CN105497622A - Method for extracting tricin from corn bracts - Google Patents
Method for extracting tricin from corn bracts Download PDFInfo
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Abstract
The invention discloses a method for extracting tricin from corn bracts. The method includes the steps that the corn bracts are subjected to normal temperature extraction with water, and extraction residues are obtained; an ethanol solution with the volume fraction of 80% to 90% is used for conducting reflux extraction on the extraction residues, an acid medium is added to the ethanol solution, an obtained extracting solution is subjected to vacuum concentration, and concentrate is obtained; the concentrate is diluted with water, the pH value is adjusted to 7.8 to 8.2, and supernatant is taken after solid-liquid separation; macroreticular resin column chromatography is conducted on the supernatant, and corn bract extract containing tricin is obtained. Normal temperature extraction is firstly conducted with water during alcohol extraction, and therefore protein, polysaccharide and other impurities can be removed in advance. The acid medium is added to the ethanol solution used for reflux extraction, and therefore the extraction efficiency of low-polarity tricin can be effectively improved. The pH value of the concentrate diluent is adjusted to 7.8 to 8.2, at the moment, chlorophyll, protein, polysaccharide and other impurities in the concentrate diluent quickly settle in the weak base environment, and the extraction period of tricin is greatly shortened.
Description
Technical field
The invention belongs to biomedicine field, be specifically related to a kind of method extracting tricin from Semen Maydis bract.
Background technology
Tricin (tricin) is also known as tricin, Wheat flavone.Tricin is yellow needles (Acetic Acid-Water), yellow powder (chloroform-methanol), fusing point 291-292 DEG C.Tricin is present in stem, the Ye Zhong of grass awns (MiscanthussinensisAnderss.), and leguminous plant alfalfa (MedicagosativaL.), in the plants such as feverfew.Tricin has relexation to isolated guinea pig intestinal tube, has slight antioxidation, epinephrine can be prevented to be oxidized, and have slight estrogen-like effects, also can be used as dyestuff intermediate.But the tricin Related product sold in the market is prepared mostly from alfalfa,
The Chinese invention patent application being CN102911146A as application publication number discloses a kind of method extracting tricin from alfalfa, the method comprises the following steps: 1) alfalfa is pulverized, add 5-8 times amount 60-80% alcohol reflux 2-3 time, extracting solution is concentrated into without alcohol, add in polyamide and adsorb, alcoholic solution gradient elution, thin layer detects, collect after high concentration flow point concentrates and add extraction into ethyl acetate, reclaim ethyl acetate and obtain crude product; 2) normal hexane, ethyl acetate, methanol, water mixing is got, get and fill high speed adverse current chromatogram post mutually, rotate main frame, pump into and do mobile phase mutually down, mobile phase dissolves crude product by injection valve sample introduction, UV-detector on-line monitoring, collects target component, merges flow point drying under reduced pressure and obtains high-purity tricin.
The deficiency that the method for said extracted tricin exists is: (1) alfalfa resource-constrained, extracts raw material resources deficient; (2) extraction process is complicated, and uses the organic solvent compared with multiple types, and not only extraction cost is high, and the organic solvent used all has larger zest and toxicity to operator and environment, and leaching process pole not environmentally; (3) step 1) in directly adopt alcohol extraction, the impurity that a large amount of polarity is larger while isolating tricin is also extracted, make before carrying out fine separation purification, in crude product, the purity of effective ingredient is low, not only reduce extraction efficiency, bring larger inconvenience also to follow-up fine separation purification; (4) product price is high.
