CN107382707A - A kind of method of efficiently purifying alpha linolenic acid - Google Patents
A kind of method of efficiently purifying alpha linolenic acid Download PDFInfo
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- CN107382707A CN107382707A CN201710654729.4A CN201710654729A CN107382707A CN 107382707 A CN107382707 A CN 107382707A CN 201710654729 A CN201710654729 A CN 201710654729A CN 107382707 A CN107382707 A CN 107382707A
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- linolenic acid
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- infusorial earth
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
Abstract
The present invention provides a kind of method of efficiently purifying alpha linolenic acid, comprises the following steps：(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, the ethanol solution that mass fraction is 95% is added, after temperature stabilization, linseed oil is added portionwise, insulation reaction 0.5h 1.5h, obtains saponification mixture；(2) pH is adjusted：The pH of saponification mixture is adjusted to 34 with hydrochloric acid, isothermal reaction, obtains acidic mixture；(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, and the aqueous phase is saturated aqueous common salt, and the organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha linolenic acid mother liquor；(4) method purifying is included：Method purifying alpha linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha linolenic acid crude product；(5) column chromatography method purifies：Column chromatography method purification of alpha flax acid crude is chromatographed using modification infusorial earth, obtains high-purity alpha linolenic acid.
Description
Technical field
The invention belongs to linolenic preparation method technical field, and specifically, the present invention provides a kind of efficiently purifying α-Asia
The method of numb acid.
Background technology
Alpha-linolenic acid (ALA) is Cis cis 9,12,15-oc-tadecatrienoic acids, is that polyunsaturated fatty acid has as ω -3
Significant pharmacological action and nutritive value.Alpha-linolenic acid is essential fatty acid, can only be absorbed from external source food, α-flax
Acid is EPA and DHA precursor, is the life core substance for maintaining the evolution of mankind's brain, has and increases intelligence, protection eyesight, delays
The multiple functions such as aging, it can effectively suppress thrombotic diseases, prevention myocardial infarction, cerebral infarction, reducing blood lipid, hypotensive, suppression
Hemorrhagic cerebral apoplexy processed, the generation for suppressing cancer and transfer, prevention and suppress senile dementia etc..
At present, alpha-linolenic acid is widely used in fields such as medicine, food, cosmetics.Its source be concentrated mainly on perilla herb oil,
Small ancestor's oil plant such as 'Heijialun ' seed oil, linseed oil, linseed oil, synthetism wood oil.
The method of currently used separating-purifying alpha-linolenic acid has urea clathrate, molecular distillation, supercritical carbon dioxide extraction
Take, silver ion complexation the methods of.Wherein urea adduct method due to its separation equipment it is simple, operating method is simple and easy, and urea can
To recycle, environmental pollution is small, the technique for turning into the purifying of the preferred fatty acid mixed of increasing enterprise.It is but single
Urea adduct method there is also the separation of unrighted acid composition is incomplete, yield is low, residual urea, single polyunsaturated fat
The shortcomings such as sour purity is low.Silver ion complexation, this method separation costs are high, introduce anion and easily produce heavy metal pollution, to food
The preparation of product raw material does not apply to, and alpha-linolenic acid is separated using silver ion silicagel column in addition, alpha-linolenic acid is oxidized easily.
In view of the above-mentioned problems, the present invention provides a kind of method of efficiently purifying alpha-linolenic acid, mainly by including method and post
Chromatography method carries out purification alpha-linolenic acid, and resveratrol is added in mobile phase, prevents that oxygen occurs for alpha-linolenic acid in purge process
Change.
The content of the invention
In order to solve the above problems, the present invention provides a kind of method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction
0.5h-1.5h, obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha-linolenic acid crude product；
(5) column chromatography method purifies：Column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth, obtains height
Pure alpha-linolenic acid；
Wherein, the modified Cucurbituril is poly-dopamine modified lithium Cucurbituril, and the modification infusorial earth connects to be polyamide modified
The diatomite of eight (oxosilanes of aminophenyl three) of branch；In the modification infusorial earth chromatography column chromatography method mobile phase be petroleum ether,
Ethanol, resveratrol.
In one embodiment, the concentration of sodium hydrate aqueous solution described in the step (1) is (2-5) mol/L.
In one embodiment, sodium hydrate aqueous solution described in the step (1) and the mass fraction are 95%
Ethanol solution, the linseed oil weight ratio be 1：(3-7)：(4-7).
In one embodiment, petroleum ether and institute described in mobile phase in the modification infusorial earth chromatography column chromatography method
State ethanol, the weight ratio of the resveratrol is 1：(0.05-0.2)：(0.005-0.015).
In one embodiment, petroleum ether and institute described in mobile phase in the modification infusorial earth chromatography column chromatography method
State ethanol, the weight ratio of the resveratrol is 1：0.15：0.008.
In one embodiment, the flow velocity of mobile phase is (1ml- in the modification infusorial earth chromatography column chromatography method
5ml)/min。
In one embodiment, the flow velocity of mobile phase is 4ml/min in the modification infusorial earth chromatography column chromatography method.
In one embodiment, Cucurbituril described in the poly-dopamine modified lithium Cucurbituril is cucurbit [8] urea.
In one embodiment, it is described that following step is included using modified Cucurbituril inclusion method purifying alpha-linolenic acid mother liquor
Suddenly：
Mixed solution, the alpha-linolenic acid mother liquor of modified Cucurbituril and ethanol are added into reactor, is warming up to 75~80 DEG C,
Insulation reaction 1-3h, 5-10 DEG C, insulation reaction 1-3h is cooled to, filtered, filtrate recycling ethanol, petroleum ether extraction, then use successively
Water, the NaCl solution that mass fraction is 10% are washed, and are dried, recycling design, are obtained alpha-linolenic acid crude product；The modified Cucurbituril with
The weight ratio of modified Cucurbituril described in the mixed solution of ethanol and the ethanol is 1：8, the mass fraction of the ethanol is
95%；The weight ratio of the modified Cucurbituril and the alpha-linolenic acid mother liquor is 1：2.5.
