CN105713053A - Extraction and separation method of glucosinolate - Google Patents
Extraction and separation method of glucosinolate Download PDFInfo
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- CN105713053A CN105713053A CN201610180408.0A CN201610180408A CN105713053A CN 105713053 A CN105713053 A CN 105713053A CN 201610180408 A CN201610180408 A CN 201610180408A CN 105713053 A CN105713053 A CN 105713053A
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- activated carbon
- thioglycoside
- extraction
- glucosinolate
- raw material
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/14—Acyclic radicals, not substituted by cyclic structures attached to a sulfur, selenium or tellurium atom of a saccharide radical
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
Abstract
The invention discloses an extraction and separation method of glucosinolate, and relates to extraction and separation of an active substance in the field of biochemical engineering, in particular to an extraction and separation method of glucosinolate prepared from the raw material of crucifer seeds. According to the method, crucifer seeds are smashed, so that the degree of cell disruption is increased, and glucosinolate is helped to be fully dissolved out; a boiling water extraction method is adopted to extract glucosinolate, and thus the extraction ratio can reach 96.0% or above; an activated carbon adsorption and elution method is adopted to purify glucosinolate, and thus the purity of the obtained glucosinolate product can be increased by 2.5-3.0 times than that of water extract. Compared with a traditional extraction and separation method of glucosinolate, the method is high in glucosinolate extraction efficiency, good in purification effect, simple in process, environmentally friendly, applicable to production and processing of food-grade or health-food-grade glucosinolate and suitable for large-scale industrial production and has good popularization prospects.
Description
Technical field
The extraction that the present invention relates to a kind of active substance in biological chemical field separates, a kind of extraction separation method preparing thioglycoside with crucifer seeds for raw material.
Background technology
The plant of Cruciferae is the class plant being widely believed that at present and having anti-cancer function.This plant being primarily due to Cruciferae contains substantial amounts of thioglycoside (glucosinolates, it is called for short GLS), thioglycoside is a kind of sulfur-bearing secondary metabolite of plant, has been found that more than 120 kind of thioglycoside at present in plant.Thioglycoside is the ionic compound of water solublity, non-volatility, heat stability.If plant cell occur breakage, sulfur for heteroside glycosylhydrolase, i.e. Semen Sinapis sulfur thuja acid enzyme (myrosinase, thioglucoside glucohydrolase；EC3.2.3.1) being released, and hydrolyze thioglycoside, generate disulfate, glucose and a series of aglucone, these aglucons are forming isothiocyanate, sulfocyanic ester, nitrile and a small amount of epithio nitrile through intramolecular rearrangement.At present, there is a lot of research to have shown that isothiocyanate has good anticancer effect and antioxidation, also there are some researches show that thioglycoside metabolism can generate isothiocyanate in vivo, then play its anticancer, antioxidation and antibacterial action.In recent years, the more thioglycoside of research includes the glucose Sulforaphane (glucophanin is called for short GRA) in broccoli seed, the glucorphanin (glucophenin is called for short GRE) etc. in radish seed both at home and abroad.Thioglycoside basic structure is as follows:
The extracting method of thioglycoside is mainly hot lifting manipulation at present, and the solvent of use includes ethanol, methanol, water and alcohol water mixed solution etc., has investigated the factor impacts on extraction efficiency such as temperature, solid-liquid ratio, time；The isolation and purification method of thioglycoside is mainly extraction, acidic alumina method and ion-exchange-resin process etc..Empirical tests, uses and extracts containing alcoholic solvent, and thioglycoside extraction ratio is relatively low and relatively costly；Using acidic alumina or ion exchange resin to be purified, introduce a large amount of salinity, desalting process is complicated and the response rate is relatively low.The Chinese invention patent application of Application No. 201210166482.9 discloses a kind of method extracting thioglycoside from broccoli stem and leaf garbage, the method by raw material after 75 DEG C of water-bath enzyme denaturing, 75% methanol aqueous solution is used for multiple times and extracts thioglycoside, then use anion exchange that sulfur glycosides is purified, enzyme denaturing is the most thorough, experiment complexity, relatively costly.The Chinese invention patent application of Application No. 2015104107303.X discloses the method for the extraction of a kind of stem sulfur mustard thioglycoside, the method is by after raw material drying enzyme denaturing, grinding and ether defatting, use methanol aqueous solution that thioglycoside is extracted by ultrasonication, and then use ethyl acetate remove impurity and anion exchange resin purification, purification process is extremely complex, energy consumption is higher, and extraction ratio is only 65%-75%, and uses the toxic reagents such as methanol, ether, ethyl acetate.