For solving the problem, Authorization Notice No. is that the Chinese patent literature of CN102040578B discloses a kind of method preparing high-purity tricin from Folium Bambusae, the method comprises: (a) makes dry Folium Bambusae 95% ethanol 60 DEG C of reflux, extract, three times, the extracting solution of merging is concentrated into without alcohol taste, use petroleum ether extraction again, aqueous phase is condensed into extractum; B () makes extractum AB-8 macroporous resin column upper after a small amount of 95% dissolve with ethanol, first use pure water eluting, then use 80% ethanol elution, and eluent is concentrated and dry; C () adds methanol hydrochloride solution in step (b) desciccate, acidolysis process is carried out in heating, neutralizes after being disposed with dilute NaOH solution; Wherein, described methanol hydrochloride solution is that both methanol and 25% hydrochloric acid are with the mixture of volume ratio 4:1, described heating refluxes in boiling water bath, and the time of described acidolysis process is 2 hours, and the ratio of described step (b) desciccate and methanol hydrochloride solution is 50mg:25ml; D () makes step (c) gained acid hydrolysis solution mix with the C18 filler of sample equivalent weight, concentrate and mix sample drying, dry C18 filler is made to mix sample solid loading again, by C18 column chromatography on the sample of 1:10 and proportion of filler, first use 20% methanol aqueous solution eluting, use 60% methanol aqueous solution eluting again, collect tricin fraction, concentrated; E () makes step (d) gained concentrate dissolve with methanol, by sample and the proportion of filler of 1:10, upper gel detached dowel, makes mobile phase eluting with pure methanol, collects tricin fraction, is concentrated to drying, obtains tricin.
The weak point of this extracting method is: directly adopt alcohol extraction in (1) step (a), the impurity that a large amount of polarity is larger while isolating tricin is also extracted, make before carrying out fine separation purification (i.e. step (c)), the purity of effective ingredient low (being only about 3%) in crude product, not only reduce extraction efficiency, bring larger inconvenience also to follow-up fine separation purification; (2) still will use the larger organic solvent of the zests such as petroleum ether in leaching process, and the consumption of ethanol is also larger.
Semen Maydis bract is the outer bract of grass family Zea plant Zea mays (ZeamaysL.), pharmacological research shows, Semen Maydis bract water extract has the blood fat reducing arteriosclerosis rabbit and the effect of defending and treating Arteries of Rabbits to harden, containing abundant tricin in bract, there is antioxidation, relaxing smooth muscle, antitumor and plant growth regulation.
China is corn planting big country, and the annual bract gathered has 1,500 ten thousand tons, after Semen Maydis of gathering every year, has a large amount of Semen Maydis bracts to go out of use, is not only the significant wastage of resource, also pollutes environment.The application is intended to provide a kind of technique extracting tricin from Semen Maydis bract, turns waste into wealth.
At present, mainly the aspects such as fuel, feedstuff and handicraft knitting are concentrated, also not to the research that the tricin in Semen Maydis bract extracts to the report of Semen Maydis bract both at home and abroad.
Summary of the invention
The invention provides a kind of method extracting tricin from Semen Maydis bract, this method solve the problem that in prior art, tricin extraction efficiency is low.
From Semen Maydis bract, extract a method for tricin, comprise the following steps:
(1) with water, extract at room temperature is carried out to Semen Maydis bract, get extraction slag;
(2) extract slag for 80 ~ 90% described in the alcoholic solution reflux, extract, being added with acid medium by volume fraction, by gained extracting solution concentrating under reduced pressure, obtain concentrate;
(3) by described concentrate thin up and adjust ph to 7.8 ~ 8.2, after solid-liquid separation, supernatant is got;
(4) macroporous adsorbent resin column chromatography is carried out to described supernatant, obtain the Semen Maydis bract extract containing tricin.
Because the polarity of tricin is less, therefore the present invention first uses water extract at room temperature between alcohol extraction, so can remove deproteinize, impurity that polysaccharide isopolarity is larger in advance, avoid these impurity to dissolve in ethanol, increase the remove impurity burden of follow-up macroporous adsorptive resins, reduce impurity content in Semen Maydis bract extract.
Meanwhile, step (2) adds acid medium in for the alcoholic solution of reflux, extract, and acid medium effectively can improve the extraction efficiency of little polarity tricin.
And, the pH value of concentrate diluent is adjusted to 7.8 ~ 8.2 by step (3), the impurity such as chlorophyll, protein, polysaccharide now in concentrate diluent precipitates rapidly under weakly alkaline environment, thus do not need low temperature for a long time leave standstill can room temperature dilution, be separated immediately, greatly shorten the extracting cycle of tricin, also further reduce the content of impurity in Semen Maydis bract extract; After macroporous adsorbent resin column chromatography removes impurity further, in the Semen Maydis bract extract of acquisition, the content of tricin has 10% at least.
As preferably, in step (1), described Semen Maydis bract is crushed to after granularity is less than 0.5cm and carries out extract at room temperature again.Suitable refinement is carried out to Semen Maydis bract, is conducive to the reflux, extract, efficiency improving alcoholic solution.