In one embodiment, it is described that purifying alpha-linolenic acid crude product in column chromatography method is chromatographed using modification infusorial earth
Method comprises the following steps：
(1) alpha-linolenic acid dissolving crude product is obtained into alpha-linolenic acid crude product solution, along polyamide chromatography column wall with mobile phase
Alpha-linolenic acid crude product solution is added, then adds mobile phase, the quality of alpha-linolenic acid crude product in the alpha-linolenic acid crude product solution
Fraction is 40%；
(2) chromatographic column lower piston, mobile phase outflow are opened；
(3) sample piecewise acquisition, the change of impurity and sample in efflux is tracked by TLC, collects pure sample product
Part, removal of solvent under reduced pressure, obtain high-purity alpha-linolenic acid.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Embodiment
Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When contradiction be present, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside the claim as entirety.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item that describes thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to represent that the present invention is not limited to this
Quantity, include the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.It is approximate in some examples
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article " one kind " before key element of the present invention or component and "one" to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means the polymer prepared by polymerizeing at least two different monomers.Generic term " EVA " includes
(its is general with term " terpolymer " for term " copolymer " (its typically to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It is also included by polymerizeing more kinds of monomers the polymer that manufactures.
" blend " means that two or more polymer mixes the polymer to be formed by physics or chemical method jointly.
The present invention provides a kind of method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction
0.5h-1.5h, obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha-linolenic acid crude product；
(5) column chromatography method purifies：Column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth, obtains height
Pure alpha-linolenic acid；
Wherein, the modified Cucurbituril is poly-dopamine modified lithium Cucurbituril, and the modification infusorial earth connects to be polyamide modified
The diatomite of eight (oxosilanes of aminophenyl three) of branch；In the modification infusorial earth chromatography column chromatography method mobile phase be petroleum ether,
Ethanol, resveratrol.
In the present invention, No. CAS of the resveratrol is 501-36-0.
In one embodiment, the concentration of sodium hydrate aqueous solution described in the step (1) is (2-5) mol/L；It is excellent
Selection of land, the concentration of sodium hydrate aqueous solution is 4mol/L described in the step (1).
In one embodiment, sodium hydrate aqueous solution described in the step (1) and the mass fraction are 95%
Ethanol solution, the linseed oil weight ratio be 1：(3-7)：(4-7)；Preferably, hydroxide described in the step (1)
Ethanol solution that sodium water solution and the mass fraction are 95%, the weight ratio of the linseed oil are 1：5：6.
In one embodiment, petroleum ether and institute described in mobile phase in the modification infusorial earth chromatography column chromatography method
State ethanol, the weight ratio of the resveratrol is 1：(0.05-0.2)：(0.005-0.015).
In one embodiment, petroleum ether and institute described in mobile phase in the modification infusorial earth chromatography column chromatography method
State ethanol, the weight ratio of the resveratrol is 1：0.15：0.008.
In one embodiment, the flow velocity of mobile phase is (1ml- in the modification infusorial earth chromatography column chromatography method
5ml)/min。
In one embodiment, the flow velocity of mobile phase is 4ml/min in the modification infusorial earth chromatography column chromatography method.
In one embodiment, Cucurbituril described in the poly-dopamine modified lithium Cucurbituril is cucurbit [8] urea.
Cucurbit [8] urea molecule is a kind of cyclic compound of tubbiness, and its cavity is hydrophobic, and both ends open, empty
Chamber two is smaller, middle very big, and for cavity by carbonyl around forming, its both ends open size is identical.Cavity can be passed through
The organic guest molecules of hydrophobic effect inclusion, while the circular multiple carbonyls of two-port can turn into cation binding site, make it
With extremely strong Subjective and Objective binding ability.Dipole polarization carbonyl can also act on key by hydrogen bond of ion-dipole and allophanyl etc.
Metal ion, organic cation and molecule object, its cavity structure rigidly have the molecule distinguishability of selection selectivity, can
Completely or partially stable Supramolecular inclusion complex is formed as molecular bulk with reference to the moderate object of many structure sizes.
The caged macrocyclic host molecule of cucurbit [8] urea has special structure, has good chemical stability and heat steady
It is qualitative, and there is very high selection recognition capability to guest molecule, pass through poly-dopamine modified lithium cucurbit [8] urea, functionalization base
Group introducings can be in various degree strengthen cyclodextrin Molecular Recognization, break its own limitation (rigidity of structure,
Low water solubility), make it have good cation bonding position around substantial amounts of carbonyl around cucurbit [8] urea cavity in addition
Point, and its port is formed by carbonyl group, so with the strong Subjective and Objective binding ability of selectivity, and then in flax acid mother liquor
The mixture of different component has good separating effect.
The preparation method of the poly-dopamine modified lithium Cucurbituril comprises the following steps：
(1) cucurbit [8] urea, ammonium persulfate, deionized water are added into reactor, stirring, nitrogen is passed through, is warming up to 80
DEG C, 2-3h is reacted, acrylic acid is slowly added dropwise, after being added dropwise, 80 DEG C of insulation reaction 8-10h, stops reaction, is cooled to room temperature,
Solution is transferred in the bag filter that molecular weight is 2000, bag filter is put into the outside system for recirculated water and dialysed,
Dialysis time is 24h；Material in bag filter is concentrated under reduced pressure into thick shape, adds acetone, is stirred, filtering, 40 DEG C are dried under reduced pressure
48h, cucurbit [8] urea bridging acrylic solid is obtained, grind, be sealed；Cucurbit [8] urea and the ammonium persulfate, institute
The mol ratio for stating acrylic acid is 1：5：16；Cucurbit [8] urea and the weight ratio of the deionized water, the acetone are 1：15：
20；
(2) cucurbit [8] urea bridging acrylic acid, 1mol/L sodium hydrate aqueous solutions in step (1), room are added into reactor
Temperature stirring 1h, filtering, 60 DEG C are dried under reduced pressure 12h, then add the dopamine solution for being dissolved in pH=8.5Tris cushioning liquid,
0.5h is stirred, is stored at room temperature 24h, filters, 100 DEG C of constant pressure and dry 10h, obtains poly-dopamine modified lithium cucurbit [8] urea, the cucurbit
[8] the weight ratio of urea bridging acrylic acid and the sodium hydrate aqueous solution, the dopamine is 1：4：1.6；The dopamine with
The weight ratio of the pH=8.5Tris cushioning liquid is 1：6.
