CN108610241A - A method of extracting hydroxytyrosol from lilac - Google Patents
A method of extracting hydroxytyrosol from lilac Download PDFInfo
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- CN108610241A CN108610241A CN201810620688.1A CN201810620688A CN108610241A CN 108610241 A CN108610241 A CN 108610241A CN 201810620688 A CN201810620688 A CN 201810620688A CN 108610241 A CN108610241 A CN 108610241A
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- ion exchange
- exchange resin
- type ion
- hydroxytyrosol
- extraction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Saccharide Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The method that the present invention provides a kind of to extract hydroxytyrosol from lilac.The present invention can be such that the ester bond in oleuropein all hydrolyzes, free state hydroxytyrosol is converted into, to increase the content of hydroxytyrosol in extract liquor by the extraction in combination hydrolysis in situ；Wherein, the OH‑Type ion exchange resin is the hydrolysis for promoting oleuropein as catalyst, and the chlorinated solvents are to extract free state hydroxytyrosol as extractant.Therefore, during extraction in combination hydrolysis in situ, the hydrolysis of oleuropein and the extraction of free state hydroxytyrosol are completed at the same time.Meanwhile extraction in combination hydrolysis in situ method provided by the invention efficiently avoids hydrolysis and extracts the lengthy and tedious of two steps operation again, saves the usage amount of operational sequence and solvent, production cost is low, and hydroxytyrosol yield is high.
Description
Technical field
The present invention relates to compound extractive technique fields, and in particular to a kind of side extracting hydroxytyrosol from lilac
Method.
Background technology
Lilac is machaka or dungarunga, is planted frequently as ornamental plant, and Regional Distribution is extensive, North gets Inner Mongol
Yunnan is arrived in Gu, south, and east arrives Heilungkiang, has extensive distribution west to river, Tibetan and other places, and the cultivation for having more than 1000 years in China is gone through
History and civil common medicinal material.Oxidation-resistant active ingredient there are many containing in lilac stem, such as：Syringin, oleuropein and
Hydroxytyrosol.
Hydroxytyrosol is a kind of natural polyphenol class compound, has a variety of biologies and pharmacological activity, such as：To treating cancer,
Angiocardiopathy, neurodegenerative disease, diabetes, inflammation infection and anti-oxidant aspect etc. all have good effect, especially
It is antioxidant activity, and it is considered as one of the natural for most removing free radical to make it.Natural hydroxytyrosol is very
It is few to exist in a free form, it is most of to be present in lilac stem in the form of carboxylate (oleuropein).
It is typically to extract hydroxytyrosol by raw material of olive in the prior art.The middle promulgated by the State Council of Publication No. CN106866383A
Bright patent describes the method that hydroxytyrosol is extracted from olive leaf.But this method needed in extraction process it is micro- into horizontal high voltage
The processing of jet stream ultramicro grinding, energy consumption is big, and experiment condition requires high；And due to the limitation of equipment manufacturing cost and safety in utilization, it is difficult to
Form industrial-scale production.The Chinese invention patent of Publication No. CN103709014A describes a kind of high conversion rate and recycling
The high hydroxytyrosol extracting method of rate.But this method arrives strong acid high temperature extraction step involved in extraction process, may cause
Hydroxytyrosol decomposes, and makes the reduction of its yield；And need to carry out secondary hydrolysis, time-consuming, is unfavorable for industrial-scale production.It is open
Number describe a kind of method boiled hydrolysis and prepare hydroxytyrosol for the Chinese invention patent of CN102276424A.But this method
The operating procedure for also relating to strong acid high temperature, is unfavorable for industrial-scale production.
Invention content
The method that the purpose of the present invention is to provide a kind of to extract hydroxytyrosol from lilac, method provided by the invention
The yield of hydroxytyrosol is high, and at low cost, suitable for industrial-scale production.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The method that the present invention provides a kind of to extract hydroxytyrosol from lilac, includes the following steps：
Lilac is extracted using the first ethanol water, obtains extracting solution；
By the extracting solution and OH-Extraction in combination hydrolysis in situ is carried out after type ion exchange resin and chlorinated solvents mixing, is obtained
Extract liquor；
The organic phase in the extract liquor is isolated, the organic phase is concentrated to dryness, using the second ethanol water pair
Resulting material is dissolved, and lysate is obtained；
The lysate is enriched with using macroporous absorbent resin, using third ethanol water to the macropore after enrichment
Absorption resin is eluted, and the solvent in removal gained eluent obtains hydroxytyrosol.
Preferably, the volumn concentration of first ethanol water is 20~70%；Second ethanol water
Volumn concentration be 20~30%；The volumn concentration of the third ethanol water is 70~90%.
Preferably, in terms of the absolute dry mass of the lilac, the lilac and the mass ratio of the first ethanol water are
1：(8~15).
Preferably, the temperature of the extraction is 70~95 DEG C, and the time is 1~5h.