As preferred further, in step (1), described extract at room temperature is immersed in water by Semen Maydis bract, and the mixed proportion of Semen Maydis bract and water is 1kg:8 ~ 10L, and soak time is 2 ~ 4h; Be more preferably and soak 3h.Can agitation as appropriate in extract at room temperature process, improve impurity dissolution rate.
As preferably, in step (2), described acid medium is hydrochloric acid.The acidity of hydrochloric acid is comparatively strong, and not only to macroporous adsorptive resins and equipment harmless (although the acidity such as sulphuric acid, nitric acid is also comparatively strong, corrosivity is also comparatively strong, unfavorable to equipment) simultaneously, only need add little amount can realize corresponding function; And follow-uply also can not to remain when carrying out macroporous adsorbent resin column chromatography (weak acid has residual, is unfavorable for macroporous adsorptive resins cleaning and direct recycling).
As do not made specified otherwise, hydrochloric acid described in the present invention refers to commercially available concentrated hydrochloric acid (mass fraction be about 37%, molar concentration be 12mol/L).
As preferred further, the addition of described acid medium is 0.01 ~ 0.05% of Semen Maydis bract quality.If the addition of acid medium is very few, then extraction effect is not obvious; If addition is too much, then tricin can be caused to decompose.
As preferred further, the addition of described hydrochloric acid is 0.03 ~ 0.05% of Semen Maydis bract quality.
In step (2), the number of times of reflux, extract, is more can improve reflux, extract, efficiency, preferably repeat extraction twice, during each extraction, the w/v of Semen Maydis bract and alcoholic solution is preferably: 1kg:8 ~ 10L, each extraction time is at least 1 hour.
As preferably, in step (3), described concentrate is diluted with water to total solid content and accounts for 5 ~ 10%.Suitable dilution ratio both avoided supernatant volume excessive, increase follow-up solvent use amount when carrying out macroporous adsorbent resin column chromatography, also can ensure the impurity such as chlorophyll, protein, polysaccharide in concentrate Precipitation fully under weakly alkaline environment.
As preferably, in step (4), described macroporous adsorbent resin column chromatography comprises: add in macroporous adsorptive resins by described supernatant, first wash with water to effluent pH value be 7.0 ~ 7.8, again successively with the alcoholic solution eluting that alcoholic solution, volume fraction that volume fraction is 15 ~ 20% are 70 ~ 80%, collected volume mark is the stripping liquid of the alcoholic solution eluting gained of 70 ~ 80%, by this stripping liquid concentrating under reduced pressure, drying, obtains the Semen Maydis bract extract containing tricin.
Because supernatant is alkalescence, the impurity that the polarity therefore after upper prop in supernatant is larger then cannot be adsorbed on macroporous adsorbent resin, first washes with water and Impurity elution larger for polarity can be got off; When effluent pH value is 7.0 ~ 7.8, the larger impurity of polarity is substantially by eluting, therefore continue to adopt volume fraction be the alcoholic solution eluting of 15 ~ 20% remove the impurity of middle polarity, thus the impurity as much as possible in removing Semen Maydis bract extract; Be finally the alcoholic solution eluting effective ingredient of 70 ~ 80% by volume fraction, obtain the Semen Maydis bract extract containing tricin.
As further preferably, in step (4), in described macroporous adsorptive resins, load low pole macroporous adsorbent resin; LX11 macroporous adsorbent resin can be selected.
As preferred further, in step (4), described drying is vacuum drying or spraying dry, and the moisture being dried to described Semen Maydis bract extract is no more than 5%.Under this moisture, microorganism is not easy breeding, the long shelf-life of Semen Maydis bract extract.
Present invention also offers a kind of Semen Maydis bract extract, this Semen Maydis bract extract is prepared from by said method of the present invention, containing the tricin of at least 10%.
