquor of 60mL pyridine, adds
0.45g3- (triethoxysilicane) propylisocyanate (the 10% of amylose 6- position hydroxyl moles).80-90 DEG C of reaction 16h,
Add 0.82g3,5- dichlorophenyl isocyanate（1 times of amylose sugar unit mole）Reaction 24h, pours 400mL methanol into
In, straight chain starch derivative Precipitation, buchner funnel sucking filtration, methanol washs, 60 DEG C of vacuum drying 8h, obtains 6- position and contains
10% triethoxy silicon substrate propyl group -2,3,6- three (3,5- Dichlorobenzene base carbamate) straight chain starch derivative.
2）Silicon ball pretreatment.By 1g8 micron silicon ball（120 angstroms of aperture）After being cleaned with distilled water, immersion by 15mL distilled water,
The mixed liquor of 1mL hydrogen peroxide composition, ammonia adjusts pH=7-8, is standing and soak for 24h, and G4 sand core funnel filters, and uses dehydrated alcohol
With distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h；Again silicon ball is immersed 15mL distilled water, 1mL mistake
The mixed liquor of hydrogen oxide composition, concentrated hydrochloric acid adjusts pH=2-4, is standing and soak for 24h, and G4 sand core funnel filters, with dehydrated alcohol and steaming
Distilled water washs silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h.
3）Surfactant assembles.The 1g that acid-alkali treatment is crossed is dried the cetyl front three that silicon ball is immersed in 20mL
Ammonium chloride solution（Concentration is 0.025mol/L）In, carry out ultrasonic 40-50min, washing with alcohol silicon ball, 60 DEG C of vacuum drying
8h.
4）Prepared by hydridization Ludox.By 0.1g step 1）Prepare straight chain starch derivative to be scattered in 35mL acetone, then plus
Enter 2mL tetraethyl orthosilicate, 2mL ethanol, 0.1g surfactant and 0.25mL hydrochloric acid.Room temperature reaction 9h, prepare organic-no
Machine hydridization Ludox.
5）Colloidal sol assembles.1g step 2）Handled silicon ball is added in 15mL hybrid inorganic-organic Ludox, assembling
2.5h, stands 1 h, ethanol centrifuge washing, 60 DEG C of vacuum drying 8h.
6）Repeat step 3-5 process, alternately assembles 6 times, and 1g silicon ball is added in 150mL ethanol, 50 DEG C of stirring 6h, G4 sand
Core funnel filters, 60 DEG C of vacuum drying 8h.Prepare top layer hybrid inorganic-organic core-shell type nano amylose chiral fixing
Phase.
Embodiment 8 top layer hybrid inorganic-organic hud typed amylopectin chiral stationary phase preparation method, specific implementation step
As follows：
1）6- contains position（3-（Triethoxy silicon substrate）The preparation of propyl group branches starch derivatives
The amylopectin that 1g is dried is dissolved in 50mL anhydrous pyridine, adds 3.5g triphenylchloromethane protection amylopectin
6- position hydroxyl, 80-90 DEG C of reaction 24h, add 3,5- dimethylphenyl isocyanate 5mL, continue reaction 24h, solution is poured into
In 400mL methanol, the amylin derivative Precipitation of 6- position triphenyl methane protection, buchner funnel sucking filtration, methanol washs.
Then this derivant of 1g is deprotected in 400mL methanol (3mL concentrated hydrochloric acid) solution interior edema solution, buchner funnel sucking filtration, methanol washs,
Obtain 6- hydroxyl -2,3- two (3,5- dimethylphenylcarbamate) amylopectin.By 6- hydroxyl amylin derivative 1g
It is dissolved in 20 mLDMAC, 1.5g anhydrous Lithium chlorides and the mixed liquor of 60mL pyridine, add 3.91g3- (triethoxysilicane) third
Based isocyanate (the 85% of amylopectin 6- position hydroxyl moles).80-90 DEG C of reaction 16h, adds 0.46g3,5- dichloro-benzenes
Based isocyanate（0.5 times of amylopectin sugar unit mole）Reaction 24h, pours in 400mL methanol, and amylin derivative sinks
Precipitation goes out, buchner funnel sucking filtration, and methanol washs, 60 DEG C of vacuum drying 8h, obtains the triethoxy that amylopectin 6 is containing 85%
Silicon substrate propyl group -2,3,6- three (3,5- dimethylphenylcarbamate) amylin derivative.