Summary of the invention
It is an object of the invention to set up efficiently, environmental protection, technique simple thioglycoside extraction and purification process method.With crucifer seeds as raw material, realize cell breakage by the method pulverized, thus improve the dissolution of thioglycoside；The method using boiling water extraction extracts thioglycoside, and boiling water extraction both can make source myrosin deactivation also can promote cell breakage further, and extraction ratio relatively alcohol water extraction is more；With 10% ethanol water as eluent, with Aqueous extracts for absorption stock solution, using activated carbon adsorption elution method purification thioglycoside, raising thioglycoside product purity is to 2.5-3.0 times, and the whole technological process gained thioglycoside response rate is up to more than 85%.
The thioglucose glycoside extraction separation technique method that the present invention is set up, extraction efficiency is high, purification effect is good, and technique is simple, environmental protection, it is adaptable to the production and processing of the thioglycoside of food stage and health care grade, has good promotion prospect.
Concrete grammar and the step of the present invention are as follows:
A kind of method using activated carbon purification thioglycoside, with crucifer seeds as raw material, in turn includes the following steps:
A. raw material is pulverized
Use pulverizer that raw material is pulverized, collect seed powder；
B. the extraction of thioglycoside
Measure deionized water heating, after deionized water seethes with excitement, according to the ratio of solid-to-liquid ratio 1:10, add the raw material after pulverizing in (1), boiling water extraction 10min, use filter cloth suction filtering to obtain Aqueous extracts；Repeat to extract once, collect thioglycoside Aqueous extracts；
C. the purification of thioglycoside
According to activated carbon: thioglycoside mass ratio is that 1000:60-80 determines activated carbon dosage, is added by Aqueous extracts in activated carbon, stirring and adsorbing 30min under the conditions of 25 DEG C, is filtrated to get the activated carbon filter cake being adsorbed with thioglycoside；Activated carbon filter cake according to being adsorbed with thioglycoside: 10% ethanol water solid-to-liquid ratio is 1:20, add 10% ethanol water, use ammonia regulation, measure eluent pH=10 through pH meter, eluting 30min is stirred under the conditions of 25 DEG C, it is filtrated to get activated carbon and eluent, it is continuing with 10% ethanol water and activated carbon is carried out secondary eluting, collect twice eluent；10% ethanol water be concentration of volume percent be the ethanol water of 10%；
Gained eluent is spin-dried for, is dissolved in water, repeat the experiment of above-mentioned absorb-elute；Final gained eluent is through decompression distillation, lyophilization.
Further, activated carbon used is craboraffin.
1. the raw material used in step (A) is crucifer seeds, such as the seed of the plants such as Caulis et Folium Brassicae capitatae, Radix Raphani, Caulis et Folium Brassicae capitatae, Brassica oleracea L. var. botrytis L..
2. in step (B), activated carbon addition refers to the saturated extent of adsorption of activated carbon, and activated carbon is 61mg/g to the saturated extent of adsorption of glucorphanin as used in the present invention, then glucorphanin Aqueous extracts need to be concentrated to about 3.0mg/ml.
3. activated carbon used in step (C) is wooden 200 mesh craboraffins.
4. in step (C), regulation and the mensuration of eluent pH value use ammonia spirit and pH meter respectively.
5. in step (C), solid-liquid separating equipment is activated carbon filter.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but these embodiments be not intended to limit the scope of the invention.Activated carbon BET specific surface area 1700-1900m employed in following example2/ g, activated carbon decolorizing rate: 180-240mg/g, but it is not limited to this.
Embodiment 1
Pretreatment of raw material: certain broccoli seed that 200gGRA content (mass percentage content, as follows) is 4.01% is pulverized, obtains 200g broccoli seed powder.
Thioglycoside extracts: taking the heating of 2.3L deionized water, after boiling, be added thereto to above-mentioned broccoli seed powder, boiling water extraction 10min, filter-cloth filtering obtains GRA Aqueous extracts.Repeating to extract once, collect GRA Aqueous extracts, GRA extraction ratio is 98.61%.
Thioglycoside purification: above-mentioned GRA Aqueous extracts is concentrated into 2.3L, is added in 115g activated carbon, stirring and adsorbing 30min under the conditions of 25 DEG C.Using activated carbon filter to carry out solid-liquid separation, obtain being adsorbed with the activated carbon of GRA, add 2.3L 10% ethanol water, regulation pH is 10.0, and eluting 30min at 25 DEG C repeats eluting once, collects GRA eluent.Above-mentioned GRA eluent is spin-dried for, adds 2.3L deionized water, as activated carbon adsorption stock solution, carry out activated carbon according to above-mentioned absorb-elute method secondarily purified.Carrying out lyophilization after being spin-dried for by the GRA eluent finally given, obtain GRA product 12.91g, product G RA purity is 49.81% (stock solution GRA purity is 17.14%, and GRA purity brings up to 2.91 times after purification), and the response rate is 81.30%.