Compared with prior art, beneficial effect of the present invention is:
(1) the present invention first uses water extract at room temperature between alcohol extraction, so can remove deproteinize, impurity that polysaccharide isopolarity is larger in advance, avoid these impurity to dissolve in ethanol, increase the remove impurity burden of follow-up macroporous adsorptive resins, reduce impurity content in Semen Maydis bract extract, the tricin that polarity is less then can be stayed to extract in slag and be extracted by alcoholic solution;
(2) the present invention adds acid medium in for the alcoholic solution of reflux, extract, and acid medium effectively can improve the extraction efficiency of little polarity tricin;
(3) pH value of concentrate diluent is adjusted to 7.8 ~ 8.2 by the present invention, the impurity such as chlorophyll, protein, polysaccharide now in concentrate diluent precipitates rapidly under weakly alkaline environment, thus do not need low temperature for a long time leave standstill can room temperature dilution, be separated immediately, greatly shorten the extracting cycle of tricin, also further reduce the content of impurity in Semen Maydis bract extract;
(4) the present invention is by weakly alkaline supernatant upper prop, and the impurity that supernatant Semi-polarity is larger cannot be adsorbed on macroporous adsorbent resin, therefore first washes with water and Impurity elution larger for polarity can be got off; When effluent pH value is 7.0 ~ 7.8, the larger impurity of polarity is substantially by eluting, therefore continue to adopt volume fraction be the alcoholic solution eluting of 15 ~ 20% remove the impurity of middle polarity, thus the impurity as much as possible in removing Semen Maydis bract extract; Be finally the alcoholic solution eluting of 70 ~ 80% by volume fraction, in the Semen Maydis bract extract of acquisition, the content of tricin has 10% at least, is more than three times of the prior art;
(5) organic solvent used in leaching process of the present invention is only second alcohol and water, the volume fraction of alcoholic solution is all lower simultaneously, not only greatly save ethanol consumption, reduce extraction cost, and water and ethanol are to operator with environment is substantially non-stimulated, avirulence, leaching process is environmental protection more;
6) extracting method rational technology of the present invention, simple to operate, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the HPLC detection figure of tricin sterling;
Fig. 2 is the HPLC detection figure of Semen Maydis bract extract in embodiment 1;
Fig. 3 is the HPLC detection figure of Semen Maydis bract extract in embodiment 2;
Fig. 4 is the HPLC detection figure of Semen Maydis bract extract in embodiment 3;
Fig. 5 is the HPLC detection figure of Semen Maydis bract extract in embodiment 4;
Fig. 6 is the HPLC detection figure of Semen Maydis bract extract in embodiment 5;
Fig. 7 is the HPLC detection figure of Semen Maydis bract extract in embodiment 6;
Fig. 8 is the HPLC detection figure of Semen Maydis bract extract in comparative example 1;
Fig. 9 is the HPLC detection figure of Semen Maydis bract extract in comparative example 2;
Figure 10 is the HPLC detection figure of Semen Maydis bract extract in comparative example 3;
Figure 11 is the HPLC detection figure of Semen Maydis bract extract in comparative example 4;
Figure 12 is the HPLC detection figure of Semen Maydis bract extract in comparative example 5;
Figure 13 is the HPLC detection figure of Semen Maydis bract extract in comparative example 6;
Figure 14 is the HPLC detection figure of Semen Maydis bract extract in comparative example 7;
Figure 15 is the HPLC detection figure of Semen Maydis bract extract in comparative example 8;
Figure 16 is the HPLC detection figure of Semen Maydis bract extract in comparative example 9;
Figure 17 is the HPLC detection figure of Semen Maydis bract extract in comparative example 10.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described in further detail.
