CN104043393B - For separating of modified mesoporous material of Polyprenols From Ginkgo Biloba L and preparation method thereof - Google Patents
For separating of modified mesoporous material of Polyprenols From Ginkgo Biloba L and preparation method thereof Download PDFInfo
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- CN104043393B CN104043393B CN201410243138.4A CN201410243138A CN104043393B CN 104043393 B CN104043393 B CN 104043393B CN 201410243138 A CN201410243138 A CN 201410243138A CN 104043393 B CN104043393 B CN 104043393B
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Abstract
The present invention relates to a kind of modified mesoporous material for separating of Polyprenols From Ginkgo Biloba L and preparation method thereof, the method comprises: (1) prepares solid extracting agent; (2) utilize the Polyprenols From Ginkgo Biloba L in solid extracting agent absorption hexane solution, and study its Adsorption thermodynamics, dynamics; (3) be adsorbed on the polypentenol on solid extracting agent with 1-hexene wash-out, optimize fixed bed elution requirement; (4) test the recycling performance of this solid extracting agent. This material reaches 153mg/g to the equilibrium adsorption capacity of polypentenol, utilize this material to make the content of polypentenol in medicinal extract bring up to 70.2% by 38.54% to carrying out enrichment processing containing polypentenol benzinum medicinal extract, reuse six times, its rate of recovery still reaches 86.5%, in the purity that ensures to improve polypentenol, has reduced silver ion loss. Method of the present invention is easy and simple to handle, strong to unsaturated compound adsorptive selectivity, and extractant can repeatedly reuse.
Description
Technical field
The present invention relates to a kind of carrying silver ion liquid modified mesoporous material for separating of enrichment polyprenols in Ginkgo biloba leavesPreparation and using method thereof.
Background technology
Polyprenols From Ginkgo Biloba L (polyprenols, PPs) is a kind of linearity that is connected and is formed by multiple isopentene group head and the tailOligomeric quasi-grease compound, wherein contains 2 trans and 12-20 cis isopentene groups, and two ends are respectively ω end group and insatiable hungerWith α end group, belong to two anti-many cisoids polypentenols. Degree of unsaturation reaches as high as 21, has very strong biologically active and pharmacology and doesWith.
The world since nineteen eighty-two, Japan's Tanaka Yasuyuki was isolated ginkgo leaf polypenthylene compounds first from ginkgo leafIn scope, its bioactive research and product development are never interrupted.
Polyprenols From Ginkgo Biloba L belongs to natural products, nontoxic to human body, without three-induced effect, to various diseases and body injuryThere is significant result for the treatment of, as: Polyprenols From Ginkgo Biloba L is external to be had good anticancer effect and lures Heps, S180, ECLead the effect of apoptosis of tumor cells; There is the immunity of enhancing, promote candidate stem cell increment and the leukemic effect of NACT;At aspect successfuls such as hepatitis virus resisting and reparation hepatic injury, liver cancer apoptosis reducings; Polyprenols From Ginkgo Biloba L and otherCompatibility of drugs associating can reduce radiation and the damage of chemotherapy to cell in the situation that not reducing drug effect.
Polyprenols From Ginkgo Biloba L is oily quasi-grease compound, is low pole. Be soluble in benzinum, n-hexane, chloroform etc.The mixture of organic solvent and they and acetone, ether, ethyl acetate. Generally to adopt weakly polar organic solvent to ginkgo leafExtract and obtain crude extract, more repeatedly with column chromatography separating purification. As the people such as Koichi adopt acetone: n-hexane (1; 1) soakCarry and pass through silica gel column chromatography, n-hexane: ether (19; 1) wash-out obtains the polypentenol acetic acid esters of certain purity. But ginkgo leafIn there is multiple nonpolar liposoluble ingredient, need to just can reach higher purity through purification by silica gel column chromatography repeatedly, thereby produceThe raw process operation time is long, and silica gel consumption is large, the shortcomings such as inefficiency. Wang Chengzhang etc. adopt molecule short-path distillation method to separate poly-pentaEnol, operating process is that solvent is slightly carried-is hydrolyzed-the freezing unsaponifiable matter that obtains, by unsaponifiable matter successively from low to high threeUnder temperature section, distill, obtain purity and be 70% Polyprenols From Ginkgo Biloba L product. The method has been avoided the use of a large amount of organic solventsThere is the feature of environment-protecting clean, there is certain physics selective. But pentenol molecular weight is large, outlet temperature while being distilled out ofBe up to 300 DEG C, cause that energy consumption is large, the two key poor stabilities of product. Yankee enlightening etc. has been set up methanol aqueous solution-silver ion ligandSystem, forms π complexing by the unsaturated bond in silver ion and polypentenol, selectively separates polyprenols,Product purity is significantly improved. But in methanol aqueous solution-silver ion coordination system, methyl alcohol saturated vapor pressure is higher, wavesSend out seriously, cause concentration of silver ions in extractant recycling process to be difficult to determine, liquid-phase extraction agent reuse difficultyIncrease. But utilize silver ion selectively high with two key p-coordination extractions, under the prerequisite of the certain separating effect of guarantee, both avoidedDistillation high temperature, than column chromatography, the time again greatly shorten, this p-coordination extraction method is worth further investigated.
