CN106732476A - A kind of preparation method of the amino modified mesoporous silicon oxide for separating and purifying taxol - Google Patents

A kind of preparation method of the amino modified mesoporous silicon oxide for separating and purifying taxol Download PDF

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CN106732476A
CN106732476A CN201611010222.7A CN201611010222A CN106732476A CN 106732476 A CN106732476 A CN 106732476A CN 201611010222 A CN201611010222 A CN 201611010222A CN 106732476 A CN106732476 A CN 106732476A
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amino modified
mesoporous silicon
silicon oxide
modified mesoporous
taxol
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范杰平
袁天桃
许小康
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Nanchang University
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Nanchang University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/14—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms condensed with carbocyclic rings or ring systems

Abstract

The present invention discloses a kind of preparation method of the amino modified mesoporous silicon oxide for separating and purifying taxol, using sol-gal process, it is functionalized reagent with the silane containing amino, using surfactant as soft template, it is carrier with 20 ~ 300 mesh preparing spherical SiO 2s, a kind of amino modified mesoporous silicon oxide is prepared on its surface.Amino modified Metaporous silicon dioxide material prepared by the method shows good selective absorption performance to taxol, and through column chromatography technology, the content of taxol in medicinal extract sample can be lifted significantly.The amino modified mesoporous silicon material prepared using the method, cost of material is cheap, and the technological operation of preparation technology and separation object is simple, and yield is high, it is easy to be applied to industrial production on a large scale.

Description

A kind of preparation of the amino modified mesoporous silicon oxide for separating and purifying taxol Method
Technical field
The invention belongs to natural drug separation technology field, and in particular to a kind of amino for separating and purifying taxol changes The preparation method of property mesoporous silicon oxide.
Background technology
Taxol（Paclitaxel）It is the important representative for having now been found that natural anti-cancer drugs, clinically uses extensively In the treatment of breast cancer, oophoroma and other position entity tumors., U.S. FAD in 1992（Food and Drug Administration）Approval Taxol is listed, and trade name Taxol is mainly used in the treatment of oophoroma.Taxol is equal to by Americanized scholar Wani A kind of diterpene-kind compound for being extracted from Chinese yew genus plants yewtree bark for 1971.In global range, day Right Chinese yew is considered as natural rare plants for anticancer, and type and quantity are rare, slow-growing, effective medicinal components in plant Content is extremely low.In China, many places are in artificial growth content Hybrid Manny Asia Chinese yew higher（Taxus media）, to meet the market demand.
Mesoporous silicon adsorption material is a kind of material favored by researcher for rising in the last few years.It is inorganic modified mesoporous Material is a kind of surface modifying material, due to its high-specific surface area and excellent absorption property, causes that scientific worker's is very big Interest.The application, as supporter, is modified using general spherical shape silica on its surface, prepares surface mesoporous and amino Modified silica, and can be used to separate and purification of paclitaxel.Common Si modification makes modified silicon ball possess good as supporter Good physical stability, surface mesoporous structure makes it have high-specific surface area, and surface amino groups are modified, and it is had taxol good Good selective adsorption capacity.So, a kind of amino modified mesoporous silicon oxide prepared by the application can show good thing Physicochemical tolerance, long service life, the features such as reusable under suitable environment temperature.In purification of pharmaceuticals, change The aspects such as catalysis and biotechnology are learned to have broad application prospects.
The method of various purifies and separates taxols is reported in document or patent, such as Chinese patent " application number 201310251956.4th, 201410388561.3 " have using the means of silica gel, alkali alumina column chromatography or recrystallization to carry Take isolation of taxol.According to being read up the literature, also find no patent and document is identical with the present invention.Advantages of the present invention：Spherical In the substrate of silica, functionalization group is combined with meso-hole structure, prepares amino modified mesoporous silicon oxide, it can be used In on column chromatography technology, the purity of taxol is improved nearly 20 times, the rate of recovery reaches more than 80%, be the big rule of taxol industrialization Mould production provides a direction.