Embodiment 1
A kind of method extracting tricin from Semen Maydis bract of the present embodiment, comprises the following steps:
(1) take dry Semen Maydis bract broken (granularity is less than 0.5cm) 10kg, put in 200L extraction pot, add water 100L, soak 3h under agitation, discard extracting solution, extract slag for subsequent use;
(2) be 80% by volume fraction and be added with this extraction slag of alcoholic solution reflux, extract, of hydrochloric acid (12mol/L), by gained extracting solution concentrating under reduced pressure, obtaining concentrate; Wherein, the addition of hydrochloric acid is 0.03% (i.e. 0.003kg) of the broken quality of Semen Maydis bract;
Be specially: 1. in extraction slag, add the alcoholic solution 100L that volume fraction is 80%, open stirring;
2. open jacket steam, when being heated to alcohol reflux, start timing, reflux, extract, 1h;
3. after reflux, extract, feed liquid is crossed 400 order filter bags, and in filtering residue, again drop into the alcoholic solution 100L that volume fraction is 80%, repeat reflux, extract, 1h;
4. repeat after reflux, extract, secondary feed liquid crossed 400 order filter bags, and by secondary filtrate with 3. in filtrate merge, and suck 100L outer circulation;
5. open outer circulation vacuum and steam, start to reclaim ethanol, to distillate without after alcohol taste, blowing, weighs, and obtains concentrate;
(3) concentrate is diluted with water to total solid content and accounts for 8%, hydro-oxidation sodium adjust ph to 8.0, more centrifugal, filtration, get supernatant;
(4) macroporous adsorbent resin column chromatography is carried out to supernatant, particularly:
1. supernatant is passed through the LX11 macroporous adsorptive resins of 25L with the flow velocity of 25L/h;
2., after upper prop, first the larger impurity of the non-adsorbable polarity of resin is removed with 150L pure water with the flow velocity eluting of 50L/h, until effluent pH value is 7.0 ~ 7.8;
3. be that the ethanol of 15% is easily with the impurity of the flow velocity eluting middle polarity of 15L/h by 50L volume fraction again;
4. finally with 25L volume fraction be the ethanol of 70% easily with the flow velocity desorbing of 10L/h, collect stripping liquid, stripping liquid concentrating under reduced pressure is reached more than 50% to solid content, vacuum drying, obtains dry extract 78.5g, be the Semen Maydis bract extract containing tricin.
Compare with tricin sterling, carry out HPLC detection to this Semen Maydis bract extract, testing conditions is:
Chromatographic column: HypersilODSC18 (4.6 × 250mm, 5 μm);
Mobile phase: methanol-water (65:35);
Flow velocity: 1.0ml/min;
Column temperature: 30 DEG C;
Determined wavelength: 349nm.
The HPLC testing result of tricin sterling is as Fig. 1, and the HPLC testing result of the present embodiment Semen Maydis bract extract is as Fig. 2.
Detect known through HPLC, in this Semen Maydis bract extract, tricin content is 12.3%.
Embodiment 2
A kind of method extracting tricin from Semen Maydis bract of the present embodiment, comprises the following steps:
(1) take dry Semen Maydis bract broken (granularity is less than 0.5cm) 300kg, put in 3000L extraction pot, add water 2400L, soak 3h under agitation, discard extracting solution, extract slag for subsequent use;
(2) extract slag for 85% described in the alcoholic solution reflux, extract, being added with hydrochloric acid (12mol/L) by volume fraction, by gained extracting solution concentrating under reduced pressure, obtain concentrate; Wherein the addition of hydrochloric acid is 0.03% (i.e. 0.09kg) of the broken quality of Semen Maydis bract;
Be specially: 1. in extraction slag, add the alcoholic solution 2400L that volume fraction is 85%, open stirring;
2. open jacket steam, when being heated to alcohol reflux, start timing, reflux, extract, 1h;
3. after reflux, extract, feed liquid is crossed 400 order filter bags, and in filtering residue, again drop into the alcoholic solution 2400L that volume fraction is 85%, repeat reflux, extract, 1h;
4. repeat after reflux, extract, secondary feed liquid crossed 400 order filter bags, and by secondary filtrate with 3. in filtrate merge, and suck 1000L outer circulation;
5. open outer circulation vacuum and steam, start to reclaim ethanol, to distillate without after alcohol taste, blowing, weighs, and obtains concentrate;
(3) concentrate is diluted with water to total solid content and accounts for 10%, hydro-oxidation sodium adjust ph to 8.1, more centrifugal, filtration, get supernatant;
(4) macroporous adsorbent resin column chromatography is carried out to supernatant, particularly:
1. supernatant is passed through the LX11 macroporous adsorptive resins of 1000L with the flow velocity of 1000L/h;
2., after upper prop, first the larger impurity of the non-adsorbable polarity of resin is removed with 2000L pure water with the flow velocity eluting of 2000L/h, until effluent pH value is 7.0 ~ 7.8;
3. be that the alcoholic solution of 15% is with the impurity of the flow velocity eluting middle polarity of 500L/h by 1000L volume fraction again;
4. be finally that the alcoholic solution of 75% is with the flow velocity desorbing of 500L/h by 1000L volume fraction, collect stripping liquid, stripping liquid concentrating under reduced pressure is reached more than 50% to solid content, vacuum drying, obtain dry extract 2.3kg, be the Semen Maydis bract extract containing tricin.
