CN101177382B - Sea weed bromophenol compound as well as preparation method and application thereof - Google Patents
Sea weed bromophenol compound as well as preparation method and application thereof Download PDFInfo
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- CN101177382B CN101177382B CN2007100101106A CN200710010110A CN101177382B CN 101177382 B CN101177382 B CN 101177382B CN 2007100101106 A CN2007100101106 A CN 2007100101106A CN 200710010110 A CN200710010110 A CN 200710010110A CN 101177382 B CN101177382 B CN 101177382B
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Abstract
The invention relates to the technical field of food additives, in particular to an algae bromophenol compound and the preparation method and purpose. The invention is characterized in that the algae bromophenol compound which is capable of deactivating radials is obtained through the extraction and separation from oceanic red algae symphyocladia latiuscula, and the constitutional formula is shown in Figure (I), wherein the R1 is OH, OCH3 or Br; R2 is OH, OCH3 or Br; R3 is H, CH3 or Ac; R1 or R2 is Br. The algae bromophenol compound from the invention has obvious function on removing DPPH free radical activity for deactivating radials, which can be used as a food addition agent to delay or prevent the oxidation and metamorphosis of edible oil or oil-retaining food caused by the inducementof free radical.
Description
Technical field
The present invention relates to the foodstuff additive field, specifically sea weed bromophenol compound and its production and application.
Background technology
The oxidizing reaction that free yl induction causes can cause food particularly oleaginous food become sour rotten.Moreover, oxidizing reaction can also cause that food fades, brown stain etc., thereby has a strong impact on the quality of food, reduces Nutritive value of food.On the other hand, many oxidation productss and intermediate product that free radical causes are the carcinogenss of generally acknowledging, the organic microbial film of meeting grievous injury, protein, enzyme and cell function directly or indirectly cause the generation of numerous disease such as cancer, atherosclerosis, diabetes, nerve degenerative diseases and organism aging process etc.
One of main path that prevents food oils and oleaginous food deterioration by oxidation commonly used at present is to add antioxidant, to prevent or to delay to comprise the generation of the caused oxidizing reaction of free-radical oxidn.Wherein BHT (tertiary butyl hydroxytoluene), BHA (butylhydroxy anisole) are than common chemical synthetized oxidation preventive agent, free-radical scavengers.But along with growth in the living standard, the mankind more and more pay close attention to the safety problem of synthetized oxidation preventive agent, free-radical scavengers, discover that particularly there are certain toxicity (it is also possible carcinogenic to cause that liver enlarges) in BHT, BHA, the research of natural antioxidants, free-radical scavengers is subjected to attention more and more widely.
Summary of the invention
The purpose of this invention is to provide a kind of natural sea weed bromophenol compound and its production and application.
For achieving the above object, the technical solution used in the present invention is:
Sea weed bromophenol compound structural formula (I)
Wherein: R
1Be OH, OCH
3Or Br; R
2Be OH, OCH
3Or Br; R
3Be H, CH
3Or Ac; R
1And R
2At least one is Br.
The preparation method of sea weed bromophenol compound comprises the steps:
1) the 60-80 order is washed, dried in the shade, is crushed to marine red alga drake feather algae, then extract 2-5 time with organic solution, united extraction liquid concentrates, and obtains crude extract;
Extract 2-5 time, united extraction liquid concentrates, and obtains crude extract;
2) will be in the crude extract in the step 1) add excessive water, and respectively extract 2-4 time with sherwood oil, ethyl acetate, propyl carbinol successively, extract concentrated separately extract accordingly, standby;
3) get step 2) in ethyl acetate extract carry out silica gel column chromatography, carry out wash-out with organic solvent, collect elutriant, elutriant through thin-layer chromatography detect, merge each component of chromatography;
4) component that obtains with wash-out under 40: 1 to 30: 1 gradients in the step 3) is carried out silica gel and dextrane gel column chromatography, after collecting elutriant and concentrating formula (I) compound.
Organic solution extracting solution in the step 1) can be ethanol or the methyl alcohol of concentration at 50-100%.
The elutriant of the gradient ethyl acetate-methyl alcohol of the chloroform-methanol of available 100: 0 to 0: 100 gradient or 100: 0 to 0: 100 carries out wash-out silicon in the step 3).