The content of the invention
It is an object of the invention to solve the above problems, there is provided a kind of for the amino modified mesoporous of separating and purifying taxol The preparation method of silica.
A kind of preparation method of the amino modified mesoporous silicon oxide for separating and purifying taxol, technical process include with Lower step：
(1) 10g preparing spherical SiO 2s are taken（20-300 mesh）It is added to 10-100mL Piranha solution（Hydrogen peroxide：The concentrated sulfuric acid =3/7, v/v）In, plus rotor stirring, 120 DEG C of oil bath, 60min.Room temperature is cooled to, Piranha solution is diluted with ethanol（Now The concentrated sulfuric acid may heat release）, cooled and filtered rinsed 5-10 times repeatedly with ethanol, is washed till neutrality.It is vacuum dried at 60 DEG C 12h, the silica for being activated is standby.
(2) under the conditions of nitrogen atmosphere, silane of the 1.5-3.5mL containing amino is dissolved in 10-100mL's as functionalized reagent Absolute ethyl alcohol, 50 DEG C of stirring 1-6h of the mixed solution, 0.1-0.9g surfactants take 1.0g activated two as soft template Silica and 0.5-2.5mL tetraethyl orthosilicates or methyl silicate or their mixture are added in system.1mol/L's urges Agent solution 3-7mL is added dropwise over, and 50 DEG C of stirring 1-2h are kept under the conditions of nitrogen atmosphere, keeps 50 DEG C to be put into shaking table concussion afterwards Hatching 1-12h.Room temperature is cooled to, by after with absolute ethyl alcohol flotation, obtaining uniform microballoon after filtering.
(3) microballoon deionized water obtained in the previous step, absolute ethyl alcohol are washed 3-10 times respectively, to remove surface-active Agent, after washing, is vacuum dried 6-12h at 60 DEG C and obtains amino modified mesoporous silicon oxide afterwards.
(4) by prepared amino modified mesoporous silicon sphere, a pillar is assembled into, dry method loading is to the thick extracted extract of Chinese yew （Content of taxol 0.4%）Carry out column chromatography.Using ethanol/water gradient elution, different stream parts are collected, recycling design obtains solid.
The silane containing amino is 3- aminopropyls-trimethoxy silane, 3- aminopropyls-triethoxysilane, N- ammonia second One kind or their mixture in base-γ-aminopropyltrimethoxysilane.
The surfactant is Pluronic F127, Pluronic P123, cetyl trimethylammonium bromide （CTAB）In one kind or their mixture.
Catalyst described above is acid（One kind or their mixture in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid）, or Alkali（NH4One kind or their mixture in OH, triethylamine, NaOH）.
The new function earth silicon material of above-mentioned preparation, can be applied to isolating and purifying for taxol.
Amino modified Metaporous silicon dioxide material prepared by the method that the present invention is provided shows good choosing to taxol Selecting property absorption property, through column chromatography technology, the content of taxol in medicinal extract sample can be lifted significantly.Prepared using the method Amino modified mesoporous silicon material, cost of material is cheap, and the technological operation of preparation technology and separation object is simple, and yield It is high, it is easy to be applied to industrial production on a large scale.
Specific implementation method
Embodiment 1：
1. 10g preparing spherical SiO 2s are taken（20 mesh）It is added to 10 Piranha solution（Hydrogen peroxide：The concentrated sulfuric acid=3/7, v/v） In, plus rotor stirring, 120 DEG C of oil bath, 60min.Room temperature is cooled to, Piranha solution is diluted with ethanol（Now the concentrated sulfuric acid may Heat release）, cooled and filtered rinsed 5 times repeatedly with ethanol, is washed till neutrality.12h is vacuum dried at 60 DEG C, is activated Silica, it is standby.