The modification infusorial earth preparation method comprises the following steps：
(1) purified silicious earth：Diatomite original soil is placed in baking oven, temperature is maintained at 120 DEG C, heats 36h, obtains drying
Diatomite original soil；Dry diatomite original soil, sulfuric acid solution are added into reactor, is warming up to 90 DEG C, 1h is stirred, is cooled to
Room temperature, filtering, deionized water elute to pH and are dried under reduced pressure 12h for 6,70 DEG C, the diatomite being acidified；The diatom of the drying
The weight ratio of native original soil and the sulfuric acid solution is 1：4；The concentration of the sulfuric acid solution is 2mol/L；By the silicon of obtained acidifying
Diatomaceous earth calcines 2h under the conditions of 850 DEG C, the diatomite after being calcined；
(2) γ-glycidyl ether oxygen propyl trimethoxy silicane is added into reactor, mass fraction is 90% ethanol
The aqueous solution, acetic acid is added dropwise and adjusts pH=3-4, after dripping off, it is transparent to solution to continue stirring, after adding step (1) obtained calcining
Diatomite, after 0.5-1h is stirred at room temperature, add eight (oxosilane of aminophenyl three) (CAS：518359-82-5), 50 DEG C of stirring 3h
After filter, filter cake reacts 2h after 50-60 DEG C of dry 2h, then at 120 DEG C of freeze-day with constant temperature, cooling, obtains (the aminophenyl three of grafting eight
Oxosilane) diatomite；It is diatomite after the calcining and the γ-glycidyl ether oxygen propyl trimethoxy silicane, described
The weight ratio for the ethanol water that eight (oxosilanes of aminophenyl three), the mass fraction are 90% is 1：0.03：0.2：10；
(3) acrylamide, deionized water are added into reactor, is warming up to 40 DEG C, and nitrogen is protected, and stirs 0.5h, so
After add ammonium persulfate, 2- acrylamide-2-methyl propane sulfonics, tetraethyl orthosilicate, insulation reaction 3h, add step (2) and obtain
Grafting eight (oxosilane of aminophenyl three) diatomite, stir 0.5h, be stored at room temperature 24h, filter, 100 DEG C of constant pressure and dries
10h, obtain modification infusorial earth；The acrylamide and the deionized water, the ammonium persulfate, the 2- acrylamides -2-
Methyl propane sulfonic acid, the tetraethyl orthosilicate, the diatomaceous weight ratio of eight (oxosilanes of aminophenyl three) of the grafting are 7：20：
0.02：2：0.3:28.
In the present invention, the preparation method of the modification infusorial earth chromatographic column comprises the following steps：
(1) filler pre-treatment：Modification infusorial earth powder is added in the absolute ethyl alcohol of 6 times of weight, after immersion, filtering,
Ethanol is removed under reduced pressure；It is then added in the 1mol/L of 6 times of weight sodium hydrate aqueous solution and stirs, filters, be washed to
It is neutral to obtain modification infusorial earth wet-milling；Modification infusorial earth wet-milling is added in the 1mol/L of 6 times of weight aqueous acetic acid and stirred
Uniformly, neutrality is washed to, then 90 DEG C of dry 6h obtain pretreated modification infusorial earth powder to constant weight；
(2) chromatographic column loads：The pretreated modification infusorial earth powder obtained in step (1) is added to 6 times of weight
Petroleum ether in, after soaking 6h, pour into the chromatographic column equipped with scheduled volume petroleum ether, allow modification infusorial earth powder natural subsidence,
After diatomite powder sedimentation to be modified is fine and close, chromatographic column lower piston is opened, allows petroleum ether slowly to flow out, until liquid level is in modified silicon
0.4cm on diatomaceous earth filler, closure piston obtain modification infusorial earth chromatographic column.
In one embodiment, the granularity of the modification infusorial earth is 100-300 mesh；Preferably, the modified diatom
The granularity of soil is 300 mesh.
In one embodiment, it is described that following step is included using modified Cucurbituril inclusion method purifying alpha-linolenic acid mother liquor
Suddenly：
Mixed solution, the alpha-linolenic acid mother liquor of modified Cucurbituril and ethanol are added into reactor, is warming up to 75~80 DEG C,
Insulation reaction 1-3h, 5-10 DEG C, insulation reaction 1-3h is cooled to, filtered, filtrate recycling ethanol, petroleum ether extraction, then use successively
Water, the NaCl solution that mass fraction is 10% are washed, and are dried, recycling design, are obtained alpha-linolenic acid crude product；The modified Cucurbituril with
The weight ratio of modified Cucurbituril described in the mixed solution of ethanol and the ethanol is 1：8, the mass fraction of the ethanol is
95%；The weight ratio of the modified Cucurbituril and the alpha-linolenic acid mother liquor is 1：2.5.
In one embodiment, it is described that purifying alpha-linolenic acid crude product in column chromatography method is chromatographed using modification infusorial earth
Method comprises the following steps：
(1) alpha-linolenic acid dissolving crude product is obtained into alpha-linolenic acid crude product solution, along polyamide chromatography column wall with mobile phase
Alpha-linolenic acid crude product solution is added, then adds mobile phase, the quality of alpha-linolenic acid crude product in the alpha-linolenic acid crude product solution
Fraction is 40%；
(2) chromatographic column lower piston, mobile phase outflow are opened；
(3) sample piecewise acquisition, the change of impurity and sample in efflux is tracked by TLC, collects pure sample product
Part, removal of solvent under reduced pressure, obtain high-purity alpha-linolenic acid.