Ionic liquid has the features such as low-steam pressure, high stability, wide liquid journey and pollution-free, reusable edible, these spiesPoint makes ionic liquid be widely used in the extraction of reactive compound in natural products. Early stage we adopt ionic liquid-Ag+System liquid-liquid extraction separates Polyprenols From Ginkgo Biloba L and also obtains good result, and ionic liquid is strong to the hold facility of silver ion,Reduce the loss of silver ion in separation process; And the low-steam pressure of ionic liquid has made up organic solvent high volatile volatile defect.But ionic liquid price is higher, directly very large as solvent use amount, increase production cost.
Liquid-solid extraction separates has that energy consumption is low, industrialization operates feature easily. With solid material, ionic liquid is carried outImmobilizedly can both bring into play the hold facility of ionic liquid to silver ion, can reduce ionic liquid consumption simultaneously. Mesopore molecular sieve materialMaterial material is because the regular feature such as in order in large, the duct of specific area is suitable for as solid carrier material very much.
Summary of the invention
The object of the invention is to provide a kind of modified mesoporous material for separating of Polyprenols From Ginkgo Biloba L, the present invention's employingLearning synthetic method makes mesoporous material surface modification become to have ionic liquid character, Adsorption For Ag ion that can be stable. By silverThe two key p-coordinations of ion and polypentenol, make polypentenol be adsorbed on solid extracting agent surface, and can make ginkgo leaf poly-Pentenol specific isolation.
The present invention is achieved by the following technical solutions:
For separating of a Modified MCM-41 mesoporous material for Polyprenols From Ginkgo Biloba L, it is characterized in that: by high adsorptionCan Modified MCM-41 mesoporous material as the adsorbent of Polyprenols From Ginkgo Biloba L, described Modified MCM-41 mesoporous material be byThe compound with ionic liquid character carries out modification.
Step prepared by Modified MCM-41 mesoporous material of the present invention comprises: MCM-41 mesoporous material synthetic; ChangeLearn the mesoporous MCM-41 of modification method Ionic Liquid Modified, be designated as ILM; ILM load tetrafluoro boron silver.
It is that silicon source, softex kw are as template, with alkali or acid that the present invention adopts ethyl orthosilicateSynthesize as organic solvent as catalyst, water or ethanol, gained pressed powder adopts the ethanolic solution of hydrochloric acid to carry outSoxhlet extracting is to obtain the former powder of mesoporous MCM-41.
Ionic liquid of the present invention is modified MCM-41 process, is to adopt chemical modification method by contained group in ionic liquid progressivelyModification is got on. Reduce the direct use of ionic liquid, cut the waste and pollute, contributed to increase economic benefit and reduce environment pressurePower.
Ionic liquid of the present invention is modified MCM-41 process for utilizing 3-r-chloropropyl trimethoxyl silane to carry out silanization, by siliconProduct after alkylation reaction is introduced imidazole radicals by reacting with butyl imidazole. Then product and hexafluorophosphoric acid silver are carried out to ion friendshipGet the mesoporous MCM-41 of modification with ionic liquid feature in return.