2. under the conditions of nitrogen atmosphere, functionalized reagent (3- aminopropyls-triethoxysilane) 1.5mL is dissolved in the nothing of 10mL Water-ethanol, 50 DEG C of stirring 1h of the mixed solution.0.1g surfactant Pluronic F127,1.0g activated titanium dioxide Silicon, tetraethyl orthosilicate（TEOS）0.5mL is added in system.The catalyst HCl3.0mL of 1mol/L is dropwise added dropwise, nitrogen atmosphere Under the conditions of keep 50 DEG C stirring 1h, afterwards keep 50 DEG C be put into shaking table concussion hatching 1h.Room temperature is cooled to, by anhydrous second after filtering After alcohol flotation, uniform microballoon is obtained.
3. microballoon deionized water obtained in the previous step, absolute ethyl alcohol distinguish 3 washings, to remove Pluronic F127, is vacuum dried 6h and obtains amino modified mesoporous silicon oxide after filtering.
4. by prepared amino modified mesoporous silicon sphere, a pillar is assembled into, dry method loading is to the thick extracted extract of Chinese yew （Content of taxol 0.4%）Carry out column chromatography.Using ethanol/water gradient elution, different stream parts are collected, recycling design obtains solid, Gu Body is 9.0% through HPLC detection taxol purity, and the taxol rate of recovery is 89%.
Embodiment 2：
1. 10g preparing spherical SiO 2s are taken（300 mesh）It is added to 10 Piranha solution（Hydrogen peroxide：The concentrated sulfuric acid=3/7, v/v） In, plus rotor stirring, 120 DEG C of oil bath, 60min.Room temperature is cooled to, Piranha solution is diluted with ethanol（Now the concentrated sulfuric acid may Heat release）, cooled and filtered rinsed 10 times repeatedly with ethanol, is washed till neutrality.12h is vacuum dried at 60 DEG C, is activated Silica, it is standby.
2. under the conditions of nitrogen atmosphere, functionalized reagent 3- aminopropyls-triethoxysilane 3.5mL is dissolved in the anhydrous second of 50mL Alcohol, 50 DEG C of stirring 6h of the mixed solution.0.59 Surfactant CTAB, 1.0g activated silica, tetraethyl orthosilicate （TEOS）2.5mL is added in system.The catalyst n H of 1mol/L4OH 7.0mL are dropwise added dropwise, and are kept under the conditions of nitrogen atmosphere 50 DEG C of stirring 2h, keep 50 DEG C to be put into shaking table concussion hatching 12h afterwards.Room temperature is cooled to, by absolute ethyl alcohol flotation after filtering, is obtained Uniform microballoon.
3. previous step obtains point 10 washings of microballoon deionized water, absolute ethyl alcohol, to remove CTAB, 60 DEG C after filtering Lower vacuum drying 12h obtains amino modified mesoporous silicon oxide.
4. by prepared modified mesoporous silicon sphere, a pillar is assembled into, dry method loading is to the thick extracted extract of Chinese yew（It is purple China fir alcohol content 0.4%）Carry out column chromatography.Using ethanol/water gradient elution, different stream parts are collected, recycling design obtains solid, solid It is 8.2% through HPLC detection taxol purity, the taxol rate of recovery is 92%.
Embodiment 3：
1. 10g preparing spherical SiO 2s are taken（200 mesh）It is added to 50mL Piranha solution（Hydrogen peroxide：The concentrated sulfuric acid=3/7, v/ v）In, plus rotor stirring, 120 DEG C of oil bath, 60min.Room temperature is cooled to, Piranha solution is diluted with ethanol（Now the concentrated sulfuric acid can Can heat release）, cooled and filtered rinsed 8 times repeatedly with ethanol, is washed till neutrality.12h is vacuum dried at 60 DEG C, is activated Silica, it is standby.
2. under the conditions of nitrogen atmosphere, functionalized reagent N- aminoethyls-γ-aminopropyltrimethoxysilane 2.5mL is dissolved in The absolute ethyl alcohol of 50mL, 50 DEG C of stirring 6h of the mixed solution.PluronicF127,1.0g are activated for 0.5g surfactants Silica, tetraethyl orthosilicate（TEOS）1.0mL is added in system.The catalyst HCl5.0mL of 1mol/L is dropwise added dropwise, nitrogen 50 DEG C of stirring 2h are kept under gas atmospheric condition, keeps 50 DEG C to be put into shaking table concussion hatching 7h afterwards.Be cooled to room temperature, after filtering by After absolute ethyl alcohol flotation, uniform microballoon is obtained.