Preferably, the OH-Type ion exchange resin is pre-processed before use, the pretreated method include with
Lower step：
(1) it is 88~92% ethanol water to OH to use volumn concentration-Type ion exchange resin is impregnated
Processing, by gained OH-Type ion exchange resin is washed；
(2) OH for using acid reagent to obtain the step (1)-Type ion exchange resin carries out immersion treatment, by gained
OH-Type ion exchange resin is washed to neutrality；
(3) OH for using base reagent to obtain the step (2)-Type ion exchange resin carries out immersion treatment, by gained
OH-Type ion exchange resin is washed to neutrality；
(4) OH for obtaining the step (3)-Type ion exchange resin carries out the place in step (2) and step (3) successively
Reason, obtains pretreated OH-Type ion exchange resin is spare.
Preferably, in terms of the absolute dry mass of the lilac, the OH-Type ion exchange resin is the 3 of lilac quality
~20%.
Preferably, the chlorinated solvents include dichloromethane, chloroform, 1,1- dichloroethanes or 1,2- dichloroethanes.
Preferably, the chlorinated solvents and the volume ratio of extracting solution are (0.4~2.5)：1.
Preferably, the extraction in combination hydrolysis in situ carries out under sealing condition；The temperature of the extraction in combination hydrolysis in situ be 70~
95 DEG C, the time is 1~5h.
Preferably, it the enrichment and is eluted under sealing condition and carries out；In the enrichment process sample concentration be 0.2~
0.7mg/mL。
The method that the present invention provides a kind of to extract hydroxytyrosol from lilac, using the first ethanol water to purple fourth
Perfume (or spice) extracts, and obtains extracting solution；By the extracting solution and OH-It is hydrolyzed after type ion exchange resin and chlorinated solvents mixing
Situ extracting obtains extract liquor；The organic phase in the extract liquor is isolated, the organic phase is concentrated to dryness, using second
Ethanol water dissolves resulting material, obtains lysate；The lysate is enriched with using macroporous absorbent resin,
The macroporous absorbent resin after enrichment is eluted using third ethanol water, the solvent in removal gained eluent obtains
Hydroxytyrosol.The present invention can be such that the ester bond in oleuropein all hydrolyzes, be converted into free by the extraction in combination hydrolysis in situ
State hydroxytyrosol, to increase the content of hydroxytyrosol in extract liquor；Wherein, the OH-Type ion exchange resin is as urging
It is to extract free state hydroxytyrosol as extractant that agent, which promotes the hydrolysis of oleuropein, the chlorinated solvents,.Therefore, it is hydrolyzing
During situ extracting, the hydrolysis of oleuropein and the extraction of free state hydroxytyrosol are completed at the same time.Meanwhile the present invention carries
The extraction in combination hydrolysis in situ method of confession efficiently avoids lengthy and tedious, saving operational sequence and the solvent of hydrolysis and extraction two steps operation again
Usage amount, production cost is low, and hydroxytyrosol yield is high.Embodiment the experimental results showed that, with hydroxytyrosol in extracting solution
Yield is 100% meter, and up to 160.44%, purity reaches the yield of the hydroxytyrosol obtained according to the method provided by the invention
39.5%.
Further, extraction in combination hydrolysis in situ, enrichment and elution process are carried out under sealing condition in the present invention, no dirt
Dye, solvent are recyclable；And the OH-Type ion exchange resin can recycle after through regeneration treatment.This into
One step reduces production cost, is produced convenient for industrial scale.
Description of the drawings
Fig. 1 is the high-efficient liquid phase chromatogram of gained extracting solution (b) and hydroxytyrosol standard items (a) in embodiment 1；
Fig. 2 is the high-efficient liquid phase chromatogram of gained extracting solution in embodiment 1；
Fig. 3 is the high-efficient liquid phase chromatogram of gained extract liquor in embodiment 1.
Specific implementation mode
The method that the present invention provides a kind of to extract hydroxytyrosol from lilac, includes the following steps：
Lilac is extracted using the first ethanol water, obtains extracting solution；
By the extracting solution and OH-Extraction in combination hydrolysis in situ is carried out after type ion exchange resin and chlorinated solvents mixing, is obtained
Extract liquor；
The organic phase in the extract liquor is isolated, the organic phase is concentrated to dryness, using the second ethanol water pair
Resulting material is dissolved, and lysate is obtained；
The lysate is enriched with using macroporous absorbent resin, using third ethanol water to the macropore after enrichment
Absorption resin is eluted, and the solvent in removal gained eluent obtains hydroxytyrosol.
The present invention extracts lilac using the first ethanol water, obtains extracting solution.In the present invention, described
The volumn concentration of one ethanol water is preferably 20~70%, and more preferably 30~50%.In the present invention, with the purple
The absolute dry mass meter of cloves, the lilac and the mass ratio of the first ethanol water are preferably 1：(8~15), more preferably 1：
(10~12).