Modified mesoporous material of the present invention adopts infusion process absorption AgBF after ionic liquid is modified4To obtain final absorptionParting material Ag+/IL·M。
Concrete steps prepared by Modified MCM-41 mesoporous material are:
Synthesizing of 1.MCM-41 mesoporous material
Using ethyl orthosilicate TEOS as silicon source, softex kw CTAB as template, using ammoniacal liquor asCatalyst, second alcohol and water are as solvent. Be specially and get CTAB and be dissolved in distilled water and alcohol mixed solution, add ammoniacal liquor at 50 DEG CLower vigorous stirring is muddy to occurring, then dropwise adds the TEOS being dissolved by ethanol; Wherein the molar ratio of each material is TEOS:CTAB: ammoniacal liquor: ethanol: water=1:0.41:14.5:53:180; In the TEOS wherein being dissolved by ethanol, the ratio of TEOS and ethanol is8:5mmol/mL. Mixture continues to adopt 0.45 μ m filter membrane decompress filter after vigorous stirring 2h, and anti-with ethanol and distilled waterAfter backwashing is washed, and product obtains white powder at 60 DEG C of vacuum drying 24h, and powder is added to 100mL1mol/LHCl ethanol according to every gramThe ratio Soxhlet extracting 24h of solution is with removed template method, then by product with after distilled water and ethanol washing at 60 DEG C vacuumDry 24h, obtains pressed powder. Vacuum drying at 60 DEG C, obtains having duct and is six side's ordered arrangements, big or small even, ratio tableThe Mesoporous silica MCM 41 that area is large.
The mesoporous MCM-41 of chemic modified method Ionic Liquid Modified
The mesoporous MCM-41 of Ionic Liquid Modified is divided into three steps:
(1) step 1 gained Mesoporous silica MCM 41 is dispersed in uniformly in the three-neck flask that 100mL is equipped with toluene, inHeating at 110 DEG C. Dropwise add 3-r-chloropropyl trimethoxyl silane, under nitrogen protection, react 10h. After reaction finishes, filter,Ether, ethanol washing, vacuum drying obtains product I; Wherein step 1 gained Mesoporous silica MCM 41: toluene: 3-chloropropyl front threeThe amount ratio of TMOS is 2:100:5g/mL/mmol.
(2) miscible after butyl imidazole and product I being dissolved in respectively in chloroform, at 70 DEG C of back flow reaction 24h. Reaction finishesRear filtration, ether washing, carries out soxhlet extraction 24h with carrene after vacuum drying and removes unreacted butyl imidazole, filtersOven dry obtains product II; Wherein butyl imidazole: product I: the amount ratio of chloroform is 5:2:75mmol/g/mL. The consumption of product IExactly the MCM-41 through silanization in (1) is all carried out to (2) reaction, lower same.
(3) product II and KFP6Be dissolved in respectively the miscible 72h that at room temperature stirs after acetone. Reaction finishes rear filtration, etherWashing, vacuum drying. Ether soxhlet extraction 24h, vacuum drying obtains ion liquid modified MCM-41, is designated as ILM; WhereinProduct II: KFP6: the usage ratio of acetone is 2/5/50g/mmol/mL.
.ILM load tetrafluoro boron silver
It is 5 ~ 25mmol/L's that mesoporous above-mentioned Ionic Liquid Modified MCM-41 (being ILM) is immersed in to concentration rangeAgBF4In acetone soln, lucifuge stirs 10h. It is dry that reaction finishes final vacuum, and resulting materials is designated as Ag+/ MIL. Wherein determineAgBF4With the ratio of ILM be 1.5:1mmol/g.
Modified mesoporous material Ag prepared by the present invention+/ ILM separates for Polyprenols From Ginkgo Biloba L, the steps include: to takeTake 25gAg+/ ILM, n-hexane wet method dress post (the high 46cm of post, bed volume (BV) is 36.1mL), before loading, 6BV is justHexane coupled columns washs, and removes the free state silver ion that may exist in duct, at 30 DEG C by PPs hexane solution with oneFixed flow velocity flows through pillar. Loading concentration 2.01mg/mL, loading speed 7.0BV/h, time of break-through is 70min; When wash-out, with1-hexene wash-out is adsorbed on the polypentenol on solid extracting agent, the wash-out flow 2.0BV/h of 1-hexene, eluant, eluent consumption6.5BV. Collect eluent, fling to solvent, obtain the polypentenol of purifying, through this step polypentenol content by 38.54%Be raised to 70.2%, the rate of recovery is 86.6%. Solid extracting agent in this fixed bed is reused through six times, the polypentenol rate of recoveryStill have 86%.