3. product deionized water obtained in the previous step, absolute ethyl alcohol point 5 washings, to remove PluronicF127, mistake 12h is vacuum dried after filter and obtains amino modified mesoporous silicon oxide.
4. by prepared amino modified mesoporous silicon sphere, a pillar is assembled into, dry method loading is to the thick extracted extract of Chinese yew （Content of taxol 0.4%）Carry out column chromatography.Using ethanol/water gradient elution, different stream parts are collected, recycling design obtains solid, Gu Body is 8.9% through HPLC detection taxol purity, and the taxol rate of recovery is 80%.
Embodiment 4：
1. 10g preparing spherical SiO 2s are taken（180 mesh）It is added to 60mL Piranha solution（Hydrogen peroxide：The concentrated sulfuric acid=3/7, v/ v）In, plus rotor stirring, 120 DEG C of oil bath, 60min.Room temperature is cooled to, Piranha solution is diluted with ethanol（Now the concentrated sulfuric acid can Can heat release）, cooled and filtered rinsed 7 times repeatedly with ethanol, is washed till neutrality.12h is vacuum dried at 60 DEG C, is activated Silica, it is standby.
2. under the conditions of nitrogen atmosphere, functionalized reagent 3- aminopropyls-triethoxysilane 2.0mL is dissolved in the anhydrous second of 40mL Alcohol, 50 DEG C of stirring 6h of the mixed solution.0.5g surfactant Pluronic P123/Pluronic F127 mixtures（1/1, g/g）, 1.0g activated silica, the mixture of tetraethyl orthosilicate/methyl silicate（1/1, mL/mL）1.0mL is added to In system.The catalyst of triethylamine 4.0mL of 1mol/L is dropwise added dropwise, and 50 DEG C of stirrings 2h, Zhi Houbao are kept under the conditions of nitrogen atmosphere Hold 50 DEG C and be put into shaking table concussion hatching 12h.Room temperature is cooled to, by after with absolute ethyl alcohol flotation, obtaining uniform micro- after filtering Ball.
3. microballoon deionized water obtained in the previous step, absolute ethyl alcohol point 5 washings, to remove surfactant, filtering Vacuum drying 12h obtains amino modified mesoporous silicon oxide afterwards.
4. by prepared amino modified mesoporous silicon sphere, a pillar is assembled into, dry method loading is to the thick extracted extract of Chinese yew （Content of taxol 0.4%）Carry out column chromatography.Using ethanol/water gradient elution, different stream parts are collected, recycling design obtains solid, Gu Body is 8.8% through HPLC detection taxol purity, and the taxol rate of recovery is 86%.
Embodiment 5：
1. 10g preparing spherical SiO 2s are taken（100 mesh）It is added to 70mL Piranha solution（Hydrogen peroxide：The concentrated sulfuric acid=3/7, v/ v）In, plus rotor stirring, 120 DEG C of oil bath, 60min.Room temperature is cooled to, Piranha solution is diluted with ethanol（Now the concentrated sulfuric acid can Can heat release）, cooled and filtered rinsed 6 times repeatedly with ethanol, is washed till neutrality.12h is vacuum dried at 60 DEG C, is activated Silica, it is standby.
2. under the conditions of nitrogen atmosphere, functionalized reagent 3- aminopropyls-triethoxysilane/3- aminopropyls-triethoxysilicane Alkane mixture（1/1, v/v）2.0mL is dissolved in the absolute ethyl alcohol of 50mL, 50 DEG C of stirring 6h of the mixed solution.0.5g surfactants Pluronic F127,1.0g activated silica, methyl silicate 1.0mL is added in system.The catalysis of 1mol/L Agent HCl4.0mL is dropwise added dropwise, and 50 DEG C of stirring 12h are kept under the conditions of nitrogen atmosphere.Room temperature is cooled to, by absolute ethyl alcohol after filtering After flotation, uniform microballoon is obtained.