Silica gel column chromatography adopts gradient to carry out wash-out at 20: 80 to 0: 100 petroleum ether-ethyl acetate in the step 4); The used eluent of dextrane gel column chromatography is that methyl alcohol or gradient are that 50: 50 chloroform-methanol carries out wash-out.
Sea weed bromophenol compound can be used as food oils or the oleaginous food additive that delays or prevent the deterioration by oxidation that free yl induction causes.
The present invention has the following advantages:
The compound that the present invention relates to is new bromine phenolic compound, belongs to the small molecules natural organic-compound, prepares easily; The bromine phenolic compound that the present invention relates to has significant DPPH freedom (α, α-diphenyl-β-picrylhydrazyl, that is, hexichol is for the bitter taste free acyl radical) activity, can be used as foodstuff additive and delay or prevent the deterioration by oxidation that food oils and oleaginous food cause because of free yl induction.
The marine red alga drake feather algae that the present invention relates to (Symphyocladia latiuscula (Harvey) Yamada) belongs to rhodophyta, Rhodomelaceae, drake feather Trentepohlia marine alga, mainly be distributed in coastlands such as China, Japan, Korea S, generally be grown on the rock of tideland.The bromine phenols natural compounds that the present invention obtains through extraction, separation by marine red alga drake feather algae, our experiments show that, this compounds has significant DPPH free radical scavenging activity, its action intensity is apparently higher than synthetic BHT under identical concentration conditions, can be widely used in food oils or the oleaginous food, instead of chemical synthetized oxidation preventive agent, free-radical scavengers prevent or the generation of the oxidizing reaction that delays to be caused by free radical, thereby extend the shelf life, improve the quality of products.
Embodiment:
Below in conjunction with embodiment the present invention is further elaborated.
Embodiment 1
The preparation method of bromine phenolic compound:
The drake feather algae of fresh collection is cleaned through seawater, removes the grit and the assorted algae of surface attachment, and shady and cool place airing is standby.Get the sample 2.5Kg behind the airing, pulverize the back and at room temperature extract three times, each three days, merge ethanol extract, at 40 ℃ of left and right sides concentrating under reduced pressure of temperature, reclaim ethanol, acquisition ethanol crude extract with 7.5 liter 95% ethanol.In crude extract, add an amount of distilled water and make it to be suspended in the water, respectively extract three times with an amount of sherwood oil, ethyl acetate, propyl carbinol successively, concentrate the back respectively and obtain corresponding sherwood oil, ethyl acetate, n-butanol extract.Ethyl acetate extract (108 gram) is carried out silicagel column (220 grams, the 200-300 order) chromatography, with chloroform-methanol with 100: 0,90: 1,85: 1,70: 1,50: 1,40: 1,30: 1,20: 1,10: 1,5: 1,3: 1,1: 1 to 0: 100 gradient is carried out wash-out, collect elutriant respectively, use thin-layer chromatography (TLC) to detect again, merge identical or similar portions, use iron trichloride as developer when thin-layer chromatography (TLC) detects, obtain nine components (I-IX).With component I V (7.1 gram), promptly carrying out silica gel column chromatography again with the component under 40: 1 to 30: 1 gradient elutions of chloroform-methanol separates and dextrane gel Sephadex LH-20 column chromatography, carry out wash-out with gradient at 20: 80 to 0: 100 petroleum ether-ethyl acetate during silica gel column chromatography, dextrane gel Sephadex LH-20 column chromatography obtains 11.0 milligrams of pure compounds with the methanol-eluted fractions of 100% concentration, elutriant through concentrating under reduced pressure.Through Spectrum Analysis, its structure is accredited as two-(2,3,6-three bromo-4,5-dihydroxy phenyl) ethane, English name Bis (2,3,6-tribromo-4,5-dihydroxyphenyl) ethane, structural formula shown in (II), i.e. R in the general formula (I)
1, R
2Be Br, R
3Compound for H
This compound has following physics and chemistry and spectral characteristic:
Yellow powder shape solid, fusing point 230-232 ℃; Proton nmr spectra (
1H NMR, acetone-d
6, 500MHz) δ 8.63 (4H, br s, OH), 3.42 (4H, s, H-7,7 ');
Carbon-13 nmr spectra (
13C NMR, acetone-d
6, 125MHz) δ 144.0 (s, C-4,4 '), 143.9 (s, C-5,5 '), 132.8 (s, C-1,1 '), 118.2 (s, C-2,2 '), 113.9 (s, C-3,3 ', 6,6 '), 37.5 (t, C-7,7 '); Low Resolution Mass Spectra EIMSm/z (%) 726 (＜1), 724 (＜1), 722 (1.6), 720 (2.4), 718 (1.6), 716 (＜1), 714 (＜1) [M]
+, 564 (1), 562 (4), 560 (6), 558 (3.5), 556 (1) [M 2Br]
+, 481 (6), 480 (10), 478 (7), 402 (6), 400 (13), 398 (7), 363 (31), 361 (96), 359 (100), 357 (35), 281 (23), 279 (20), 201 (11), 199 (13), 131 (23), 91 (22), 82 (84), 80 (88), 79 (35), 63 (25); High resolution mass spectrum HRFABMSm/z719.5485[M+H]
+(calcd for C
14H
8 79Br
3 81Br
3O
4, 719.5461).