In the present invention, the lilac is preferably the lilac stem after natural air drying；In the present invention, the lilac
For stem after natural air drying, moisture content is 20% hereinafter, in not necessary any drying process processing before.In the present invention, institute
It states lilac and is preferably crushing processing using preceding, cross 40 mesh sieve, it is for use to obtain lower part of screen point lilac powder.
In the present invention, the temperature of the extraction is preferably 70~95 DEG C, more preferably 75~85 DEG C；In the reality of the present invention
It applies in example, the temperature of the extraction is specially the reflux temperature of first ethanol water.In the present invention, the extraction
Time is preferably 1~5h, more preferably 2~4h.In the present invention, in order to ensure fully to extract hydroxytyrosol, the extraction
Number be preferably 2~4 times, more preferably 3 times.
After completing the extraction, gained system is preferably separated by solid-liquid separation by the present invention, using obtained liquid material as
Extracting solution.The present invention does not have the mode of the separation of solid and liquid special restriction, using side well known to those skilled in the art
Formula is specific as filtered.
The present invention extracts lilac using the first ethanol water, and raw material is not required to additionally dry directly use, energy
Consumption is few；And hydroxytyrosol yield is high, fire safety evaluating hidden danger is low；Meanwhile first ethanol water can remove the purple fourth
The larger ingredient of polarity in perfume (or spice), such as polysaccharide and protein.
After obtaining extracting solution, the present invention is by the extracting solution and OH-Type ion exchange resin and chlorinated solvents mixing are laggard
Row extraction in combination hydrolysis in situ, obtains extract liquor.In the present invention, the chlorinated solvents and the volume ratio of extracting solution be preferably (0.4~
2.5)：1, more preferably (1~2)：1.In the present invention, the chlorinated solvents preferably include dichloromethane, chloroform, 1,1-
Dichloroethanes or 1,2- dichloroethanes.
In the present invention, in terms of the absolute dry mass of the lilac, the OH-Type ion exchange resin is preferably lilac
The 3~20% of quality, more preferably 5~17%, most preferably 8~12%.
The present invention is for the OH-The type of type ion exchange resin and source do not have special restriction, using this field
The OH of the known type of technical staff-The commercial goods of type ion exchange resin.In the present invention, the OH-Type ion exchange
The model of resin preferably includes 201*7, D261, D280, D290, D296, D301-G or D301-R.
In the present invention, the OH-The model and property of type ion exchange resin are as shown in the table：
OH-The model and property of type ion exchange resin
In the present invention, the OH-Type ion exchange resin is pre-processed before use, the pretreated method packet
Include following steps：
(1) it is 88~92% ethanol water to OH to use volumn concentration-Type ion exchange resin is impregnated
Processing, by gained OH-Type ion exchange resin is washed；
(2) OH for using acid reagent to obtain the step (1)-Type ion exchange resin carries out immersion treatment, by gained
OH-Type ion exchange resin is washed to neutrality；
(3) OH for using base reagent to obtain the step (2)-Type ion exchange resin carries out immersion treatment, by gained
OH-Type ion exchange resin is washed to neutrality；
(4) OH for obtaining the step (3)-Type ion exchange resin carries out the place in step (2) and step (3) successively
Reason, obtains pretreated OH-Type ion exchange resin is spare.
Present invention preferably employs volumn concentration be 88~92% ethanol water to OH-Type ion exchange resin into
Row immersion treatment, by gained OH-Type ion exchange resin is washed.In the present invention, the volume hundred of the ethanol water
Point content is preferably 90%.In the present invention, the time of the immersion treatment is preferably 22~26h, more preferably for 24 hours.At this
In invention, water used by the washing is preferably distilled water；The present invention can incite somebody to action the not special restriction of the washing
Gained OH after immersion treatment-Ethyl alcohol in type ion exchange resin is cleaned.
After the completion of using volumn concentration to carry out immersion treatment and washing for 88~92% ethanol water, the present invention
It is preferred that using acid reagent to gained OH-Type ion exchange resin carries out immersion treatment, by gained OH-Type ion exchange resin is washed
To neutrality.In the present invention, the acid reagent is preferably HCl solution.The present invention is not special for the concentration of the HCl solution
Restriction, using concentration well known to those skilled in the art；In an embodiment of the present invention, the concentration of the HCl solution
Specially 0.1mol/L.In the present invention, the time of the immersion treatment is preferably 3~5h, more preferably 4h.In the present invention
In, water used by the washing is preferably distilled water；The present invention can will impregnate the not special restriction of the washing
Gained OH after processing-Type ion exchange resin is washed till neutrality.
After the completion of carrying out immersion treatment and washing using acid reagent, present invention preferably employs base reagents to gained OH-Type from
Sub-exchange resin carries out immersion treatment, by gained OH-Type ion exchange resin is washed to neutrality.In the present invention, the alkali examination
Agent is preferably NaOH solution.The present invention does not have the concentration of the NaOH solution special restriction, using people in the art
Concentration known to member；In an embodiment of the present invention, the concentration of the NaOH solution is specially 0.1mol/L.In the present invention
In, the time of the immersion treatment is preferably 3~5h, more preferably 4h.In the present invention, water used by the washing is preferred
For distilled water；The present invention, can be by gained OH after immersion treatment for the not special restriction of the washing-Type amberlite
Fat is washed till neutrality.