3. microballoon deionized water obtained in the previous step, absolute ethyl alcohol point 8 washings, to remove Pluronic F127, 10h is vacuum dried after filtering and obtains amino modified mesoporous silicon oxide.
4. by prepared modified mesoporous silicon sphere, a pillar is assembled into, dry method loading is to the thick extracted extract of Chinese yew（It is purple China fir alcohol content 0.4%）Carry out column chromatography.Using ethanol/water gradient elution, different stream parts are collected, recycling design obtains solid, solid It is 6.5% through HPLC detection taxol purity, the taxol rate of recovery is 94%.
Embodiment 6：
1. 10g preparing spherical SiO 2s are taken（120 mesh）It is added to 80mL Piranha solution（Hydrogen peroxide：The concentrated sulfuric acid=3/7, v/ v）In, plus rotor stirring, 120 DEG C of oil bath, 60min.Room temperature is cooled to, Piranha solution is diluted with ethanol（Now the concentrated sulfuric acid can Can heat release）, cooled and filtered rinsed 9 times repeatedly with ethanol, is washed till neutrality.12h is vacuum dried at 60 DEG C, is activated Silica, it is standby.
2. under the conditions of nitrogen atmosphere, functionalization examination 3- aminopropyls-triethoxysilane agent 2.5mL is dissolved in the anhydrous of 100mL Ethanol, 65 DEG C of stirring 6h of the mixed solution.0.5g surfactants F127,1.0g activated silica, tetraethyl orthosilicate 1.0mL is added in system.The catalyst nitric acid 3.0mL of 1mol/L is dropwise added dropwise, and 65 DEG C of stirrings are kept under the conditions of nitrogen atmosphere 2h, keeps 65 DEG C to be put into shaking table concussion hatching 7h afterwards.Room temperature is cooled to, by after with absolute ethyl alcohol flotation, obtaining size after filtering Homogeneous microballoon.
3. microballoon deionized water obtained in the previous step, absolute ethyl alcohol are washed 8 times respectively, to remove surfactant, are washed After washing, 8h is vacuum dried at 60 DEG C afterwards and obtains amino modified mesoporous silicon oxide.
4. by prepared modified mesoporous silicon sphere, a pillar is assembled into, dry method loading is to the thick extracted extract of Chinese yew（It is purple China fir alcohol content 0.4%）Carry out column chromatography.Using ethanol/water gradient elution, different stream parts are collected, recycling design obtains solid, solid It is 7.8% through HPLC detection taxol purity, the taxol rate of recovery is 85%..
Embodiment 7：
1. 10g preparing spherical SiO 2s are taken（120 mesh）It is added to 80mL Piranha solution（Hydrogen peroxide：The concentrated sulfuric acid=3/7, v/ v）In, plus rotor stirring, 120 DEG C of oil bath, 60min.Room temperature is cooled to, Piranha solution is diluted with ethanol（Now the concentrated sulfuric acid can Can heat release）, cooled and filtered rinsed 9 times repeatedly with ethanol, is washed till neutrality.12h is vacuum dried at 60 DEG C, is activated Silica, it is standby.
2. under the conditions of nitrogen atmosphere, functionalization examination 3- aminopropyls-triethoxysilane agent 2.5mL is dissolved in the acetonitrile of 50mL, 65 DEG C of stirring 6h of the mixed solution.0.5g surfactant Pluronic F127,1.0g activated silica, positive silicic acid Ethyl ester（TEOS）1.0mL is added in system.The catalyst HCl and acetate mixture of 1mol/L（1/1, v/v）4.0mL is dropwise It is added dropwise, 65 DEG C of stirring 2h is kept under the conditions of nitrogen atmosphere, keeps 65 DEG C to be put into shaking table concussion hatching 12h afterwards.It is cooled to room temperature, By after with absolute ethyl alcohol flotation, obtaining uniform microballoon after filtering.