Detect (testing conditions is identical with embodiment 1) known (see Fig. 3) through HPLC, in this Semen Maydis bract extract, tricin content is 13.3%.
Embodiment 3
A kind of method extracting tricin from Semen Maydis bract of the present embodiment, comprises the following steps:
(1) take dry Semen Maydis bract broken (granularity is less than 0.5cm) 200kg, put in 3000L extraction pot, add water 2000L, soak 3h under agitation, discard extracting solution, extract slag for subsequent use;
(2) extract slag for 90% described in the alcoholic solution reflux, extract, being added with hydrochloric acid (12mol/L) by volume fraction, by gained extracting solution concentrating under reduced pressure, obtain concentrate; Wherein the addition of hydrochloric acid is 0.03% (i.e. 0.06kg) of the broken quality of Semen Maydis bract;
Be specially: 1. in extraction slag, add above-mentioned alcoholic solution 2000L, open stirring;
2. open jacket steam, when being heated to alcohol reflux, start timing, reflux, extract, 2h;
3. after reflux, extract, feed liquid is crossed 400 order filter bags, and in filtering residue, again drop into above-mentioned alcoholic solution 2000L, repeat reflux, extract, 1h;
4. repeat after reflux, extract, secondary feed liquid crossed 400 order filter bags, and by secondary filtrate with 3. in filtrate merge, and suck 1000L outer circulation;
5. open outer circulation vacuum and steam, start to reclaim ethanol, to distillate without after alcohol taste, blowing, weighs, and obtains concentrate;
(3) concentrate is diluted with water to total solid content and accounts for 10%, hydro-oxidation sodium adjust ph to 8.2, more centrifugal, filtration, get supernatant;
(4) macroporous adsorbent resin column chromatography is carried out to supernatant, particularly:
1. supernatant is passed through the LX11 macroporous adsorptive resins of 1000L with the flow velocity of 1000L/h;
2., after upper prop, first the larger impurity of the non-adsorbable polarity of resin is removed with 2000L pure water with the flow velocity eluting of 2000L/h, until effluent pH value is 7.0 ~ 7.8;
3. be that the alcoholic solution of 15% is with the impurity of the flow velocity eluting middle polarity of 500L/h by 8000L volume fraction again;
4. be finally that the alcoholic solution of 80% is easily with the flow velocity desorbing of 400L/h by 1200L volume fraction, collect stripping liquid, stripping liquid concentrating under reduced pressure is reached more than 50% to solid content, vacuum drying, obtain dry extract 1.5kg, be the Semen Maydis bract extract containing tricin.
Detect (testing conditions is identical with embodiment 1) known (see Fig. 4) through HPLC, in this Semen Maydis bract extract, tricin content is 14.6%.
Embodiment 4
Adopt the method identical with embodiment 3 to obtain the Semen Maydis bract extract containing tricin, but in the middle alcoholic solution of step (2), the addition of hydrochloric acid change 0.01% of the broken quality of Semen Maydis bract into.
Detect (testing conditions is identical with embodiment 1) known (see Fig. 5) through HPLC, in this Semen Maydis bract extract, tricin content is 11.6%.
Embodiment 5
Adopt the method identical with embodiment 3 to obtain the Semen Maydis bract extract containing tricin, but in the middle alcoholic solution of step (2), the addition of hydrochloric acid change 0.05% of the broken quality of Semen Maydis bract into.
Detect (testing conditions is identical with embodiment 1) known (see Fig. 6) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 13.5%.