The A1 in diatomite original soil after pickling processes2O3, Fe2O3, CaO, MgO, K2The impurity such as O largely reduce and silicon
The micropore of frond is revealed, and the aperture of silica discs is effectively dredged, and diatomaceous adsorptivity, which responds, to be carried
It is high；Diatomite is accompanied by the change than surface, pore structure in thermal histories, diatomite after roasting, surface water and its
Its organic matter removes, and reaches maximum than surface, by being grafted eight (oxosilanes of aminophenyl three) over celite, introduces amino
And benzene radicals, diatomaceous mechanical strength and stability are improved, the Hyarogen-bonding with composition for separating, promotes leukotrienes to mix
The separation of compound；Polar group is further introduced into additionally by the diatomite of eight (oxosilanes of aminophenyl three) of polyamide modified grafting
Group, the separation of alpha-linolenic acid and gamma-Linolenic acid is further improved, obtains the alpha-linolenic acid of high-purity.
Resveratrol is added in the present invention in mobile phase, alpha-linolenic acid can preferably be purified, it is therefore prevented that α-
Oxidation in leukotrienes purge process；Other resveratrol has very high health value, using more preferable with effect meeting in food.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used be all it is commercially available, be purchased from traditional Chinese medicines chemical reagent.
Embodiment 1
The method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction 1h,
Obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha-linolenic acid crude product；
(5) column chromatography method purifies：Column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth, obtains height
Pure alpha-linolenic acid；
Wherein, the modified Cucurbituril is poly-dopamine modified lithium Cucurbituril, and the modification infusorial earth connects to be polyamide modified
The diatomite of eight (oxosilanes of aminophenyl three) of branch；In the modification infusorial earth chromatography column chromatography method mobile phase be petroleum ether,
Ethanol, resveratrol；The concentration of sodium hydrate aqueous solution is 4mol/L described in the step (1)；Described in the step (1)
Ethanol solution that sodium hydrate aqueous solution and the mass fraction are 95%, the weight ratio of the linseed oil are 1：5：6；It is described
The weight ratio of petroleum ether and the ethanol, the resveratrol is described in mobile phase in modification infusorial earth chromatography column chromatography method
1：0.15：0.008；The flow velocity of mobile phase is 4ml/min in the modification infusorial earth chromatography column chromatography method；The poly-dopamine
Cucurbituril is cucurbit [8] urea described in modified Cucurbituril；The granularity of the modification infusorial earth is 300 mesh；
The method for including method purifying alpha-linolenic acid mother liquor using modified Cucurbituril comprises the following steps：
Mixed solution, the alpha-linolenic acid mother liquor of modified Cucurbituril and ethanol are added into reactor, is warming up to 75~80 DEG C,
Insulation reaction 2h, 5-10 DEG C, insulation reaction 3h is cooled to, filtered, filtrate recycling ethanol, petroleum ether extraction, then successively with water, matter
Measure the NaCl solution that fraction is 10% to wash, dry, recycling design, obtain alpha-linolenic acid crude product；The modified Cucurbituril and ethanol
Mixed solution described in the weight ratio of modified Cucurbituril and the ethanol be 1：8, the mass fraction of the ethanol is 95%；Institute
The weight ratio for stating modified Cucurbituril and the alpha-linolenic acid mother liquor is 1：2.5.
The method that column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth is comprised the following steps：
(1) alpha-linolenic acid dissolving crude product is obtained into alpha-linolenic acid crude product solution, along polyamide chromatography column wall with mobile phase
Alpha-linolenic acid crude product solution is added, then adds mobile phase, the quality of alpha-linolenic acid crude product in the alpha-linolenic acid crude product solution
Fraction is 40%；
(2) chromatographic column lower piston, mobile phase outflow are opened；
(3) sample piecewise acquisition, the change of impurity and sample in efflux is tracked by TLC, collects pure sample product
Part, removal of solvent under reduced pressure, obtain high-purity alpha-linolenic acid.
The preparation method of the poly-dopamine modified lithium Cucurbituril comprises the following steps：
(1) cucurbit [8] urea, ammonium persulfate, deionized water are added into reactor, stirring, nitrogen is passed through, is warming up to 80
DEG C, 2h is reacted, acrylic acid is slowly added dropwise, after being added dropwise, 80 DEG C of insulation reaction 8h, stops reaction, room temperature is cooled to, by solution
It is transferred in the bag filter that molecular weight is 2000, bag filter is put into the outside system for recirculated water and dialysed, during dialysis
Between be 24h；Material in bag filter is concentrated under reduced pressure into thick shape, adds acetone, is stirred, filtering, 40 DEG C are dried under reduced pressure 48h, obtain
Cucurbit [8] urea bridging acrylic solid, grinding, is sealed；Cucurbit [8] urea and the ammonium persulfate, the acrylic acid
Mol ratio be 1：5：16；Cucurbit [8] urea and the weight ratio of the deionized water, the acetone are 1：15：20；
(2) cucurbit [8] urea bridging acrylic acid, 1mol/L sodium hydrate aqueous solutions in step (1), room are added into reactor
Temperature stirring 1h, filtering, 60 DEG C are dried under reduced pressure 12h, then add the dopamine solution for being dissolved in pH=8.5Tris cushioning liquid,
0.5h is stirred, is stored at room temperature 24h, filters, 100 DEG C of constant pressure and dry 10h, obtains poly-dopamine modified lithium cucurbit [8] urea, the cucurbit
[8] the weight ratio of urea bridging acrylic acid and the sodium hydrate aqueous solution, the dopamine is 1：4：1.6；The dopamine with
The weight ratio of the pH=8.5Tris cushioning liquid is 1：6.