Embodiment 2
Difference from Example 1 is:
With the drake feather algae of drying and crushing with the extraction using alcohol of concentration 50% 4 times, each three days, united extraction liquid, concentrating under reduced pressure obtains crude extract under the room temperature, ethanol reclaims simultaneously.Crude extract is suspended in water, respectively extract three times with sherwood oil, ethyl acetate, propyl carbinol successively, concentrate the back respectively and obtain corresponding sherwood oil, ethyl acetate, n-butanol extract.Ethyl acetate extract is carried out silicagel column (220 grams, 200-300 order) chromatography, is that the ethyl acetate-methyl alcohol of 100: 0 to 0: 100 gradient carries out gradient elution with gradient, collects elutriant respectively, detects with thin-layer chromatography (TLC), merges identical component; Will be with the elutriant of ethyl acetate-methyl alcohol under 40: 1 to 30: 1 gradient elutions, carry out silica gel column chromatography again and separate and dextrane gel Sephadex LH-20 column chromatography, silica gel column chromatography employing gradient is carried out wash-out at 20: 80 to 0: 100 petroleum ether-ethyl acetate; The used eluent of dextrane gel column chromatography is that gradient is that 50: 50 chloroform-methanol carries out wash-out; material behind the elutriant concentrating under reduced pressure adopts aceticanhydride and pyridine to carry out acetylization reaction by ordinary method and obtains its corresponding acetyl derivatives, and it also has significant DPPH free radical scavenging activity.
Embodiment 3
Difference from Example 1 is:
Will be by the bromine phenolic compound that obtains among the embodiment 1, adopt methylating reagent (diazomethane) to carry out the methylation reaction derivative that methylated accordingly by ordinary method, it also has significant DPPH free radical scavenging activity.
Embodiment 4
The experiment of DPPH free radical scavenging activity:
DPPH is a kind of stable free radical, is purple in organic solvent, and strong absorption is arranged near 517nm, and behind the adding antioxidant, a part of free radical is eliminated, and makes to absorb and weakens, and can estimate the power of its anti-oxidant activity, free radical scavenging activity whereby.This method is easy and simple to handle, favorable reproducibility.
Experimental technique:
In 2mL embodiment 1, add in the gained sample 2mL DPPH (methanol solution, 0.16mmol/L) mix after, after 50min is placed in the room temperature dark place, in 517nm place its absorbance A of mensuration
Sample
In 2mL embodiment 1, add the 2mL methanol solution in the gained sample and measure its absorbance A in the 517nm place
Sample blank
Add 2mL methyl alcohol chloroform mixed solvent among the 2mLDPPH and measure its absorbance A in the 517nm place
Control
Add 2mL methyl alcohol chloroform mixed solvent in the 2mL methyl alcohol and measure its absorbance A in the 517nm place
Blank
The calculating of free radical scavenging activity:
Clearance rate %=100-(A
Sample-A
Sample blank) * 100/ (A
Control-A
Blank).
With sample test respectively under 2 μ g/mL, 10 μ g/mL, 50 μ g/mL different concns that embodiment 1 obtains, each concentration replicate(determination) three times, averaging is the sample clearance rate, and calculates IC
50Value.All tests all are that standard substance are as positive control with BHT.