3. microballoon deionized water obtained in the previous step, absolute ethyl alcohol point 5 washings, to remove Pluronic F127, 12h is vacuum dried after filtering and obtains amino modified mesoporous silicon oxide.
4. by prepared amino modified mesoporous silicon sphere, a pillar is assembled into, dry method loading is to the thick extracted extract of Chinese yew （Content of taxol 0.4%）Carry out column chromatography.Using ethanol/water gradient elution, different stream parts are collected, recycling design obtains solid, Gu Body is 5.3% through HPLC detection taxol purity, and the taxol rate of recovery is 91%.
Embodiment 8：
1. 10g preparing spherical SiO 2s are taken（120 mesh）It is added to 80mL Piranha solution（Hydrogen peroxide：The concentrated sulfuric acid=3/7, v/ v）In, plus rotor stirring, 120 DEG C of oil bath, 60min.Room temperature is cooled to, Piranha solution is diluted with ethanol（Now the concentrated sulfuric acid can Can heat release）, cooled and filtered rinsed 9 times repeatedly with ethanol, is washed till neutrality.12h is vacuum dried at 60 DEG C, is activated Silica, it is standby.
2. under the conditions of nitrogen atmosphere, functionalization examination 3- aminopropyls-triethoxysilane agent 2.5mL is dissolved in the anhydrous second of 50mL Alcohol, 50 DEG C of stirring 6h of the mixed solution.0.5g surfactants F127,1.0g activated silica, tetraethyl orthosilicate （TEOS）1.0mL is added in system.The catalyst n aOH4.0mL of 1mol/L is dropwise added dropwise, and 50 are kept under the conditions of nitrogen atmosphere DEG C stirring 2h, is fitted into afterwards 100mL polytetrafluoroethylene (PTFE) bottle in keep 100 DEG C be put into shaking table concussion hatch 12h.It is cooled to room temperature, By after with absolute ethyl alcohol flotation, obtaining uniform microballoon after filtering.
3. microballoon deionized water obtained in the previous step, absolute ethyl alcohol are washed 6 times respectively, to remove surfactant, are washed After washing, 6h is vacuum dried at 60 DEG C afterwards and obtains amino modified mesoporous silicon oxide.
4. by prepared modified mesoporous silicon sphere, a pillar is assembled into, dry method loading is to the thick extracted extract of Chinese yew（It is purple China fir alcohol content 0.4%）Carry out column chromatography.Using ethanol/water gradient elution, different stream parts are collected, recycling design obtains solid, solid It is 6.3% through HPLC detection taxol purity, the taxol rate of recovery is 87%.
Embodiment 9：
1. 10g preparing spherical SiO 2s are taken（80 mesh）It is added to 60mL Piranha solution（Hydrogen peroxide：The concentrated sulfuric acid=3/7, v/v） In, plus rotor stirring, 120 DEG C of oil bath, 60min.Room temperature is cooled to, Piranha solution is diluted with ethanol（Now the concentrated sulfuric acid may Heat release）, cooled and filtered rinsed 6 times repeatedly with ethanol, is washed till neutrality.12h is vacuum dried at 60 DEG C, is activated Silica, it is standby.
2. under the conditions of nitrogen atmosphere, functionalized reagent 3- aminopropyls-triethoxysilane 2.0mL is dissolved in the anhydrous second of 40mL Alcohol, 50 DEG C of stirring 6h of the mixed solution.0.5g surfactant Pluronic P123,1.0g activated silica, just The mixture of silester/methyl silicate（1/1, mL/mL）1.0mL is added in system.The catalyst n aOH/ of 1mol/L NH4OH mixtures（1/1, v/v）4.0mL is dropwise added dropwise, and 50 DEG C of stirring 2h are kept under the conditions of nitrogen atmosphere, and 50 DEG C are kept afterwards It is put into shaking table concussion hatching 12h.Room temperature is cooled to, by after with absolute ethyl alcohol flotation, obtaining uniform microballoon after filtering.