After the completion of carrying out immersion treatment and washing using base reagent, the present invention is preferably tried according to above-mentioned technical proposal using acid
Agent is to gained OH-Type ion exchange resin carries out immersion treatment, by gained OH-Type ion exchange resin is washed to neutrality；Then it presses
According to above-mentioned technical proposal using base reagent to gained OH-Type ion exchange resin carries out immersion treatment, by gained OH-Type ion is handed over
It changes resin and is washed to neutrality, obtain pretreated OH-Type ion exchange resin is spare.
In the present invention, the OH-Often contain a small amount of oligomer in type ion exchange resin commercial goods and does not participate in anti-
The inorganic impurities such as the monomer answered, also iron, lead, copper, when it is contacted with other solution, above-mentioned substance will be transferred to solution
In, influence the quality of final product.Therefore, to the OH-Type ion exchange resin carry out pretreatment can prevent it is therein solvable
Property impurity is transferred in solution, using initial stage, pollutes the water quality of water outlet.
In the present invention, the extraction in combination hydrolysis in situ preferably carries out under sealing condition；The temperature of the extraction in combination hydrolysis in situ
Preferably 70~95 DEG C of degree, more preferably 75~90 DEG C, most preferably 80~85 DEG C；Time is preferably 1~5h, and more preferably 2
~3h.The present invention can be such that the ester bond in oleuropein all hydrolyzes, be converted into free state hydroxyl by the extraction in combination hydrolysis in situ
Base tyrosol, to increase the content of hydroxytyrosol in extract liquor；Wherein, the OH-Type ion exchange resin is as catalyst
It is to extract free state hydroxytyrosol as extractant to promote the hydrolysis of oleuropein, the chlorinated solvents.Therefore, in situ in hydrolysis
In extraction process, the hydrolysis of oleuropein and the extraction of free state hydroxytyrosol are completed at the same time.Meanwhile it is provided by the invention
Extraction in combination hydrolysis in situ method efficiently avoids the lengthy and tedious of hydrolysis and extraction two steps operation again, and saving operational sequence and solvent make
Dosage, production cost is low, and hydroxytyrosol yield is high.In addition, the extraction in combination hydrolysis in situ carries out under sealing condition, it is pollution-free,
Solvent is recyclable, the OH-Through regeneration treatment (with the OH after type ion exchange resin use-Type ion exchange resin
Pretreatment using preceding progress is consistent, is no longer repeated herein) it can recycle, it is produced convenient for industrial scale.
After obtaining extract liquor, the present invention isolates the organic phase in the extract liquor, and the organic phase is concentrated to dryness, is adopted
Resulting material is dissolved with the second ethanol water, obtains lysate.The present invention preferably by the extract liquor stratification,
To isolate organic phase.The present invention is for the not special restriction of the concentration, using well known to those skilled in the art dense
The technical solution of contracting.In the present invention, the volumn concentration of second ethanol water is preferably 20~30%, more
Preferably 23~27%.In the present invention, in terms of absolute dry mass, the organic phase is concentrated to dryness rear resulting material and the second ethyl alcohol
The mass ratio of aqueous solution is preferably 1：(25~35), more preferably 1：30.
After obtaining lysate, the present invention is enriched with the lysate using macroporous absorbent resin, using third ethyl alcohol
Aqueous solution elutes the macroporous absorbent resin after enrichment, and the solvent in removal gained eluent obtains hydroxytyrosol.This hair
It is bright there is no special restriction for the type of the macroporous absorbent resin and source, using type known to those skilled in the art
The commercial goods of macroporous absorbent resin.In the present invention, the model of the macroporous absorbent resin preferably include HPD80,
HPD100, HPD300, HPD5000, AB-8, D101, HPD-D, DM-130, ADS-17, HPD826, ADS-7 or DA-201.
In the present invention, the model and property of the macroporous absorbent resin are as shown in the table：
The model and property of macroporous absorbent resin
In the present invention, the macroporous absorbent resin is pre-processed before use, and the pretreated method is preferably wrapped
Include following steps：
Macroporous absorbent resin is impregnated into 8~12h in the ethyl alcohol that volumn concentration is 90~95%, using distilled water pair
Macroporous absorbent resin after immersion is washed to remove remaining ethyl alcohol, the filtering of family name's funnel, and port grinding bottle seals 22~26h balances up for safekeeping
It is for use to obtain pretreated macroporous absorbent resin for moisture.
In the present invention, sample concentration is preferably 0.2~0.7mg/mL in the enrichment process, more preferably 0.3~
0.5mg/mL.In the present invention, the volumn concentration of the third ethanol water is preferably 70~90%, and more preferably 75
~85%.