2）Silicon ball pretreatment.By 1g5 micron silicon ball（120 angstroms of aperture）After being cleaned with distilled water, immersion by 15mL distilled water,
The mixed liquor of 1mL hydrogen peroxide composition, ammonia adjusts pH=7-8, is standing and soak for 24h, and G4 sand core funnel filters, and uses dehydrated alcohol
With distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h；Again silicon ball is immersed 15mL distilled water, 1mL mistake
The mixed liquor of hydrogen oxide composition, concentrated hydrochloric acid adjusts pH=2-4, is standing and soak for 24h, and G4 sand core funnel filters, with dehydrated alcohol and steaming
Distilled water washs silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h.
3）Surfactant assembles.The 1g that acid-alkali treatment is crossed is dried the dodecyl front three that silicon ball is immersed in 20mL
Ammonium chloride solution（Concentration is 0.025mol/L）In, carry out ultrasonic 40-50min, washing with alcohol silicon ball, 60 DEG C of vacuum drying
8h.
4）Prepared by hydridization Ludox.By 0.4g step 1）Preparation nanometer amylin derivative is dissolved in 35mLDMF, then plus
Enter 9mL tetraethyl orthosilicate, 2mL ethanol, 0.1g surfactant and 0.25mL acid catalyst.Room temperature reaction 9h, has prepared
Machine-inorganic hybridization Ludox.
5）Colloidal sol assembles.1g step 2）Handled silicon ball is added in 12mL hybrid inorganic-organic Ludox, assembling
0.5h, stands 1 h, ethanol centrifuge washing, 60 DEG C of vacuum drying 8h.
6）Repeat step 3-5 process, alternately assembles 8 times, and 1g silicon ball is added in 150mL ethanol, 50 DEG C of stirring 6h, G4 sand
Core funnel filters, 60 DEG C of vacuum drying 8h.Prepare top layer hybrid inorganic-organic hud typed amylopectin chiral stationary phase.
Embodiment 9 top layer hybrid inorganic-organic hud typed Microcrystalline Cellulose chiral stationary phase preparation method, is embodied as walking
Suddenly as follows：
1）6- contains position（3-（Triethoxy silicon substrate））The preparation of propyl group microcrystalline cellulose derivative
The Microcrystalline Cellulose that 1g is dried is dissolved in 50mL anhydrous pyridine, adds 3.5g triphenylchloromethane protection cellulose
6- position hydroxyl, 80-90 DEG C of reaction 24h, add 3,5- dichlorophenyl isocyanate 5mL, continue reaction 24h, solution is poured into
In 400mL methanol, the microcrystalline cellulose derivative Precipitation of 6- position triphenyl methane protection, buchner funnel sucking filtration, methanol is washed
Wash.Then this derivant of 1 g is deprotected in 400mL methanol (3mL concentrated hydrochloric acid) solution interior edema solution, buchner funnel sucking filtration, methanol
Washing, obtains 6- hydroxyl -2,3- bis- (3,5- Dichlorobenzene base carbamate) cellulose.By 6- hydroxylated cellulose derivant 1g
It is dissolved in 20mLDMF, 1.5g anhydrous Lithium chloride and the mixed liquor of 1mL pyridine, add 4.5g3- (triethoxysilicane) propyl group different
Cyanate (the 99.9% of cellulose 6- position hydroxyl moles).80-90 DEG C of reaction 16h, adds 0.46g3,5- Dichlorobenzene base is different
Cyanate（0.5 times of cellulose mole）Reaction 24h, pours in 400mL methanol, cellulose derivative Precipitation, and Bu Shi leaks
Bucket sucking filtration, methanol washs, 60 DEG C of vacuum drying 8h, obtains triethoxy silicon substrate propyl group -2 that cellulose 6 is containing 99.9%, and 3,
6- tri- (3,5- Dichlorobenzene base carbamate) cellulose derivative.