Embodiment 2
Pretreatment of raw material: certain broccoli seed that 100gGRA content is 6.72% is pulverized, obtains 200g broccoli seed powder.
Thioglycoside extracts: taking the heating of 1.9L deionized water, after boiling, be added thereto to above-mentioned broccoli seed powder, boiling water extraction 10min, filter-cloth filtering obtains GRA Aqueous extracts.Repeating to extract once, collect GRA Aqueous extracts, GRA extraction ratio is 98.56%.
Thioglycoside purification: above-mentioned GRA Aqueous extracts is concentrated into 1.9L, is added in 95g activated carbon, stirring and adsorbing 30min under the conditions of 25 DEG C.Using activated carbon filter to carry out solid-liquid separation, obtain being adsorbed with the activated carbon of GRA, add 1.9L 10% ethanol water, regulation pH is 10.0, and eluting 30min at 25 DEG C repeats eluting once, collects GRA eluent.Above-mentioned GRA eluent is spin-dried for, adds 1.9L deionized water, as activated carbon adsorption stock solution, carry out activated carbon according to above-mentioned absorb-elute method secondarily purified.Carrying out lyophilization after being spin-dried for by the GRA eluent finally given, obtain GRA and produce 7.63g, product G RA purity is 69.55% (stock solution GRA purity is 27.80%, and GRA purity brings up to 2.50 times after purification), and the response rate is 80.09%.
Embodiment 3
Pretreatment of raw material: certain broccoli seed that 200gGRA content is 3.47% is pulverized, obtains 200g broccoli seed powder.
Thioglycoside extracts: taking the heating of 2.0L deionized water, after boiling, be added thereto to above-mentioned broccoli seed powder, boiling water extraction 10min, filter-cloth filtering obtains GRA Aqueous extracts.Repeating to extract once, collect GRA Aqueous extracts, GRA extraction ratio is 96.98%.
Thioglycoside purification: above-mentioned GRA Aqueous extracts is concentrated into 2.0L, is added in 100g activated carbon, stirring and adsorbing 30min under the conditions of 25 DEG C.Using activated carbon filter to carry out solid-liquid separation, obtain being adsorbed with the activated carbon of GRA, add 2.0L 10% ethanol water, regulation pH is 10.0, and eluting 30min at 25 DEG C repeats eluting once, collects GRA eluent.Above-mentioned GRA eluent is spin-dried for, adds 2.0L deionized water, as activated carbon adsorption stock solution, carry out activated carbon according to above-mentioned absorb-elute method secondarily purified.Carrying out lyophilization after being spin-dried for by the GRA eluent finally given, obtain GRA product 12.70g, product G RA purity is 45.49% (stock solution GRA purity is 15.74%, and GRA purity brings up to 2.89 times after purification), and the response rate is 83.11%.
Embodiment 4
Pretreatment of raw material: certain radish seed that 100gGRE content is 7.29% is pulverized, obtains 200g broccoli seed powder.
Thioglycoside extracts: taking the heating of 2.4L deionized water, after boiling, be added thereto to above-mentioned broccoli seed powder, boiling water extraction 10min, filter-cloth filtering obtains GRE Aqueous extracts.Repeating to extract once, collect GRE Aqueous extracts, GRE extraction ratio is 98.04%.
Thioglycoside purification: above-mentioned GRE Aqueous extracts is concentrated into 2.4L, is added in 120g activated carbon, stirring and adsorbing 30min under the conditions of 25 DEG C.Using activated carbon filter to carry out solid-liquid separation, obtain being adsorbed with the activated carbon of GRE, add 2.4L 10% ethanol water, regulation pH is 10.0, and eluting 30min at 25 DEG C repeats eluting once, collects GRE eluent.Above-mentioned GRE eluent is spin-dried for, adds 2.4L deionized water, as activated carbon adsorption stock solution, carry out activated carbon according to above-mentioned absorb-elute method secondarily purified.Carrying out lyophilization after being spin-dried for by the GRE eluent finally given, obtain GRA product 7.29g, product G RE purity is 79.77% (stock solution GRA purity is 31.04%, and GRE purity brings up to 2.57 times after purification), and the response rate is 81.32%.
Embodiment 5
Pretreatment of raw material: certain radish seed that 100gGRE content is 6.13% is pulverized, obtains 200g broccoli seed powder.
Thioglycoside extracts: taking the heating of 2..0L deionized water, after boiling, be added thereto to above-mentioned broccoli seed powder, boiling water extraction 10min, filter-cloth filtering obtains GRE Aqueous extracts.Repeating to extract once, collect GRE Aqueous extracts, GRE extraction ratio is 97.68%.