In the present invention, the enrichment and elution preferably carry out under sealing condition, and pollution-free, solvent is recyclable to be made
With convenient for industrial scale production.The present invention does not have special restriction for the concrete operation method of the enrichment and elution, adopts
With the technical solution of enrichment and elution well known to those skilled in the art.Macroporous absorbent resin is preferably filled column by the present invention,
Under sealing condition, the lysate is enriched with using gained closing column, then uses the third ethanol water pair
Closing column after enrichment is eluted.In the present invention, the blade diameter length ratio of the closing column is preferably 1：(18~22), more preferably
1:20；The volume of the lysate is preferably close column volume 3~4 times, more preferably 3.5 times；The third ethyl alcohol is water-soluble
The volume of liquid is preferably close column volume 15~25 times, more preferably 20 times.
The method of solvent does not have special restriction in gained eluent after the present invention elutes removal, using this field skill
The technical solution of removal solvent known to art personnel is specific as being evaporated under reduced pressure.In the present invention, molten in gained eluent
Agent preferably carries out recycling, to reduce production cost.
After solvent in removal gained eluent, preferably resulting material is dried by the present invention, obtains hydroxytyrosol.
In the present invention, the drying is preferably dried in vacuo；In the present invention, the vacuum drying temperature is preferably 35~45 DEG C,
More preferably 40 DEG C；The time is preferably 5~7h, more preferably 6h.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
Lilac diameter after natural air drying is crushed into processing, the lilac powder that grain size is 20~40 mesh is obtained, claims
It takes 10.0g lilacs powder to be put into round-bottomed flask (in terms of absolute dry mass), then presses lilac powder and ethanol water
Mass ratio is 1：8 meters, are added the ethanol water that volumn concentration is 80%, and the refluxing extraction 2h in 90 DEG C of water-baths continues
Repeat extraction 2 times, merges resulting material after extraction, filtering, using obtained liquid material as extracting solution；
To OH-Type ion exchange resin (model 201*7) is pre-processed, specifically use volumn concentration for
90% ethanol water is to OH-Type ion exchange resin carries out immersion treatment for 24 hours, by gained OH-Type ion exchange resin uses
Distilled water is washed；Using the HCl solution of 0.1mol/L to gained OH-Type ion exchange resin carries out immersion treatment 4h, will
Gained OH-Type ion exchange resin is washed to neutrality using distillation；Using the NaOH solution of 0.1mol/L to gained OH-Type ion
Exchanger resin carries out immersion treatment 4h, by gained OH-Type ion exchange resin is washed to neutrality using distillation；It repeats to use
The HCl solution of 0.1mol/L carries out immersion treatment, distillation is washed to neutral and is impregnated using the NaOH solution of 0.1mol/L
Processing, distillation are washed to neutral step, obtain pretreated OH-Type ion exchange resin；
By the extracting solution and pretreated OH-Type ion exchange resin 3.0g and 30mL 1, the mixing of 2- dichloroethanes,
Under sealing condition, reflux progress extraction in combination hydrolysis in situ 2h, obtains extract liquor in 85 DEG C of water-baths；
By the extract liquor stratification, organic phase is isolated, the organic phase is concentrated to dryness, then presses resulting material
The mass ratio of (in terms of absolute dry mass) and ethanol water is 1：It is water-soluble that the ethyl alcohol that volumn concentration is 30% is added in 30 meters
Liquid makes the organic phase be concentrated to dryness rear resulting material dissolving, obtains lysate；
Macroporous absorbent resin (model AB-8) is impregnated into 10h in the ethyl alcohol that volumn concentration is 95%, using steaming
Distilled water washs the macroporous absorbent resin after immersion to remove remaining ethyl alcohol, and the filtering of family name's funnel, port grinding bottle is sealed up for safekeeping puts down for 24 hours
The pretreated macroporous absorbent resin of gained is filled column by Hengshui point, and under sealing condition, column (blade diameter length ratio 1 is closed using gained：
20, volume 11.8mL) lysate is enriched with, sample concentration is 0.6mg/mL in the enrichment process；Then it adopts
The ethanol water for being 80% with volumn concentration (volume is close column volume 20 times) carries out the closing column after enrichment
Elution, vacuum distillation remove the solvent in gained eluent, obtain hydroxytyrosol.
The content of hydroxytyrosol in extracting solution is measured, yield is calculated；Meanwhile it calculating according to hydroxyl obtained by method in embodiment 1
The yield of base tyrosol.The result shows that being in terms of 100%, obtained by method in embodiment 1 by the yield of hydroxytyrosol in extracting solution
The yield of hydroxytyrosol is 160.44%.During extraction in combination hydrolysis in situ, hydroxytyrosol is combined into this explanation with glucose
Glycosides compound, i.e. oleuropein is converted into free state hydroxytyrosol, to improve the yield of hydroxytyrosol (specifically such as
Shown in Fig. 2 and Fig. 3).To carrying out purity analysis according to hydroxytyrosol obtained by method in embodiment 1, the results showed that, gained hydroxyl junket
The purity of alcohol is up to 39.5%.Wherein, the content and purity of the hydroxytyrosol are by high performance liquid chromatography detection and to calculate
It obtains, it is specific as shown in Figure 1.