Experimental result:
Referring to table 1, data show that the bromine phenolic compound of above-mentioned acquisition has significant DPPH and removes activity, and the activity of bromine phenolic compound and BHT are suitable under lower concentration, and activity is significantly higher than BHT when middle concentration and high density.In addition, experiment shows, the IC of BHT
50Be 81.8 μ M, and the IC of bromine phenolic compound
50Be 10.2 μ M, 1/8th of only positive contrast BHT shows that the free radical scavenging activity of bromine phenolic compound is significantly higher than positive control BHT.
Table 1
Embodiment 5
The application of bromine phenolic compound in food oils are anti-oxidant:
Get 1 kilogram of food oils, the weight ratio according to 0.02% adds in the bromine phenolic compound that obtains among the foregoing description 1-3, mixes, and makes the food oils of Green Tea Extract oxidation.Compare with the food oils that do not contain bromine phenolic compound, its preservation period of food oils that contains bromine phenolic compound be the former more than 2 times.
Bromine phenolic compound involved in the present invention can be applicable in any food oils, to prevent or to delay the deterioration by oxidation that free radical causes, extends the shelf life.
Claims (4)
1. a sea weed bromophenol compound is characterized in that: shown in the structural formula (I)
Wherein: R
1Be Br; R
2Be Br; R
3Be H.
2. the preparation method of the described sea weed bromophenol compound of claim 1 is characterized in that comprising the steps:
1) the 60-80 order is washed, dried in the shade, is crushed to marine red alga drake feather algae, then extract 2-5 time with organic solution, united extraction liquid concentrates, and obtains crude extract; The organic solution of extracting is ethanol or the methyl alcohol of concentration at 50-100%;
2) will be in the crude extract in the step 1) add excessive water, and respectively extract 2-4 time with sherwood oil, ethyl acetate, propyl carbinol successively, extract concentrated separately extract accordingly, standby;
3) get step 2) in ethyl acetate extract carry out silica gel column chromatography, carry out wash-out with organic solvent, collect elutriant, elutriant through thin-layer chromatography detect, merge each component of chromatography; The elutriant that organic solvent carries out wash-out is chloroform-methanol or ethyl acetate-methyl alcohol;
4) will carry out silica gel and dextrane gel column chromatography with the component under 40: 1 to 30: 1 gradient elutions in the step 3), after collecting elutriant and concentrating target compound.
3. by the described preparation method of claim 2, it is characterized in that: the used elutriant of silica gel column chromatography is a petroleum ether-ethyl acetate in the step 4); The used elutriant of dextrane gel column chromatography is methyl alcohol or chloroform-methanol.
4. the application of the described sea weed bromophenol compound of claim 1 is characterized in that: described compound is used to delay or prevent food oils or the oleaginous food deterioration by oxidation that free yl induction causes as foodstuff additive.
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| CN101177382B true CN101177382B (en) | 2010-12-01 |
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| CN101643442B (en) * | 2008-08-07 | 2011-05-18 | 中国科学院海洋研究所 | Seaweed bromphenol urea compounds, preparation method and application thereof |
| CN101602653B (en) * | 2009-07-16 | 2013-07-31 | 山西医科大学 | Halogenated hydroxyl aromatic methane compounds, preparation method and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105798A (en) * | 1985-09-09 | 1987-04-08 | 陶氏化学公司 | Brominated hydroxyaromatic compounds |
| CN1202334A (en) * | 1998-05-28 | 1998-12-23 | 中国科学院海洋研究所 | Preparation of seeweed polyphenol antioxidation agent and its applying method |
| CN1772721A (en) * | 2004-11-10 | 2006-05-17 | 中国科学院海洋研究所 | Bromophenol compound and its prepn and application |
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2007
- 2007-01-19 CN CN2007100101106A patent/CN101177382B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105798A (en) * | 1985-09-09 | 1987-04-08 | 陶氏化学公司 | Brominated hydroxyaromatic compounds |
| CN1202334A (en) * | 1998-05-28 | 1998-12-23 | 中国科学院海洋研究所 | Preparation of seeweed polyphenol antioxidation agent and its applying method |
| CN1772721A (en) * | 2004-11-10 | 2006-05-17 | 中国科学院海洋研究所 | Bromophenol compound and its prepn and application |
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