Thioglycoside purification: above-mentioned GRE Aqueous extracts is concentrated into 2.0L, is added in 100g activated carbon, stirring and adsorbing 30min under the conditions of 25 DEG C.Using activated carbon filter to carry out solid-liquid separation, obtain being adsorbed with the activated carbon of GRE, add 2.0L 10% ethanol water, regulation pH is 10.0, and eluting 30min at 25 DEG C repeats eluting once, collects GRE eluent.Above-mentioned GRE eluent is spin-dried for, adds 2.0L deionized water, as activated carbon adsorption stock solution, carry out activated carbon according to above-mentioned absorb-elute method secondarily purified.Carrying out lyophilization after being spin-dried for by the GRE eluent finally given, obtain GRE product 7.79g, product G RA purity is 62.49% (stock solution GRA purity is 23.23%, and GRA purity brings up to 2.69 times after purification), and the response rate is 81.32%.
Claims (3)
1. the method using activated carbon purification thioglycoside, with crucifer seeds be
Raw material, in turn includes the following steps:
A. raw material is pulverized
Use pulverizer that raw material is pulverized, collect seed powder；
B. the extraction of thioglycoside
Measure deionized water heating, after deionized water seethes with excitement, according to the ratio of solid-to-liquid ratio 1:10,
Add the raw material after pulverizing in (1), boiling water extraction 10min, use filter cloth suction filtering to obtain Aqueous extracts；
Repeat to extract once, collect thioglycoside Aqueous extracts；
C. the purification of thioglycoside
According to activated carbon: thioglycoside mass ratio is that 1000:60-80 determines activated carbon dosage, will
Aqueous extracts adds in activated carbon, and stirring and adsorbing 30min under the conditions of 25 DEG C is filtrated to get and is adsorbed with
The activated carbon filter cake of thioglycoside；Activated carbon filter cake according to being adsorbed with thioglycoside:
10% ethanol water solid-to-liquid ratio is 1:20, adds 10% ethanol water, uses ammonia regulation, warp
PH meter measures eluent pH=10, stirs eluting 30min, be filtrated to get activity under the conditions of 25 DEG C
Charcoal and eluent, be continuing with 10% ethanol water and activated carbon carry out secondary eluting, collect two
Secondary eluent；10% ethanol water be concentration of volume percent be the ethanol water of 10%；
Gained eluent is spin-dried for, is dissolved in water, repeat the experiment of above-mentioned absorb-elute；Final gained is washed
De-liquid is through decompression distillation, lyophilization.
Method the most according to claim 1, is characterized in that: the raw material used in step A is
Caulis et Folium Brassicae capitatae, Radix Raphani, rocket salad, Caulis et Folium Brassicae capitatae or cauliflower seed.
Method the most according to claim 1, is characterized in that: activated carbon used is craboraffin.
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| CN201610180408.0A CN105713053B (en) | 2016-03-26 | 2016-03-26 | A kind of glucosinolate extraction separation method |
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| CN201610180408.0A CN105713053B (en) | 2016-03-26 | 2016-03-26 | A kind of glucosinolate extraction separation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501354A (en) * | 2017-08-18 | 2017-12-22 | 赣州华汉生物科技有限公司 | A kind of method for extracting high-purity glucorphanin |
| CN110638011A (en) * | 2019-11-05 | 2020-01-03 | 严钦武 | Pickling method of leaf mustard |
| CN110697714A (en) * | 2019-10-17 | 2020-01-17 | 北京化工大学 | Radish-derived nitrogen-doped graded porous carbon and preparation method and application thereof |
| CN111387399A (en) * | 2020-04-07 | 2020-07-10 | 天津市食品研究所有限公司 | Process method for deodorizing radish juice and obtained radish juice |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501354A (en) * | 2017-08-18 | 2017-12-22 | 赣州华汉生物科技有限公司 | A kind of method for extracting high-purity glucorphanin |
| CN110697714A (en) * | 2019-10-17 | 2020-01-17 | 北京化工大学 | Radish-derived nitrogen-doped graded porous carbon and preparation method and application thereof |
| CN110638011A (en) * | 2019-11-05 | 2020-01-03 | 严钦武 | Pickling method of leaf mustard |
| CN111387399A (en) * | 2020-04-07 | 2020-07-10 | 天津市食品研究所有限公司 | Process method for deodorizing radish juice and obtained radish juice |
| CN111387399B (en) * | 2020-04-07 | 2024-02-23 | 天津市食品研究所有限公司 | Technological method for deodorizing radish juice and radish juice obtained by same |
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| CN105713053B (en) | 2018-09-21 |
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