According to OH-Type ion exchange resin carries out pretreated method, and the OH after situ extracting will be hydrolyzed-Type from
Sub-exchange resin is regenerated.The result shows that by the OH after regeneration-Type ion exchange resin is reused 4 times, and hydrolysis efficiency is
The 93.5% of first hydrolysis efficiency.
Embodiment 2
Lilac diameter after natural air drying is crushed into processing, the lilac powder that grain size is 20~40 mesh is obtained, claims
It takes 100.0g lilacs powder to be put into round-bottomed flask (in terms of absolute dry mass), then presses lilac powder and ethanol water
Mass ratio is 1：10 meters, the ethanol water that addition volumn concentration is 80%, the refluxing extraction 3.5h in 95 DEG C of water-baths, after
It is continuous to repeat extraction 2 times, merge resulting material after extraction, filtering, using obtained liquid material as extracting solution；
To OH-Type ion exchange resin (model 201*7) is pre-processed, specifically use volumn concentration for
90% ethanol water is to OH-Type ion exchange resin carries out immersion treatment for 24 hours, by gained OH-Type ion exchange resin uses
Distilled water is washed；Using the HCl solution of 0.1mol/L to gained OH-Type ion exchange resin carries out immersion treatment 4h, will
Gained OH-Type ion exchange resin is washed to neutrality using distillation；Using the NaOH solution of 0.1mol/L to gained OH-Type ion
Exchanger resin carries out immersion treatment 4h, by gained OH-Type ion exchange resin is washed to neutrality using distillation；It repeats to use
The HCl solution of 0.1mol/L carries out immersion treatment, distillation is washed to neutral and is impregnated using the NaOH solution of 0.1mol/L
Processing, distillation are washed to neutral step, obtain pretreated OH-Type ion exchange resin；
By the extracting solution and pretreated OH-Type ion exchange resin 3.0g and 30mL 1, the mixing of 2- dichloroethanes,
Under sealing condition, reflux progress extraction in combination hydrolysis in situ 3h, obtains extract liquor in 85 DEG C of water-baths；
By the extract liquor stratification, organic phase is isolated, the organic phase is concentrated to dryness, then presses resulting material
The mass ratio of (in terms of absolute dry mass) and ethanol water is 1：It is water-soluble that the ethyl alcohol that volumn concentration is 30% is added in 25 meters
Liquid makes the organic phase be concentrated to dryness rear resulting material dissolving, obtains lysate；
Macroporous absorbent resin (model AB-8) is impregnated into 10h in the ethyl alcohol that volumn concentration is 95%, using steaming
Distilled water washs the macroporous absorbent resin after immersion to remove remaining ethyl alcohol, and the filtering of family name's funnel, port grinding bottle is sealed up for safekeeping puts down for 24 hours
The pretreated macroporous absorbent resin of gained is filled column by Hengshui point, and under sealing condition, column (blade diameter length ratio 1 is closed using gained：
20, volume 11.8mL) lysate is enriched with, sample concentration is 0.5mg/mL in the enrichment process；Then it adopts
The ethanol water for being 85% with volumn concentration (volume is close column volume 15 times) carries out the closing column after enrichment
Elution, vacuum distillation remove the solvent in gained eluent, obtain hydroxytyrosol.
The content of hydroxytyrosol in extracting solution is measured, yield is calculated；Meanwhile it calculating according to hydroxyl obtained by method in embodiment 2
The yield of base tyrosol.The result shows that being in terms of 100%, obtained by method in embodiment 2 by the yield of hydroxytyrosol in extracting solution
The yield of hydroxytyrosol is 155.63%.During extraction in combination hydrolysis in situ, hydroxytyrosol is combined into this explanation with glucose
Glycosides compound, i.e. oleuropein is converted into free state hydroxytyrosol, to improve the yield of hydroxytyrosol.
To carrying out purity analysis according to hydroxytyrosol obtained by method in embodiment 2, the results showed that, gained hydroxytyrosol it is pure
It spends up to 36.3%.
According to OH-Type ion exchange resin carries out pretreated method, and the OH after situ extracting will be hydrolyzed-Type from
Sub-exchange resin is regenerated.The result shows that by the OH after regeneration-Type ion exchange resin is reused 4 times, and hydrolysis efficiency is
The 92.4% of first hydrolysis efficiency.
