CN102225995B - Single-type melanins and their preparation methods and applications - Google Patents
Single-type melanins and their preparation methods and applications Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 235000019750 Crude protein Nutrition 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 238000013016 damping Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 108010029541 Laccase Proteins 0.000 claims description 4
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 claims description 4
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 230000005501 phase interface Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 241000143442 Daldinia Species 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 241000173554 Daldinia eschscholzii IFB-TL01 Species 0.000 abstract description 2
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- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- 239000002537 cosmetic Substances 0.000 abstract 3
- 229940079593 drug Drugs 0.000 abstract 2
- 230000008030 elimination Effects 0.000 abstract 2
- 238000003379 elimination reaction Methods 0.000 abstract 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000037308 hair color Effects 0.000 abstract 1
- 239000002917 insecticide Substances 0.000 abstract 1
- 235000010288 sodium nitrite Nutrition 0.000 abstract 1
- HVGQWHMSVYODLJ-GFCCVEGCSA-N melanochrome Natural products CC1(C)Oc2cc3OC(=CC(=O)c3c(O)c2C[C@H]1O)CO HVGQWHMSVYODLJ-GFCCVEGCSA-N 0.000 description 14
- 238000004435 EPR spectroscopy Methods 0.000 description 11
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 241000233866 Fungi Species 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- 210000002752 melanocyte Anatomy 0.000 description 3
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000118 hair dye Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- OENHRRVNRZBNNS-UHFFFAOYSA-N naphthalene-1,8-diol Chemical compound C1=CC(O)=C2C(O)=CC=CC2=C1 OENHRRVNRZBNNS-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- HQFLTUZKIRYQSP-UHFFFAOYSA-N 3-ethyl-2h-1,3-benzothiazole-6-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2N(CC)CSC2=C1 HQFLTUZKIRYQSP-UHFFFAOYSA-N 0.000 description 1
- 241000186361 Actinobacteria <class> Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241000371652 Curvularia clavata Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
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- 239000002738 chelating agent Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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Abstract
The invention discloses single-type melanins, their preparation methods and their applications in drugs and cosmetics. The preparation method comprises that a dihydroxynaphthlene-melanin (DHN-melanin) in powder form is prepared through a reaction of 1,8-dihydroxynaphthlene as a raw material and NaNO2 in an acid condition, and a DHN-melanin in flake form is prepared through a catalytic action of a fungus Daldiniaeschscholzii IFB-TL01 extracellular crude protein. The melanins prepared respectively in the two forms both have strong activities of elimination of hydroxyl free radicals. The melanins can be utilized in cosmetics and have effects of oxidation and radiation resistance and hydroxyl free elimination. The melanins can be utilized in hair colorings and have adornment effects. The melanins also can be utilized in the biological insecticide field and act as photoprotectants. The melanins are suitable for the biomedical technical field comprising drugs, cosmetics and the like.
Description
Technical field
The invention belongs to the biological medicine technology field, be specifically related to a kind of melanochrome and compound method thereof and the application in medicine and makeup.
Background technology
Melanochrome (melanin) is water insoluble and the amorphous small-particle of nearly all solvent, and melanochrome extensively is present in heterogeneous type of polyphenol polymer in plant-animal and the mikrobe.The extraction of natural black pigment at present mainly is with animal tissues (Gallus Domesticus, octopus etc.), plant (black rice, Semen Sesami Nigrum etc.), mikrobe (producing melanochrome actinomycetes, fungi etc.).Melanic being widely used can also can be used to treat some nervous system disorders relevant with short of melanin as the pharmaceutical carrier of UV light absorber, inhibitor, free-radical scavengers, cation chelating agent and new type natural.In addition, melanochrome has wide application prospect at the decoration function of makeup, hair dye and the aspects such as bright protective agent of biotic pesticide.