Detailed description of the invention
Embodiment 1
Synthesizing of 1.MCM-41 mesoporous material
Using ethyl orthosilicate as silicon source, softex kw as template, using ammoniacal liquor as catalyst, secondAlcohol and water is as solvent. Be specially and get 2.4gCTAB and be dissolved in 50mL distilled water and 40mL alcohol mixed solution, add 13mLAmmoniacal liquor occurs muddy at 50 DEG C after vigorous stirring 2min, then dropwise add the 16mmolTEOS(being dissolved by 10mL ethanol eachThe molar ratio of material is TEOS:CTAB: ammoniacal liquor: ethanol: water=1:0.41:14.5:53:180). Mixture continues vigorous stirringAfter 2h, adopt 0.45 μ m filter membrane decompress filter, and with ethanol and distilled water cyclic washing, product obtains at 60 DEG C of vacuum drying 24h whiteToner end, by powder according to the ratio Soxhlet extracting 24h of every gram of 100mL1mol/LHCl ethanolic solution with removed template method, soAfter by product with after the washing of distilled water and ethanol at 60 DEG C vacuum drying 24h, obtain pressed powder. This pressed powder adopts denseDegree is that the ethanolic solution of 1M hydrochloric acid carries out Soxhlet extracting 24h. Vacuum drying at 60 DEG C, obtains having duct and is six sides and arranges in orderThe Mesoporous silica MCM 41 that row, size are evenly, specific area is large.
The mesoporous MCM-41 of chemic modified method Ionic Liquid Modified
The mesoporous MCM-41 of Ionic Liquid Modified is divided into three steps:
(1) 2gMCM-41 is dispersed in uniformly in the three-neck flask that 100mL is equipped with toluene to heating at 110 DEG C.Dropwise add 5mmol3-r-chloropropyl trimethoxyl silane, under nitrogen protection, react 10h. After reaction finishes, filter, ether,Ethanol washing, vacuum drying obtains product I.
(2) miscible after 5mmol butyl imidazole and product I being dissolved in respectively in 75ml chloroform, 70 DEG C of back flow reaction 24H. Reaction finishes rear filtration, and ether washing, carries out soxhlet extraction 24h with carrene after vacuum drying and remove unreacted fourthBase imidazoles, filtering drying obtains product II.
(3) KFP of product II and 5mmol6Be dissolved in respectively after mixing in 50ml acetone and at room temperature stir 72h. Reaction knotFiltration after bundle, ether washing, vacuum drying. Ether soxhlet extraction 24h, vacuum drying obtains ion liquid modified MCM-41,Be designated as ILM.
.ILM load tetrafluoro boron silver
Mesoporous above-mentioned Ionic Liquid Modified MCM-41 (being ILM) is immersed in to certain density AgBF4In acetone soln,Lucifuge stirs 10h. It is dry that reaction finishes final vacuum, and resulting materials is designated as Ag+/ MIL. Wherein AgBF4With the ratio of ILM be1.5mmol/g。
Experimental example 1Ag+Static Adsorption and the desorb of/MIL to PPs
Accurately claim Ag+/ ILM50mg is placed in and in 50mL tool plug triangular flask, adds the certain density PPs n-hexane of 10mLSolution, stirs after some hours 3200r/min centrifugation 5min at 30 DEG C. Get supernatant syringe needle filter filter after warpHPLC analyzes, and records the concentration of PPs. Precipitation is washed fast through n-hexane, adds 10mL1-hexene at room temperature to stir 2h, fromThe heart separates. Repeat aforesaid operations twice rear merging filtrate, volatilize and be settled to 10mL with n-hexane afterwards. Record desorbed solution through HPLCThe concentration of middle PPs. Ag+Equilibrium adsorption capacity 153mg/g, the equilibrium adsorption rate 91.9% of/ILM to PPs, desorption efficiency 90.1%.
Experimental example 2Ag+The Dynamic Adsorption desorb of/MIL to PPs
Take 25gAg+/ILM, n-hexane wet method dress post (the high 46cm of post, bed volume (BV) is 36.1mL). OnBefore sample, 4BV n-hexane coupled columns washs, and removes the free state material that may exist in material duct. At 30 DEG C by concentrationFor the PPs hexane solution of 2.01mg/g flows through pillar with the flow velocity of 7BV/h, time of break-through is 120 minutes. Absorption finishesAfter, after the n-hexane wash-out impurity with 4.0BV, taking 1-hexene as eluant, eluent, elution flow rate 2.0BV/h, eluant, eluent consumption6.5BV. After solid-phase extraction column purifying, the content of polypentenol rises to 70.2% by 38.54%, and the rate of recovery is 86.6%.
Experimental example 3Ag+The regeneration of/MIL adsorbent and recycling
Accurately take Ag+/ ILM50mg is in 50mL tool plug triangular flask, and adding respectively concentration is 0.832mg/mLPolyprenols From Ginkgo Biloba L 10mL is in 30 DEG C of extraction 10min, centrifugation. Precipitation adopts equal-volume 1-hexene to resolve 2h, repeatsAfter resolving 2 times, merge desorbed solution, after desorbed solution volatilizes again constant volume to 10mL. Two kinds of adsorbents all repeat aforesaid operations six times.Raffinate and desorbed solution sample detect through HPLC respectively. Ag in seven recycling experiments+Adsorbance, the PPs of/ILM to PPsPurity and the rate of recovery are in table 1.