Embodiment 3
Lilac diameter after natural air drying is crushed into processing, the lilac powder that grain size is 20~40 mesh is obtained, claims
It takes 1000.0g lilacs powder to be put into (in terms of absolute dry mass) in pilot scale round-bottomed flask, then presses lilac powder and ethanol water
The mass ratio of solution is 1：The ethanol water that volumn concentration is 80%, the refluxing extraction in 85 DEG C of water-baths is added in 12 meters
4h continues to repeat extraction 2 times, merges resulting material after extraction, filtering, using obtained liquid material as extracting solution；
To OH-Type ion exchange resin (model 201*7) is pre-processed, specifically use volumn concentration for
90% ethanol water is to OH-Type ion exchange resin carries out immersion treatment for 24 hours, by gained OH-Type ion exchange resin uses
Distilled water is washed；Using the HCl solution of 0.1mol/L to gained OH-Type ion exchange resin carries out immersion treatment 4h, will
Gained OH-Type ion exchange resin is washed to neutrality using distillation；Using the NaOH solution of 0.1mol/L to gained OH-Type ion
Exchanger resin carries out immersion treatment 4h, by gained OH-Type ion exchange resin is washed to neutrality using distillation；It repeats to use
The HCl solution of 0.1mol/L carries out immersion treatment, distillation is washed to neutral and is impregnated using the NaOH solution of 0.1mol/L
Processing, distillation are washed to neutral step, obtain pretreated OH-Type ion exchange resin；
By the extracting solution and pretreated OH-Type ion exchange resin 3.0g and 30mL 1, the mixing of 2- dichloroethanes,
Under sealing condition, reflux progress extraction in combination hydrolysis in situ 4h, obtains extract liquor in 95 DEG C of water-baths；
By the extract liquor stratification, organic phase is isolated, the organic phase is concentrated to dryness, then presses resulting material
The mass ratio of (in terms of absolute dry mass) and ethanol water is 1：It is water-soluble that the ethyl alcohol that volumn concentration is 25% is added in 30 meters
Liquid makes the organic phase be concentrated to dryness rear resulting material dissolving, obtains lysate；
Macroporous absorbent resin (model AB-8) is impregnated into 10h in the ethyl alcohol that volumn concentration is 95%, using steaming
Distilled water washs the macroporous absorbent resin after immersion to remove remaining ethyl alcohol, and the filtering of family name's funnel, port grinding bottle is sealed up for safekeeping puts down for 24 hours
The pretreated macroporous absorbent resin of gained is filled column by Hengshui point, and under sealing condition, column (blade diameter length ratio 1 is closed using gained：
20, volume 11.8mL) lysate is enriched with, sample concentration is 0.6mg/mL in the enrichment process；Then it adopts
The ethanol water for being 80% with volumn concentration (volume is close column volume 20 times) carries out the closing column after enrichment
Elution, vacuum distillation remove the solvent in gained eluent, obtain hydroxytyrosol.
The content of hydroxytyrosol in extracting solution is measured, yield is calculated；Meanwhile it calculating according to hydroxyl obtained by method in embodiment 3
The yield of base tyrosol.The result shows that being in terms of 100%, obtained by method in embodiment 3 by the yield of hydroxytyrosol in extracting solution
The yield of hydroxytyrosol is 152.38%.During extraction in combination hydrolysis in situ, hydroxytyrosol is combined into this explanation with glucose
Glycosides compound, i.e. oleuropein is converted into free state hydroxytyrosol, to improve the yield of hydroxytyrosol.
To carrying out purity analysis according to hydroxytyrosol obtained by method in embodiment 3, the results showed that, gained hydroxytyrosol it is pure
It spends up to 35.2%.
According to OH-Type ion exchange resin carries out pretreated method, and the OH after situ extracting will be hydrolyzed-Type from
Sub-exchange resin is regenerated.The result shows that by the OH after regeneration-Type ion exchange resin is reused 4 times, and hydrolysis efficiency is
The 92.6% of first hydrolysis efficiency.
As seen from the above embodiment, the present invention can make the ester bond in oleuropein complete by the extraction in combination hydrolysis in situ
Portion hydrolyzes, and free state hydroxytyrosol is converted into, to increase the content of hydroxytyrosol in extract liquor；Wherein, the OH-Type ion
Exchanger resin is the hydrolysis for promoting oleuropein as catalyst, and the chlorinated solvents are to extract free state hydroxyl as extractant
Tyrosol.Therefore, during extraction in combination hydrolysis in situ, the hydrolysis of oleuropein and the extraction of free state hydroxytyrosol are to be completed at the same time
's.Meanwhile extraction in combination hydrolysis in situ method provided by the invention efficiently avoids lengthy and tedious, the section of hydrolysis and extraction two steps operation again
The usage amount of operational sequence and solvent is saved, production cost is low, and hydroxytyrosol yield is high.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method for extracting hydroxytyrosol from lilac, includes the following steps：
Lilac is extracted using the first ethanol water, obtains extracting solution；
By the extracting solution and OH-Extraction in combination hydrolysis in situ is carried out after type ion exchange resin and chlorinated solvents mixing, is extracted
Liquid；
The organic phase in the extract liquor is isolated, the organic phase is concentrated to dryness, using the second ethanol water to gained
Material is dissolved, and lysate is obtained；
The lysate is enriched with using macroporous absorbent resin, using third ethanol water to the macroporous absorption after enrichment
Resin is eluted, and the solvent in removal gained eluent obtains hydroxytyrosol.