Embodiment 6
A kind of method extracting tricin from Semen Maydis bract of the present embodiment, comprises the following steps:
(1) take dry Semen Maydis bract broken (granularity is less than 0.5cm) 200kg, put in 3000L extraction pot, add water 2000L, soak 3h under agitation, discard extracting solution, extract slag for subsequent use;
(2) extract slag for 90% described in the alcoholic solution reflux, extract, being added with hydrochloric acid (12mol/L) by volume fraction, by gained extracting solution concentrating under reduced pressure, obtain concentrate; Wherein the addition of hydrochloric acid is 0.03% (i.e. 0.06kg) of the broken quality of Semen Maydis bract;
Be specially: 1. in extraction slag, add above-mentioned alcoholic solution 2000L, open stirring;
2. open jacket steam, when being heated to alcohol reflux, start timing, reflux, extract, 2h;
3. after reflux, extract, feed liquid is crossed 400 order filter bags, and in filtering residue, again drop into above-mentioned alcoholic solution 2000L, repeat reflux, extract, 1h;
4. repeat after reflux, extract, secondary feed liquid crossed 400 order filter bags, and by secondary filtrate with 3. in filtrate merge, and suck 1000L outer circulation;
5. open outer circulation vacuum and steam, start to reclaim ethanol, to distillate without after alcohol taste, blowing, weighs, and obtains concentrate;
(3) concentrate is diluted with water to total solid content and accounts for 10%, hydro-oxidation sodium adjust ph to 7.8, more centrifugal, filtration, get supernatant;
(4) macroporous adsorbent resin column chromatography is carried out to supernatant, particularly:
1. supernatant is passed through the LX11 macroporous adsorptive resins of 1000L with the flow velocity of 1000L/h;
2., after upper prop, first the larger impurity of the non-adsorbable polarity of resin is removed with 2000L pure water with the flow velocity eluting of 2000L/h, until effluent pH value is 7.0 ~ 7.8;
3. be that the alcoholic solution of 20% is with the impurity of the flow velocity eluting middle polarity of 500L/h by 8000L volume fraction again;
4. be finally that the alcoholic solution of 80% is easily with the flow velocity desorbing of 400L/h by 1200L volume fraction, collect stripping liquid, stripping liquid concentrating under reduced pressure is reached more than 50% to solid content, vacuum drying, obtain dry extract 1.5kg, be the Semen Maydis bract extract containing tricin.
Detect (testing conditions is identical with embodiment 1) known (see Fig. 7) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 13.5%.
Comparative example 1
Adopt the method identical with embodiment 3 to obtain the Semen Maydis bract extract containing tricin, but do not add hydrochloric acid in the alcoholic solution of step (2).
Detect (testing conditions is identical with embodiment 1) known (see Fig. 8) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 8.6%.
Comparative example 2
Adopt the method identical with embodiment 3 to obtain the Semen Maydis bract extract containing tricin, but in the alcoholic solution of step (2), the addition of hydrochloric acid change 0.07% of the broken quality of Semen Maydis bract into.。
Detect (testing conditions is identical with embodiment 1) known (see Fig. 9) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 11.4%.
In this Semen Maydis bract extract, tricin content is close with embodiment 4, shows that excessive hydrochloric acid can impel tricin to degrade, and improves unhelpful to extraction ratio.
Comparative example 3
Adopt the method identical with embodiment 3 to obtain Semen Maydis bract extract containing tricin, but lack step (1), namely directly broken for Semen Maydis bract utilization volume fraction is 90% and the alcoholic solution being added with hydrochloric acid carries out reflux, extract.
Detect (testing conditions is identical with embodiment 1) known (see Figure 10) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 9.8%.
Comparative example 4
Adopt the method identical with embodiment 3 to obtain the Semen Maydis bract extract containing tricin, but in step (2), the volume fraction of alcoholic solution is 95%.
Detect (testing conditions is identical with embodiment 1) known (see Figure 11) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 12.1%.
Though tricin content is higher in this Semen Maydis bract extract, but still with close even slightly low during 80% alcoholic solution reflux, extract, be save ethanol consumption, do not adopt volume fraction be 95% alcoholic solution.
Comparative example 5 adopts the method identical with embodiment 3 to obtain the Semen Maydis bract extract containing tricin, but by concentrate diluent pH regulator to 6.8 in step (3).
Detect (testing conditions is identical with embodiment 1) known (see Figure 12) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 12.0%.
Though tricin content is higher in this Semen Maydis bract extract, when pH is 6.8, in step (3), precipitation is not easily separated out, and causes the time of solid-liquid separation longer, extends the production cycle.
Comparative example 6
The method identical with embodiment 3 is adopted to obtain the Semen Maydis bract extract containing tricin, but by concentrate diluent pH regulator to 8.5 in step (3).
Detect (testing conditions is identical with embodiment 1) known (see Figure 13) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 11.8%.
After pH improves, extraction ratio does not improve and reduces on the contrary, may be because tricin is unstable under the environment that alkalescence is stronger, easily decompose.
Comparative example 7 adopts the method identical with embodiment 3 to obtain Semen Maydis bract extract containing tricin, and the middle employing volume fraction of but step (4)-is 3. the alcoholic solution of 25%.