The preparation method of the modification infusorial earth chromatographic column comprises the following steps：
(1) filler pre-treatment：Modification infusorial earth powder is added in the absolute ethyl alcohol of 6 times of weight, after immersion, filtering,
Ethanol is removed under reduced pressure；It is then added in the 1mol/L of 6 times of weight sodium hydrate aqueous solution and stirs, filters, be washed to
It is neutral to obtain modification infusorial earth wet-milling；Modification infusorial earth wet-milling is added in the 1mol/L of 6 times of weight aqueous acetic acid and stirred
Uniformly, neutrality is washed to, then 90 DEG C of dry 6h obtain pretreated modification infusorial earth powder to constant weight；
(2) chromatographic column loads：The pretreated modification infusorial earth powder obtained in step (1) is added to 6 times of weight
Petroleum ether in, after soaking 6h, pour into the chromatographic column equipped with scheduled volume petroleum ether, allow modification infusorial earth powder natural subsidence,
After diatomite powder sedimentation to be modified is fine and close, chromatographic column lower piston is opened, allows petroleum ether slowly to flow out, until liquid level is in modified silicon
0.4cm on diatomaceous earth filler, closure piston obtain modification infusorial earth chromatographic column.
The modification infusorial earth preparation method comprises the following steps：
(1) purified silicious earth：Diatomite original soil is placed in baking oven, temperature is maintained at 120 DEG C, heats 36h, obtains drying
Diatomite original soil；Dry diatomite original soil, sulfuric acid solution are added into reactor, is warming up to 90 DEG C, 1h is stirred, is cooled to
Room temperature, filtering, deionized water elute to pH and are dried under reduced pressure 12h for 6,70 DEG C, the diatomite being acidified；The diatom of the drying
The weight ratio of native original soil and the sulfuric acid solution is 1：4；The concentration of the sulfuric acid solution is 2mol/L；By the silicon of obtained acidifying
Diatomaceous earth calcines 2h under the conditions of 850 DEG C, the diatomite after being calcined；
(2) γ-glycidyl ether oxygen propyl trimethoxy silicane is added into reactor, mass fraction is 90% ethanol
The aqueous solution, acetic acid is added dropwise and adjusts pH=3-4, after dripping off, it is transparent to solution to continue stirring, after adding step (1) obtained calcining
Diatomite, after 1h is stirred at room temperature, eight (oxosilanes of aminophenyl three) are added, are filtered after 50 DEG C of stirring 3h, filter cake is in 55 DEG C of dryings
After 2h, 2h is reacted then at 120 DEG C of freeze-day with constant temperature, is cooled, obtains the diatomite of grafting eight (oxosilane of aminophenyl three)；The calcining
It is diatomite afterwards and the γ-glycidyl ether oxygen propyl trimethoxy silicane, eight (oxosilanes of aminophenyl three), described
The weight ratio for the ethanol water that mass fraction is 90% is 1：0.03：0.2：10；
(3) acrylamide, deionized water are added into reactor, is warming up to 40 DEG C, and nitrogen is protected, and stirs 0.5h, so
After add ammonium persulfate, 2- acrylamide-2-methyl propane sulfonics, tetraethyl orthosilicate, insulation reaction 3h, add step (2) and obtain
Grafting eight (oxosilane of aminophenyl three) diatomite, stir 0.5h, be stored at room temperature 24h, filter, 100 DEG C of constant pressure and dries
10h, obtain modification infusorial earth；The acrylamide and the deionized water, the ammonium persulfate, the 2- acrylamides -2-
Methyl propane sulfonic acid, the tetraethyl orthosilicate, the diatomaceous weight ratio of eight (oxosilanes of aminophenyl three) of the grafting are 7：20：
0.02：2：0.3:28.
Embodiment 2
The method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction 1h,
Obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha-linolenic acid crude product；
(5) column chromatography method purifies：Column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth, obtains height
Pure alpha-linolenic acid；
Wherein, the modified Cucurbituril is poly-dopamine modified lithium Cucurbituril, and the modification infusorial earth connects to be polyamide modified
The diatomite of eight (oxosilanes of aminophenyl three) of branch；In the modification infusorial earth chromatography column chromatography method mobile phase be petroleum ether,
Ethanol, resveratrol；The concentration of sodium hydrate aqueous solution is 4mol/L described in the step (1)；Described in the step (1)
Ethanol solution that sodium hydrate aqueous solution and the mass fraction are 95%, the weight ratio of the linseed oil are 1：3：6；It is described
The weight ratio of petroleum ether and the ethanol, the resveratrol is described in mobile phase in modification infusorial earth chromatography column chromatography method
1：0.15：0.008；The flow velocity of mobile phase is 4ml/min in the modification infusorial earth chromatography column chromatography method；The poly-dopamine
Cucurbituril is cucurbit [8] urea described in modified Cucurbituril；The granularity of the modification infusorial earth is 300 mesh；
It is described that the method for method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, described chromatographed using modification infusorial earth
The method of purifying alpha-linolenic acid crude product, the preparation method of the poly-dopamine modified lithium Cucurbituril, the modification in column chromatography method
The preparation method of diatomite chromatographic column, the modification infusorial earth preparation method are the same as embodiment 1.
Embodiment 3
The method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction 1h,
Obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha-linolenic acid crude product；
(5) column chromatography method purifies：Column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth, obtains height
Pure alpha-linolenic acid；
Wherein, the modified Cucurbituril is poly-dopamine modified lithium Cucurbituril, and the modification infusorial earth connects to be polyamide modified
The diatomite of eight (oxosilanes of aminophenyl three) of branch；In the modification infusorial earth chromatography column chromatography method mobile phase be petroleum ether,
Ethanol, resveratrol；The concentration of sodium hydrate aqueous solution is 4mol/L described in the step (1)；Described in the step (1)
Ethanol solution that sodium hydrate aqueous solution and the mass fraction are 95%, the weight ratio of the linseed oil are 1：6：7；It is described
The weight ratio of petroleum ether and the ethanol, the resveratrol is described in mobile phase in modification infusorial earth chromatography column chromatography method
1：0.15：0.008；The flow velocity of mobile phase is 4ml/min in the modification infusorial earth chromatography column chromatography method；The poly-dopamine
Cucurbituril is cucurbit [8] urea described in modified Cucurbituril；The granularity of the modification infusorial earth is 300 mesh；
It is described that the method for method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, described chromatographed using modification infusorial earth
The method of purifying alpha-linolenic acid crude product, the preparation method of the poly-dopamine modified lithium Cucurbituril, the modification in column chromatography method
The preparation method of diatomite chromatographic column, the modification infusorial earth preparation method are the same as embodiment 1.