2）Silicon ball pretreatment.By 1g5 micron silicon ball（100 angstroms of aperture）After being cleaned with distilled water, immersion by 15mL distilled water,
The mixed liquor of 1mL hydrogen peroxide composition, ammonia adjusts pH=7-8, is standing and soak for 24h, and G4 sand core funnel filters, and uses dehydrated alcohol
With distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h；Again silicon ball is immersed 15mL distilled water, 1mL mistake
The mixed liquor of hydrogen oxide composition, concentrated hydrochloric acid adjusts pH=2-4, is standing and soak for 24h, and G4 sand core funnel filters, with dehydrated alcohol and steaming
Distilled water washs silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h.
3）Surfactant assembles.The 1g that acid-alkali treatment is crossed is dried the octadecyl front three that silicon ball is immersed in 20mL
Ammonium chloride solution（Concentration is 0.025mol/L）In, carry out ultrasonic 40-50min, washing with alcohol silicon ball, 60 DEG C of vacuum drying
8h.
4）Prepared by hydridization Ludox.By 0.1g step 1）Cellulose derivative is dissolved in 35mL acetone for preparation, adds 4mL
Tetraethyl orthosilicate, 2mL ethanol, 0.1g surfactant and 0.25mL acid catalyst.Room temperature reaction 9h, prepare organic-no
Machine hydridization Ludox.
5）Colloidal sol assembles.1g step 2）Handled silicon ball is added in 10mL hybrid inorganic-organic Ludox, assembling
3h, stands 1h, ethanol centrifuge washing, 60 DEG C of vacuum drying 8h.
6）Repeat step 3-5 process, alternately assembles 5 times, and 1g silicon ball is added in 150mL ethanol, 50 DEG C of stirring 6h, G4 sand
Core funnel filters, 60 DEG C of vacuum drying 8h.Prepare the hud typed Cellulose chiral stationaryphase of top layer hybrid inorganic-organic.
Embodiment 10 top layer hybrid inorganic-organic core-shell type nano amylopectin chiral stationary phase preparation method, specifically real
Apply step as follows：
1）6- contains position（3-（Triethoxy silicon substrate））The preparation of propyl group nanometer amylin derivative
The nanometer amylopectin that 1g is dried is dissolved in 50mL anhydrous pyridine, adds 3.5g triphenylchloromethane protection nanometer
Amylopectin 6- position hydroxyl, 80-90 DEG C of reaction 24h, add 3,5- dichlorophenyl isocyanate 5mL, continue reaction 24h, will be molten
Liquid is poured in 400mL methanol, the nanometer amylin derivative Precipitation of 6- position triphenyl methane protection, and buchner funnel is taken out
Filter, methanol washs.Then this derivant of 1g is deprotected in 400mL methanol (3mL concentrated hydrochloric acid) solution interior edema solution, buchner funnel is taken out
Filter, methanol washs, and obtains 6- hydroxyl -2,3- bis- (3,5- Dichlorobenzene base carbamate) nanometer amylopectin.6- hydroxyl is received
Rice amylin derivative 1g is dissolved in 20 mLDMAC, 1.5g anhydrous Lithium chlorides and the mixed liquor of 60mL pyridine, adds
0.45g3- (triethoxysilicane) propylisocyanate (the 10% of amylopectin 6- position hydroxyl moles).80-90 DEG C of reaction 16h,
Add 0.82g3,5- dichlorophenyl isocyanate（1 times of amylopectin sugar unit mole）Reaction 24h, pours 400mL methanol into
In, nanometer amylin derivative Precipitation, buchner funnel sucking filtration, methanol washs, 60 DEG C of vacuum drying 8h, obtains 6- position and contains
There is 10% triethoxy silicon substrate propyl group -2,3,6- three (3,5- Dichlorobenzene base carbamate) nanometer amylin derivative.
2）Silicon ball pretreatment.By 1g6 micron silicon ball（150 angstroms of aperture）After being cleaned with distilled water, immersion by 15mL distilled water,
The mixed liquor of 1mL hydrogen peroxide composition, ammonia adjusts pH=7-8, is standing and soak for 24h, and G4 sand core funnel filters, and uses dehydrated alcohol
With distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h；Again silicon ball is immersed 15mL distilled water, 1mL mistake
The mixed liquor of hydrogen oxide composition, concentrated hydrochloric acid adjusts pH=2-4, is standing and soak for 24h, and G4 sand core funnel filters, with dehydrated alcohol and steaming
Distilled water washs silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h.