3. microballoon deionized water obtained in the previous step, absolute ethyl alcohol point 5 washings, to remove surfactant, filtering Vacuum drying 12h obtains amino modified mesoporous silicon oxide afterwards.
4. by prepared amino modified mesoporous silicon sphere, a pillar is assembled into, dry method loading is to the thick extracted extract of Chinese yew （Content of taxol 0.4%）Carry out column chromatography.Using ethanol/water gradient elution, different stream parts are collected, recycling design obtains solid, Gu Body is 8.1% through HPLC detection taxol purity, and the taxol rate of recovery is 88%.

Claims (7)

1. a kind of preparation method of amino modified mesoporous silicon oxide for separating and purifying taxol is comprised the following steps：
(1) preparing spherical SiO 2 for taking 10g20-300 mesh is added to the hydrogen peroxide and dense sulphur that 10-100mL volume ratios are 3/7 In acid solution, plus rotor stirring, 120 DEG C of oil bath, 60min；Room temperature is cooled to, Piranha solution, mistake after cooling are diluted with ethanol Filter, is rinsed 5-10 times repeatedly with ethanol, is washed till neutrality, and 12h is vacuum dried at 60 DEG C, and the silica for being activated is standby With；
(2) under the conditions of nitrogen atmosphere, silane of the 1.5-3.5mL containing amino is dissolved in the anhydrous of 10-100mL as functionalized reagent Ethanol, 50 DEG C of stirring 1-6h of the mixed solution, 0.1-0.9g surfactants take the activated titanium dioxides of 1.0g as soft template Silicon and 0.5-2.5mL tetraethyl orthosilicates or methyl silicate or their mixture are added in system, the catalyst of 1mol/L Solution 3-7mL is added dropwise over, and 50 DEG C of stirring 1-2h are kept under the conditions of nitrogen atmosphere, keeps 50 DEG C to be put into shaking table concussion hatching afterwards 1-12h, is cooled to room temperature, by after with absolute ethyl alcohol flotation, obtaining uniform microballoon after filtering；
(3) microballoon deionized water obtained in the previous step, absolute ethyl alcohol are washed 3-10 times respectively, to remove surfactant, are washed 6-12h is vacuum dried after washing, at 60 DEG C obtain amino modified mesoporous silicon oxide.
2. the preparation side of a kind of amino modified mesoporous silicon oxide for separating and purifying taxol according to claim 1 Method, it is characterised in that：The silane containing amino is 3- aminopropyls-trimethoxy silane, 3- aminopropyls-triethoxysilane, One kind or their mixture in N- aminoethyls-γ-aminopropyltrimethoxysilane.
3. the preparation side of a kind of amino modified mesoporous silicon oxide for separating and purifying taxol according to claim 1 Method, it is characterised in that：The surfactant is Pluronic F127, Pluronic P123, cetyl trimethyl bromination One kind or their mixture in ammonium.
4. the preparation side of a kind of amino modified mesoporous silicon oxide for separating and purifying taxol according to claim 1 Method, it is characterised in that：The catalyst is acid or alkali.
5. the preparation side of a kind of amino modified mesoporous silicon oxide for separating and purifying taxol according to claim 4 Method, it is characterised in that：The acid is the one kind or their mixture in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid.
6. the preparation side of a kind of amino modified mesoporous silicon oxide for separating and purifying taxol according to claim 4 Method, it is characterised in that：The alkali is NH4One kind or their mixture in OH, triethylamine, NaOH.
7. the preparation side of a kind of amino modified mesoporous silicon oxide for separating and purifying taxol according to claim 1 Method, it is characterised in that：The new function earth silicon material of the preparation, can be applied to isolating and purifying for taxol.
CN201611010222.7A 2016-11-17 2016-11-17 A kind of preparation method of the amino modified mesoporous silicon oxide for separating and purifying taxol Pending CN106732476A (en)

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