2. according to the method described in claim 1, it is characterized in that, the volumn concentration of first ethanol water is 20
~70%；The volumn concentration of second ethanol water is 20~30%；The volume hundred of the third ethanol water
It is 70~90% to divide content.
3. method according to claim 1 or 2, which is characterized in that in terms of the absolute dry mass of the lilac, the purple fourth
The fragrant mass ratio with the first ethanol water is 1：(8~15).
4. according to the method described in claim 3, it is characterized in that, the temperature of the extraction be 70~95 DEG C, the time be 1~
5h。
5. according to the method described in claim 1, it is characterized in that, the OH-Type ion exchange resin is located in advance using preceding
Reason, the pretreated method include the following steps：
(1) it is 88~92% ethanol water to OH to use volumn concentration-Type ion exchange resin carries out immersion treatment,
By gained OH-Type ion exchange resin is washed；
(2) OH for using acid reagent to obtain the step (1)-Type ion exchange resin carries out immersion treatment, by gained OH-Type
Ion exchange resin is washed to neutrality；
(3) OH for using base reagent to obtain the step (2)-Type ion exchange resin carries out immersion treatment, by gained OH-Type
Ion exchange resin is washed to neutrality；
(4) OH for obtaining the step (3)-Type ion exchange resin carries out the processing in step (2) and step (3) successively, obtains
To pretreated OH-Type ion exchange resin is spare.
6. method according to claim 1 or 5, which is characterized in that in terms of the absolute dry mass of the lilac, the OH-Type
Ion exchange resin is the 3~20% of lilac quality.
7. according to the method described in claim 1, it is characterized in that, the chlorinated solvents include dichloromethane, chloroform, 1,
1- dichloroethanes or 1,2- dichloroethanes.
8. method according to claim 1 or claim 7, which is characterized in that the chlorinated solvents and the volume ratio of extracting solution are
(0.4~2.5)：1.
9. according to the method described in claim 1, it is characterized in that, the extraction in combination hydrolysis in situ carries out under sealing condition；Institute
The temperature for stating extraction in combination hydrolysis in situ is 70~95 DEG C, and the time is 1~5h.
10. according to the method described in claim 1, it is characterized in that, the enrichment and being eluted under sealing condition and carrying out；It is described
Sample concentration is 0.2~0.7mg/mL in enrichment process.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563172A (en) * | 2021-09-23 | 2021-10-29 | 江西中医药大学 | Azulene compound and preparation method and application thereof |
| CN114105751A (en) * | 2022-01-25 | 2022-03-01 | 江西中医药大学 | Terpenoid and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009013596A2 (en) * | 2007-07-23 | 2009-01-29 | Probelte Pharma, S.A. | Fortification of nutritional products with olive extracts containing hydroxytyrosol and hydroxytyrosol fortified nutritional products |
| CN104725197A (en) * | 2015-03-19 | 2015-06-24 | 黑龙江八一农垦大学 | Method for preparing hydroxytyrosol by converting oleuropein through ion exchange resin |
-
2018
- 2018-06-15 CN CN201810620688.1A patent/CN108610241B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009013596A2 (en) * | 2007-07-23 | 2009-01-29 | Probelte Pharma, S.A. | Fortification of nutritional products with olive extracts containing hydroxytyrosol and hydroxytyrosol fortified nutritional products |
| CN104725197A (en) * | 2015-03-19 | 2015-06-24 | 黑龙江八一农垦大学 | Method for preparing hydroxytyrosol by converting oleuropein through ion exchange resin |
Non-Patent Citations (3)
| Title |
|---|
| MARTINWEISSENBERG: "Isolation of solasodine and other steroidal alkaloids and sapogenins by direct hydrolysis-extraction of Solanum plants or glycosides therefrom", 《PHYTOCHEMISTRY》 * |
| 原姣姣: "橄榄苦苷提取物的酶解机制及酚类产物的活性构效关系研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 马春慧: "北五味子活性成分高效分离纯化技术及资源多级利用工艺研究", 《中国博士学位论文全文数据库 农业科技辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563172A (en) * | 2021-09-23 | 2021-10-29 | 江西中医药大学 | Azulene compound and preparation method and application thereof |
| CN113563172B (en) * | 2021-09-23 | 2021-12-17 | 江西中医药大学 | Azulene compound and preparation method and application thereof |
| CN114105751A (en) * | 2022-01-25 | 2022-03-01 | 江西中医药大学 | Terpenoid and preparation method and application thereof |
| CN114105751B (en) * | 2022-01-25 | 2022-04-15 | 江西中医药大学 | Terpenoid and preparation method and application thereof |
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