3）Surfactant assembles.The 1g that acid-alkali treatment is crossed is dried the octadecyl front three that silicon ball is immersed in 20mL
Ammonium chloride solution（Concentration is 0.025mol/L）In, carry out ultrasonic 40-50min, washing with alcohol silicon ball, 60 DEG C of vacuum drying
8h.
4）Prepared by hydridization Ludox.By 0.2g step 1）Preparation nanometer amylin derivative is scattered in 35mLTHF, then
Add the double three silica butyldimethylsilyl of 6mL, 2mL ethanol, 0.1g surfactant and 0.25mL sulphuric acid.Room temperature reaction 9h, preparation
Obtain hybrid inorganic-organic Ludox.
5）Colloidal sol assembles.1g step 2）Handled silicon ball is added in 10mL hybrid inorganic-organic Ludox, assembling
4h, stands 0.5h, ethanol centrifuge washing, 60 DEG C of vacuum drying 8h.
6）Repeat step 3-5 process, alternately assembles 8 times, and 1g silicon ball is added in 150mL ethanol, 50 DEG C of stirring 6h, G4 sand
Core funnel filters, 60 DEG C of vacuum drying 8h.Prepare top layer hybrid inorganic-organic core-shell type nano amylopectin chiral fixing
Phase.
Embodiment 11 top layer hybrid inorganic-organic core-shell type nano Amylose Chiral Stationary Phase preparation method, specifically real
Apply step as follows：
1）6- contains position（3-（Triethoxy silicon substrate））The preparation of propyl group nanometer straight chain starch derivative
The nanometer amylose that 1g is dried is dissolved in 50mL anhydrous pyridine, adds 3.5g triphenylchloromethane protection nanometer
Amylose 6- position hydroxyl, 80-90 DEG C of reaction 24h, add 3,5- dimethylphenyl isocyanate 5mL, continue reaction 24h, will
Solution is poured in 400mL methanol, the nanometer straight chain starch derivative Precipitation of 6- position triphenyl methane protection, and buchner funnel is taken out
Filter, methanol washs.Then this derivant of 1 g is deprotected in 400mL methanol (3mL concentrated hydrochloric acid) solution interior edema solution, buchner funnel
Sucking filtration, methanol washs, and obtains 6- hydroxyl -2,3- bis- (3,5- dimethylphenylcarbamate) nanometer amylose.By 6- hydroxyl
Base nanometer straight chain starch derivative 1g is dissolved in 20mLDMAC, 1.5g anhydrous Lithium chloride and the mixed liquor of 1mL pyridine, adds
4.5g3- (triethoxysilicane) propylisocyanate (the 99.9% of amylose 6- position hydroxyl moles).80-90 DEG C of reaction 16h,
Add 0.82g3,5- dimethylphenyl isocyanate（0.5 times of amylose sugar unit mole）Reaction 24h, pours 400mL into
In methanol, straight chain starch derivative Precipitation, buchner funnel sucking filtration, methanol washs, 60 DEG C of vacuum drying 8h, obtains 6- position and contains
There is 99.9% triethoxy silicon substrate propyl group -2,3,6- three (3,5- dimethylphenylcarbamate) straight chain starch derivative.
2）Silicon ball pretreatment.By 1g5 micron silicon ball（100 angstroms of aperture）After being cleaned with distilled water, immersion by 15mL distilled water,
The mixed liquor of 1mL hydrogen peroxide composition, ammonia adjusts pH=7-8, is standing and soak for 24h, and G4 sand core funnel filters, and uses dehydrated alcohol
With distilled water wash silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h；Again silicon ball is immersed 15mL distilled water, 1mL mistake
The mixed liquor of hydrogen oxide composition, concentrated hydrochloric acid adjusts pH=2-4, is standing and soak for 24h, and G4 sand core funnel filters, with dehydrated alcohol and steaming
Distilled water washs silicon ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying 4h.