Embodiment 4
The method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction 1h,
Obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha-linolenic acid crude product；
(5) column chromatography method purifies：Column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth, obtains height
Pure alpha-linolenic acid；
Wherein, the modified Cucurbituril is poly-dopamine modified lithium Cucurbituril, and the modification infusorial earth connects to be polyamide modified
The diatomite of eight (oxosilanes of aminophenyl three) of branch；In the modification infusorial earth chromatography column chromatography method mobile phase be petroleum ether,
Ethanol, resveratrol；The concentration of sodium hydrate aqueous solution is 4mol/L described in the step (1)；Described in the step (1)
Ethanol solution that sodium hydrate aqueous solution and the mass fraction are 95%, the weight ratio of the linseed oil are 1：5：6；It is described
The weight ratio of petroleum ether and the ethanol, the resveratrol is described in mobile phase in modification infusorial earth chromatography column chromatography method
1：0.05：0.01；The flow velocity of mobile phase is 4ml/min in the modification infusorial earth chromatography column chromatography method；The poly-dopamine
Cucurbituril is cucurbit [8] urea described in modified Cucurbituril；The granularity of the modification infusorial earth is 300 mesh；
It is described that the method for method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, described chromatographed using modification infusorial earth
The method of purifying alpha-linolenic acid crude product, the preparation method of the poly-dopamine modified lithium Cucurbituril, the modification in column chromatography method
The preparation method of diatomite chromatographic column, the modification infusorial earth preparation method are the same as embodiment 1.
Embodiment 5
The method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction 1h,
Obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha-linolenic acid crude product；
(5) column chromatography method purifies：Column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth, obtains height
Pure alpha-linolenic acid；
Wherein, the modified Cucurbituril is poly-dopamine modified lithium Cucurbituril, and the modification infusorial earth connects to be polyamide modified
The diatomite of eight (oxosilanes of aminophenyl three) of branch；In the modification infusorial earth chromatography column chromatography method mobile phase be petroleum ether,
Ethanol, resveratrol；The concentration of sodium hydrate aqueous solution is 4mol/L described in the step (1)；Described in the step (1)
Ethanol solution that sodium hydrate aqueous solution and the mass fraction are 95%, the weight ratio of the linseed oil are 1：5：6；It is described
The weight ratio of petroleum ether and the ethanol, the resveratrol is described in mobile phase in modification infusorial earth chromatography column chromatography method
1：0.2：0.005；The flow velocity of mobile phase is 4ml/min in the modification infusorial earth chromatography column chromatography method；The poly-dopamine
Cucurbituril is cucurbit [8] urea described in modified Cucurbituril；The granularity of the modification infusorial earth is 300 mesh；
It is described that the method for method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, described chromatographed using modification infusorial earth
The method of purifying alpha-linolenic acid crude product, the preparation method of the poly-dopamine modified lithium Cucurbituril, the modification in column chromatography method
The preparation method of diatomite chromatographic column, the modification infusorial earth preparation method are the same as embodiment 1.
Embodiment 6
The method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction 1h,
Obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha-linolenic acid crude product；
(5) column chromatography method purifies：Column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth, obtains height
Pure alpha-linolenic acid；
Wherein, the modified Cucurbituril is poly-dopamine modified lithium Cucurbituril, and the modification infusorial earth connects to be polyamide modified
The diatomite of eight (oxosilanes of aminophenyl three) of branch；In the modification infusorial earth chromatography column chromatography method mobile phase be petroleum ether,
Ethanol, resveratrol；The concentration of sodium hydrate aqueous solution is 4mol/L described in the step (1)；Described in the step (1)
Ethanol solution that sodium hydrate aqueous solution and the mass fraction are 95%, the weight ratio of the linseed oil are 1：5：6；It is described
The weight ratio of petroleum ether and the ethanol, the resveratrol is described in mobile phase in modification infusorial earth chromatography column chromatography method
1：0.15：0.008；The flow velocity of mobile phase is 4ml/min in the modification infusorial earth chromatography column chromatography method；The poly-dopamine
Cucurbituril is cucurbit [8] urea described in modified Cucurbituril；The granularity of the modification infusorial earth is 200 mesh；
It is described that the method for method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, described chromatographed using modification infusorial earth
The method of purifying alpha-linolenic acid crude product, the preparation method of the poly-dopamine modified lithium Cucurbituril, the modification in column chromatography method
The preparation method of diatomite chromatographic column, the modification infusorial earth preparation method are the same as embodiment 1.
Comparative example 1
The method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction 1h,
Obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha-linolenic acid crude product；
(5) column chromatography method purifies：Column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth, obtains height
Pure alpha-linolenic acid；
Wherein, the modified Cucurbituril is poly-dopamine modified lithium Cucurbituril, and the modification infusorial earth connects to be polyamide modified
The diatomite of eight (oxosilanes of aminophenyl three) of branch；In the modification infusorial earth chromatography column chromatography method mobile phase be petroleum ether,
Ethanol, resveratrol；The concentration of sodium hydrate aqueous solution is 4mol/L described in the step (1)；Described in the step (1)
Ethanol solution that sodium hydrate aqueous solution and the mass fraction are 95%, the weight ratio of the linseed oil are 1：5：6；It is described
The weight ratio of petroleum ether and the ethanol, the resveratrol is described in mobile phase in modification infusorial earth chromatography column chromatography method
1：0.15：0.008；The flow velocity of mobile phase is 4ml/min in the modification infusorial earth chromatography column chromatography method；The poly-dopamine
Cucurbituril is cucurbit [7] urea described in modified Cucurbituril；The granularity of the modification infusorial earth is 300 mesh；
It is described that the method for method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, described chromatographed using modification infusorial earth
The method of purifying alpha-linolenic acid crude product, the preparation method of the poly-dopamine modified lithium Cucurbituril, the modification in column chromatography method
The preparation method of diatomite chromatographic column, the modification infusorial earth preparation method are the same as embodiment 1.