Table 1Ag+/ ILML recovery test
Claims (1)
1. for separating of a preparation method for the modified mesoporous material of Polyprenols From Ginkgo Biloba L, carry out in the steps below:
(A) MCM-41 mesoporous material is synthetic
Using ethyl orthosilicate TEOS as silicon source, softex kw CTAB is as template, using ammoniacal liquor as catalysisAgent, second alcohol and water be as solvent, is specially to get CTAB and be dissolved in distilled water and alcohol mixed solution, adds ammoniacal liquor acute at 50 DEG CThere is muddiness in strong being stirred to, then dropwise adds the TEOS being dissolved by ethanol; Wherein the molar ratio of each material is TEOS:CTAB: ammoniacal liquor: ethanol: water=1:0.41:14.5:53:180; In the TEOS wherein being dissolved by ethanol, the ratio of TEOS and ethanol is8:5mmol/mL; Mixture continues to adopt 0.45 μ m filter membrane decompress filter after vigorous stirring 2h, and anti-with ethanol and distilled waterAfter backwashing is washed, and product obtains white powder at 60 DEG C of vacuum drying 24h, and powder is added to 100mL1mol/LHCl ethanol according to every gramThe ratio Soxhlet extracting 24h of solution is with removed template method, then by product with after distilled water and ethanol washing at 60 DEG C vacuumDry 24h, obtains pressed powder, i.e. Mesoporous silica MCM 41;
(B) the mesoporous MCM-41 of chemic modified method Ionic Liquid Modified
The mesoporous MCM-41 of Ionic Liquid Modified is divided into three steps:
(1) step (A) gained Mesoporous silica MCM 41 is dispersed in the three-neck flask that toluene is housed uniformly, at 110 DEG CHeating, dropwise adds 3-r-chloropropyl trimethoxyl silane, under nitrogen protection, reacts 10h, after reaction finishes, filters ether, secondAlcohol washing, vacuum drying obtains product I; Wherein steps A gained Mesoporous silica MCM 41: toluene: 3-r-chloropropyl trimethoxyl siliconThe amount ratio of alkane is 2:100:5g/mL/mmol;
(2) miscible after butyl imidazole and product I being dissolved in respectively in chloroform, at 70 DEG C of back flow reaction 24h, reaction finishes rear mistakeFilter, ether washing, carries out soxhlet extraction 24h with carrene after vacuum drying and removes unreacted butyl imidazole, filtering dryingObtain product II; Wherein butyl imidazole: product I: the amount ratio of chloroform is 5:2:75mmol/g/mL;
(3) product II and KFP6Be dissolved in respectively the miscible 72h that at room temperature stirs after acetone, reaction finish rear filtration, ether washing,Vacuum drying; Ether soxhlet extraction 24h, vacuum drying obtains ion liquid modified MCM-41, is designated as ILM; Wherein productⅡ：KFP6: the usage ratio of acetone is 2/5/50g/mmol/mL;
(C) ILM load tetrafluoro boron silver
The ILM of step (B) gained is immersed in to the AgBF that concentration range is 5 ~ 25mmol/L4In acetone soln, lucifuge stirs10h; It is dry that reaction finishes final vacuum, and resulting materials is designated as Ag+/ MIL; Wherein determine AgBF4With the ratio of ILM be 1.5:1mmol/g。
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| CN102603483A (en) * | 2012-03-13 | 2012-07-25 | 江苏大学 | Method for extracting polyprenols from ginkgo leaves |
| CN103691400A (en) * | 2013-12-20 | 2014-04-02 | 华南理工大学 | Functionalized ionic liquid hybrid mesoporous molecular sieve MCM-48 composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102603483A (en) * | 2012-03-13 | 2012-07-25 | 江苏大学 | Method for extracting polyprenols from ginkgo leaves |
| CN103691400A (en) * | 2013-12-20 | 2014-04-02 | 华南理工大学 | Functionalized ionic liquid hybrid mesoporous molecular sieve MCM-48 composite material and preparation method and application thereof |
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| Title |
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| 银离子配位萃取银杏叶中多萜长链化合物的研究;杨克迪等;《无机化学学报》;20060228;第22卷(第02期);243-247 * |
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