3）Surfactant assembles.The 1g that acid-alkali treatment is crossed is dried the cetyl front three that silicon ball is immersed in 20mL
Ammonium chloride solution（Concentration is 0.025mol/L）In, carry out ultrasonic 40-50min, washing with alcohol silicon ball, 60 DEG C of vacuum drying
8h.
4）Prepared by hydridization Ludox.By 0.3g step 1）Prepare straight chain starch derivative to be scattered in 30mL pyridine, then plus
Enter 4mL tetraethyl orthosilicate, 2mL ethanol, 0.1g surfactant and 0.25mL nitric acid.Room temperature reaction 9h, prepare organic-no
Machine hydridization Ludox.
5）Colloidal sol assembles.1g step 2）Handled silicon ball is added in 15mL hybrid inorganic-organic Ludox, assembling
3h, stands 1h, ethanol centrifuge washing, 60 DEG C of vacuum drying 8h.
6）Repeat step 3-5 process, alternately assembles 8 times, and 1g silicon ball is added in 150mL ethanol, 50 DEG C of stirring 6h, G4 sand
Core funnel filters, 60 DEG C of vacuum drying 8h.Prepare top layer hybrid inorganic-organic core-shell type nano amylose chiral fixing
Phase.
Claims (7)
1. a kind of preparation method of the hud typed polysaccharide chiral stationary phase of top layer hybrid inorganic-organic is it is characterised in that step is：
1）The preparation of polysaccharide derivates：The Microcrystalline Cellulose being dried is dissolved in anhydrous pyridine, adds triphenylchloromethane protection
Cellulose 6- position hydroxyl, 80-90 DEG C of reaction, add 3,5- dimethylphenyl isocyanate, continue reaction, solution is poured into methanol
In, the cellulose derivative Precipitation of 6- position triphenyl methane protection, buchner funnel sucking filtration, methanol washs；Then this is spread out
In the deprotection of the methanol solution interior edema solution containing a small amount of hydrochloric acid, sucking filtration, methanol washs biology, obtains 6- hydroxyl -2,3- bis- (3,5-
Dimethylphenylcarbamate) cellulose；6- hydroxylated cellulose derivant is dissolved in N, N '-dimethyl acetylamide, anhydrous
In the mixed liquor of lithium chloride and pyridine, add 3- (triethoxysilicane) propylisocyanate, 80-90 DEG C of reaction, add 1.5 times
3, the 5- dimethylphenyl isocyanate reaction of cellulose mole, pours in methanol, and cellulose derivative Precipitation is taken out
Filter, methanol washs, 60 DEG C of vacuum drying, obtains triethoxy silicon substrate propyl group -2 containing different content for the cellulose 6- position, 3- bis-
(3,5- Dichlorobenzene base carbamate) cellulose derivative；
2）Silicon ball pretreatment：After silicon ball is cleaned with distilled water, successively immerse by mixing that distilled water, ammonia, hydrogen peroxide form
Close liquid and the mixed liquor being made up of distilled water, concentrated hydrochloric acid, hydrogen peroxide, be standing and soak for, with dehydrated alcohol and distilled water wash silicon
Ball, until cleaning mixture is neutrality, 60 DEG C of vacuum drying；
3）Surfactant assembles：The dring silicon bead that acid-alkali treatment is crossed is immersed in cetyl trimethylammonium bromide table
In the activator solution of face, carry out supersound process, washing with alcohol silicon ball, 60 DEG C of vacuum drying；
4）Prepared by hydridization Ludox：By step 1）Preparation cellulose derivative is dissolved in N, in N '-dimethylformamide, adds silicon
Alkane reagent, ethanol, surfactant and acid catalyst, room temperature reaction, prepare hybrid inorganic-organic Ludox；
5）Colloidal sol assembles：Step 2）Handled silicon ball is added in hybrid inorganic-organic Ludox, assembles 0.5-3h, standing
0.5-1h, ethanol centrifuge washing, 60 DEG C of vacuum drying；
6）Repeat step 3）To 5）Process, alternately assembles for several times, silicon ball is added in ethanol, and stirring is filtered, 60 DEG C of vacuum are done
Dry, prepare the Cellulose chiral stationaryphase of hybrid inorganic-organic nucleocapsid structure.