Comparative example 2
The method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction 1h,
Obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Using urea adduct method purifying alpha-linolenic acid mother liquor, alpha-linolenic acid crude product is obtained；
(5) column chromatography method purifies：Column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth, obtains height
Pure alpha-linolenic acid；
Wherein, the modification infusorial earth is the polyamide modified diatomite for being grafted eight (oxosilanes of aminophenyl three)；It is described
Mobile phase is petroleum ether, ethanol, resveratrol in modification infusorial earth chromatography column chromatography method；Hydrogen-oxygen described in the step (1)
The concentration for changing sodium water solution is 4mol/L；Sodium hydrate aqueous solution described in the step (1) is 95% with the mass fraction
Ethanol solution, the linseed oil weight ratio be 1：5：6；In the modification infusorial earth chromatography column chromatography method in mobile phase
The weight ratio of the petroleum ether and the ethanol, the resveratrol is 1：0.15：0.008；The modification infusorial earth chromatographic column
The flow velocity of mobile phase is 4ml/min in chromatography method；The granularity of the modification infusorial earth is 300 mesh；
It is described that the method for purifying alpha-linolenic acid crude product, the modified diatom in column chromatography method are chromatographed using modification infusorial earth
The preparation method of native chromatographic column, the modification infusorial earth preparation method are the urea substituting modification calabash with embodiment 1, difference
Reed urea.
Comparative example 3
The method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction 1h,
Obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha-linolenic acid crude product；
(5) column chromatography method purifies：Column chromatography method purifying alpha-linolenic acid crude product is chromatographed using modification infusorial earth, obtains height
Pure alpha-linolenic acid；
Wherein, the modified Cucurbituril is poly-dopamine modified lithium Cucurbituril, and the modification infusorial earth is eight (aminobenzenes of grafting
The oxosilane of base three) diatomite；Mobile phase is petroleum ether, ethanol, white black false hellebore in the modification infusorial earth chromatography column chromatography method
Alcohol；The concentration of sodium hydrate aqueous solution is 4mol/L described in the step (1)；Sodium hydroxide water described in the step (1)
Ethanol solution that solution and the mass fraction are 95%, the weight ratio of the linseed oil are 1：5：6；The modification infusorial earth
It is 1 to chromatograph the weight ratio of petroleum ether described in mobile phase and the ethanol, the resveratrol in column chromatography method：0.15：
0.008；The flow velocity of mobile phase is 4ml/min in the modification infusorial earth chromatography column chromatography method；The poly-dopamine modified lithium calabash
Cucurbituril described in reed urea is cucurbit [8] urea；The granularity of the modification infusorial earth is 300 mesh；
It is described that the method for method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, described chromatographed using modification infusorial earth
The method of purifying alpha-linolenic acid crude product, the preparation method of the poly-dopamine modified lithium Cucurbituril, the modification in column chromatography method
The preparation method of diatomite chromatographic column, the modification infusorial earth preparation method are the modification infusorial earth with embodiment 1, difference
To be grafted the diatomite of eight (oxosilanes of aminophenyl three).
Comparative example 4
The method of efficiently purifying alpha-linolenic acid, comprises the following steps：
(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, adding mass fraction is
95% ethanol solution, after temperature stabilization, linseed oil is added portionwise, stirring while adding to uniform to mix, insulation reaction 1h,
Obtain saponification mixture；
(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；
(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, the aqueous phase is saturated aqueous common salt,
The organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；
(4) method purifying is included：Using urea adduct method purifying alpha-linolenic acid mother liquor, alpha-linolenic acid crude product is obtained；
(5) column chromatography method purifies：Using polyamide chromatography column chromatography method purifying alpha-linolenic acid crude product, obtain high-purity α-
Leukotrienes；
Wherein, mobile phase is petroleum ether, ethanol, resveratrol in the polyamide chromatography column chromatography method；The step
(1) concentration of sodium hydrate aqueous solution described in is 4mol/L；Sodium hydrate aqueous solution described in the step (1) and the matter
It is 1 to measure ethanol solution, the weight ratio of the linseed oil that fraction is 95%：5：6；In the polyamide chromatography column chromatography method
The weight ratio of petroleum ether described in mobile phase and the ethanol, the resveratrol is 1：0.15：0.008；The aramid layer
The flow velocity for analysing mobile phase in column chromatography method is 4ml/min；The granularity of the polyamide is 200 mesh；
Difference is urea adduct method purifying substituting modification Cucurbituril inclusion method purifying, polyamide in column chromatography method purifying
Substituting modification diatomite.
Performance test：
Purity through high-pressure liquid chromatography alpha-linolenic acid；
The high pressure liquid chromatography test condition is：Analytical column：Agilent XDB-C18 posts (4.6 × 259mm,
P.N.990967-902)；Mobile phase：Ethanol -0.005%EDTA the aqueous solution (90:10)；Column temperature：30℃；Detection wavelength：
210nm；Sample size：5μl.
The alpha-linolenic acid mother liquor that step (3) is concentrated to give accounts for the percentage for participating in reaction linseed oil mass, i.e. alpha-linolenic acid
The yield of mother liquor=(amount × 100% of the amount of the alpha-linolenic acid mother liquor after concentration/participation reaction linseed oil；Step (4) includes
The alpha-linolenic acid crude product that method purifies to obtain accounts for the percentage for participating in reaction linseed oil mass, that is, include method yield after purification=
(amount of the amount for the liquid containing alpha-linolenic acid that inclusion method obtains after purification/participation reaction linseed oil) × 100%；It is because sub-
80% unrighted acid is contained up in flaxseed oil, so the alpha-linolenic acid that calculation procedure (5) column chromatography method obtains
Liquid phase purity after ultimate yield=(yield/80% after column chromatography method) × column chromatography method.