Detect (testing conditions is identical with embodiment 1) known (see Figure 14) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 11.8%.
Comparative example 8
Adopt the method identical with embodiment 3 to obtain Semen Maydis bract extract containing tricin, in but step (4)-3., adopt volume fraction to be the alcoholic solution of 10%.
Detect (testing conditions is identical with embodiment 1) known (see Figure 15) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 11.5%.Show the too low effective removal being unfavorable for middle polarity impurity of the eluted fraction of alcoholic solution.
Comparative example 9
Adopt the method identical with embodiment 3 to obtain Semen Maydis bract extract containing tricin, in but step (4)-4., adopt volume fraction to be the alcoholic solution of 65%.
Detect (testing conditions is identical with embodiment 1) known (see Figure 16) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 11.7%.Show the too low desorbing being unfavorable for effective ingredient of the volume fraction of alcoholic solution.
Comparative example 10
Adopt the method identical with embodiment 3 to obtain Semen Maydis bract extract containing tricin, in but step (4)-4., adopt volume fraction to be the alcoholic solution of 85%.
Detect (testing conditions is identical with embodiment 1) known (see Figure 17) through HPLC, in the Semen Maydis bract extract obtained, tricin content is 12.1%.Show the too high probability that can increase little polar impurity and be eluted of the volume fraction of alcoholic solution.
Claims (10)
1. from Semen Maydis bract, extract a method for tricin, it is characterized in that, comprise the following steps:
(1) with water, extract at room temperature is carried out to Semen Maydis bract, get extraction slag;
(2) extract slag for 80 ~ 90% described in the alcoholic solution reflux, extract, being added with acid medium by volume fraction, by gained extracting solution concentrating under reduced pressure, obtain concentrate;
(3) by described concentrate thin up and adjust ph to 7.8 ~ 8.2, after solid-liquid separation, supernatant is got;
(4) macroporous adsorbent resin column chromatography is carried out to described supernatant, obtain the Semen Maydis bract extract containing tricin.
2. from Semen Maydis bract, extract the method for tricin as claimed in claim 1, it is characterized in that, in step (1), described Semen Maydis bract is crushed to after granularity is less than 0.5cm and carries out extract at room temperature again.
3. from Semen Maydis bract, extract the method for tricin as claimed in claim 1 or 2, it is characterized in that, in step (1), described extract at room temperature is immersed in water by Semen Maydis bract, the mixed proportion of Semen Maydis bract and water is 1kg:8 ~ 10L, and soak time is 2 ~ 4h.
4. from Semen Maydis bract, extract the method for tricin as claimed in claim 1, it is characterized in that, in step (2), described acid medium is hydrochloric acid.
5. as described in claim 1 or 4, extract the method for tricin from Semen Maydis bract, it is characterized in that, the addition of described acid medium is 0.01 ~ 0.05% of Semen Maydis bract quality.
6. from Semen Maydis bract, extract the method for tricin as claimed in claim 5, it is characterized in that, the addition of described hydrochloric acid is 0.03 ~ 0.05% of Semen Maydis bract quality.
7. from Semen Maydis bract, extract the method for tricin as claimed in claim 1, it is characterized in that, in step (3), described concentrate is diluted with water to total solid content and accounts for 5 ~ 10%.
8. from Semen Maydis bract, extract the method for tricin as claimed in claim 1, it is characterized in that, in step (4), described macroporous adsorbent resin column chromatography comprises: add in macroporous adsorptive resins by described supernatant, first wash with water to effluent pH value be 7.0 ~ 7.8, be the alcoholic solution of 15 ~ 20% by volume fraction successively again, volume fraction is the alcoholic solution eluting of 70 ~ 80%, collected volume mark is the stripping liquid of the alcoholic solution eluting gained of 70 ~ 80%, by this stripping liquid concentrating under reduced pressure, dry, obtain the Semen Maydis bract extract containing tricin.
9. from Semen Maydis bract, extract the method for tricin as claimed in claim 8, it is characterized in that, in described macroporous adsorptive resins, load low pole macroporous adsorbent resin.
10. a Semen Maydis bract extract, is characterized in that, is prepared from by the arbitrary described method of claim 1 ~ 9, containing the tricin of at least 10%.
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