2. the method for claim 1 is it is characterised in that step 1）6 hydroxyl protections of polysaccharide derivates react agents useful for same
Proportionate relationship be, Microcrystalline Cellulose：Pyridine：Triphenylchloromethane：Phenyl isocyanate derivant：Methanol=1g:50mL:
3.5g:5mL:400mL；The proportionate relationship of 6 protective reaction agents useful for same of polysaccharide derivates is, polysaccharide derivates：Hydrochloric acid：First
Alcohol=1g：3mL：400mL；The proportionate relationship of polysaccharide 6- position hydroxyl derivatization reaction agents useful for same is, polysaccharide derivates：DMAC：Chlorination
Lithium：Pyridine：Methanol=1g: 20mL: 1.5g:60mL:400mL, adds 6 hydroxyl moles 2-99.9% of polysaccharide derivates
3-（The base of three ethoxy silicon）Propylisocyanate, carries out regioselectivity derivatization reaction, 3- on polysaccharide 6- position to the 6- position of polysaccharide
（Three ethoxy silicon substrates）The substitution value of propyl group is 2-99.9%, then polysaccharide 6- position residual hydroxyl is derived with phenyl isocyanate again
Thing reacts.
3. the method for claim 1 is it is characterised in that step 2）In 5-20 micron, aperture is described silicon ball particle diameter
100-1000 angstrom；The volume ratio of distilled water and hydrogen peroxide solution is 15mL:1mL, alkaline mixed solution adjusts pH=by ammonia
7-8；Acid mixed solution adjusts pH=2-4 by concentrated hydrochloric acid；Silicon ball quality is 1g with the volume ratio of mixed liquor: 15-20mL.
4. the method for claim 1 is it is characterised in that step 3）The concentration of surfactant used is 0.025mol/L,
Silicon ball quality is 1g with the volume ratio of surfactant: 20mL.
5. the method for claim 1 is it is characterised in that step 4）Silane reagent used is tetraethyl orthosilicate, 1,2- is double
（Triethoxysilicane）Ethane, double three silica butyldimethylsilyl or (triethoxy silicon substrate) hexamethylene；Acid catalyst used is salt
Acid, sulphuric acid, phosphoric acid or nitric acid one or two；The proportionate relationship of agents useful for same is, polysaccharide derivates：Dissolving polysaccharide derives
Thing solvent：Silane reagent：Water：Ethanol：Surfactant：Acid catalyst=0.05-0.40 g: 25-45 mL: 1-10 mL:
2 mL: 0.1 g: 0.25mL.
6. the method for claim 1 is it is characterised in that step 5）Described silicon ball quality is molten with hybrid inorganic-organic silicon
The volume ratio of glue is 1g:10-20mL.
7. the method for claim 1 is it is characterised in that step 6）Described assembling number of times is 2-8 time, adds silicon ball
Quality is 1g with the volume ratio of ethanol: 150mL.
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| US20130303766A1 (en) * | 2012-05-09 | 2013-11-14 | Pusan National University Industry-University Cooperation Foundation | Organic-Inorganic Hybrid Mesoporous Silica Material Modified by Sulfonic Acid Group for Selective Adsorption of Metal Ions and Method of Manufacturing the Same |
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| CN101417227A (en) * | 2008-10-31 | 2009-04-29 | 北京化工大学 | Silica gel bonded double-chirality active center chromatogram filler, preparation method and use thereof |
| CN102516400A (en) * | 2011-12-05 | 2012-06-27 | 聊城大学 | Preparation method for mesoporous-silica-based cellulose bonding chiral stationary phase |
| CN102553550A (en) * | 2012-01-13 | 2012-07-11 | 浙江大学 | Hybridization chirality stationary phase based on cellulose derivative and preparation method thereof |
| US20130303766A1 (en) * | 2012-05-09 | 2013-11-14 | Pusan National University Industry-University Cooperation Foundation | Organic-Inorganic Hybrid Mesoporous Silica Material Modified by Sulfonic Acid Group for Selective Adsorption of Metal Ions and Method of Manufacturing the Same |
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