The performance test results of table 1
It is seen from the above data that the method for efficiently purifying alpha-linolenic acid provided by the invention, can improve α-flax
The purity of acid, makes alpha-linolenic acid purity after purification reach more than 90%.
Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim
It is intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology will not formed due to the inaccuracy of language performance and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim covers.
Claims (10)
- A kind of 1. method of efficiently purifying alpha-linolenic acid, it is characterised in that comprise the following steps：(1) saponification：Sodium hydrate aqueous solution is added into reactor, after being heated to 70 DEG C, it is 95% to add mass fraction Ethanol solution, after temperature stabilization, be added portionwise linseed oil, stirring while adding to uniform to mix, insulation reaction 0.5h- 1.5h, obtain saponification mixture；(2) pH is adjusted：The pH of saponification mixture is arrived into 3-4 with hydrochloric acid regulation, isothermal reaction, obtains acidic mixture；(3) extract：Aqueous phase is added in oxytropism mixture and organic phase is extracted, and the aqueous phase is saturated aqueous common salt, described Organic phase is petroleum ether, and the organic phase after being extracted, be concentrated under reduced pressure organic phase, obtains alpha-linolenic acid mother liquor；(4) method purifying is included：Method purifying alpha-linolenic acid mother liquor is included using modified Cucurbituril, obtains alpha-linolenic acid crude product；(5) column chromatography method purifies：Using modification infusorial earth chromatograph column chromatography method purifying alpha-linolenic acid crude product, obtain high-purity α- Leukotrienes；Wherein, the modified Cucurbituril is poly-dopamine modified lithium Cucurbituril, and the modification infusorial earth is polyamide modified grafting eight The diatomite of (oxosilane of aminophenyl three)；In the modification infusorial earth chromatography column chromatography method mobile phase be petroleum ether, ethanol, Resveratrol.
- 2. the method for efficiently purifying alpha-linolenic acid according to claim 1, it is characterised in that hydrogen described in the step (1) The concentration of aqueous solution of sodium oxide is (2-5) mol/L.
- 3. the method for efficiently purifying alpha-linolenic acid according to claim 1, it is characterised in that hydrogen described in the step (1) Ethanol solution that aqueous solution of sodium oxide and the mass fraction are 95%, the weight ratio of the linseed oil are 1：(3-7)：(4- 7)。
- 4. the method for efficiently purifying alpha-linolenic acid according to claim 1, it is characterised in that the modification infusorial earth chromatographic column The weight ratio of petroleum ether described in mobile phase and the ethanol, the resveratrol is 1 in chromatography method：(0.05-0.2)： (0.005-0.015)。
- 5. the method for efficiently purifying alpha-linolenic acid according to claim 4, it is characterised in that the modification infusorial earth chromatographic column The weight ratio of petroleum ether described in mobile phase and the ethanol, the resveratrol is 1 in chromatography method：0.15：0.008.
- 6. the method for efficiently purifying alpha-linolenic acid according to claim 1, it is characterised in that the modification infusorial earth chromatographic column The flow velocity of mobile phase is (1ml-5ml)/min in chromatography method.
- 7. the method for efficiently purifying alpha-linolenic acid according to claim 6, it is characterised in that the modification infusorial earth chromatographic column The flow velocity of mobile phase is 4ml/min in chromatography method.
- 8. the method for efficiently purifying alpha-linolenic acid according to claim 1, it is characterised in that the poly-dopamine modified lithium cucurbit Cucurbituril described in urea is cucurbit [8] urea.
- 9. the method for efficiently purifying alpha-linolenic acid according to claim 1, it is characterised in that described using modified Cucurbituril bag Legal purifying alpha-linolenic acid mother liquor comprises the following steps：Mixed solution, the alpha-linolenic acid mother liquor of modified Cucurbituril and ethanol are added into reactor, is warming up to 75~80 DEG C, insulation 1-3h is reacted, is cooled to 5-10 DEG C, insulation reaction 1-3h, is filtered, filtrate recycling ethanol, petroleum ether extraction, then successively with water, matter Measure the NaCl solution that fraction is 10% to wash, dry, recycling design, obtain alpha-linolenic acid crude product；The modified Cucurbituril and ethanol Mixed solution described in the weight ratio of modified Cucurbituril and the ethanol be 1：8, the mass fraction of the ethanol is 95%；Institute The weight ratio for stating modified Cucurbituril and the alpha-linolenic acid mother liquor is 1：2.5.
- 10. the method for efficiently purifying alpha-linolenic acid according to claim 1, it is characterised in that described to use modification infusorial earth The method of purifying alpha-linolenic acid crude product comprises the following steps in chromatography column chromatography method：(1) alpha-linolenic acid dissolving crude product is obtained into alpha-linolenic acid crude product solution with mobile phase, added along polyamide chromatography column wall Alpha-linolenic acid crude product solution, then adds mobile phase, the mass fraction of alpha-linolenic acid crude product in the alpha-linolenic acid crude product solution For 40%；(2) chromatographic column lower piston, mobile phase outflow are opened；(3) sample piecewise acquisition, the change of impurity and sample in efflux is tracked by TLC, collects pure sample product portion Point, removal of solvent under reduced pressure, obtain high-purity alpha-linolenic acid.
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| WO2019190046A1 (en) * | 2018-03-30 | 2019-10-03 | 울산대학교 산학협력단 | Method for concentrating pathogen using diatoms and cucurbiturils |
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| WO2019182248A1 (en) * | 2018-03-19 | 2019-09-26 | 울산대학교 산학협력단 | Method for water desalination and purification using diatoms and cucurbiturils |
| WO2019190046A1 (en) * | 2018-03-30 | 2019-10-03 | 울산대학교 산학협력단 | Method for concentrating pathogen using diatoms and cucurbiturils |
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