In the melanocyte organization work of research frog's egg, just propose melanocyte as far back as Commoner in 1954 and can capture radical, and be stabilized in them in the melanocyte matrix, that is contain radical in the explanation melanochrome.EPR (Electron Paramagnetic Resonance; EPR) principle of work is that unpaired electron absorbs the state that microwave radiation can change electron spinning in externally-applied magnetic field; So the EPR wave spectrum can be used for detecting whether radical exists, the structure of the EPR spectrum of number of free radical, paramagnetic substance and proof radical, the crest size is represented the number of unpaired electron content.
Since melanochrome water insoluble with other organic easily, can not be with its complicated structure of technical measurements such as nucleus magnetic resonance, and ir spectra (Infrared Spectroscopy; IR) can test solid-state sample, and test is easy to operate rapidly; Good reproducibility, highly sensitive.IR can provide many information about functional group, can help to confirm part and even whole molecule type and structure, is commonly used to measure solid samples such as melanochrome.
Present known melanochrome is compound melanochrome, does not see the melanic report of single type as yet.
Summary of the invention
The problem that the present invention need solve is to disclose a kind of single type melanochrome and preparation method thereof and the application in medicine and makeup.Melanic characteristic according to the invention is the high molecular polymer of black, and water insoluble, strong acid and other organic solvents are slightly soluble in highly basic, and the EPR test shows that it contains 1, the 8-DHN radical.
The technical scheme that the present invention adopted is: the one, with 1, the 8-dihydroxy naphthlene be raw material under acidic conditions with equimolar NaNO
2Effect, product are crossed filter cake and are given a baby a bath on the third day after its birth time with ETHYLE ACETATE, and the black powder that obtains is Powdered DHN-melanin.The 2nd, with 1; The 8-dihydroxy naphthlene is that raw material adds in Hydrocerol A-Sodium phosphate, dibasic damping fluid of pH5 that crude protein (containing laccase) carries out catalysis outside the fungi TL01 born of the same parents; Reaction solution is used ethyl acetate extraction, and there is insolubles at water/organic phase interface, collects insolubles; Water, methanol rinse obtain sheet DHN-melanin after drying respectively.
One, the preparation method of Powdered DHN-melanin
(1) with 1,8-DHN adds in the acidic buffer, stir,
(2) constantly add NaNO in the whipping process
2To waiting mole, stirring at room half a hour,
(3) reaction product is filtered, the deposition that obtains is used ETHYLE ACETATE, methyl alcohol, water rinse twice respectively,
(4) the deposition nature dries, and turns out to be powder DHN-melanin through EPR test, IR test, electron microscopic observation.
Two, the preparation method of sheet DHN-melanin
(1) the ammonium sulfate method of enrichment prepare fungi IFB-TL01 (
Daldinia eschscholziiIFB-TL01 is deposited in Chinese typical culture collection center at present, and deposit number is: CCTCCM 207198, and preservation date is 2007.12.13) the outer crude protein of born of the same parents, utilize the ABTS method to measure oxydase such as containing laccase in the crude protein,
(2) ph optimum of crude protein is 5, at Hydrocerol A-Na of 10ml pH5
2HPO
4Add 5 mg 1 in the damping fluid, the crude protein of 8-DHN, 200U, 28 ℃, 180 rpm react 8 h,
(3) reaction solution is used ethyl acetate extraction; Organic phase/aqueous phase interface has insolubles, and insolubles is collected, and uses twice of methyl alcohol, water rinse respectively; Obtain the sheet black solid after drying, turn out to be sheet DHN-melanin through EPR test, IR test, electron microscopic observation.
The Powdered relatively DHN-melanin of EPR test specification sheet DHN-melanin of melanin contains more radical.Electronic Speculum result shows that Powdered DHN-melanin is inhomogenous particle, and size is between 400-1200 nm; Sheet DHN-melanin is irregular sheet.
Beneficial effect of the present invention is embodied in: the melanic preparation method who discloses a kind of single type; Can be used in and play anti-oxidant and ray in the makeup, remove radical; Can be used in and play decoration function in the hair dye, also can be used on the biotic pesticide aspect and play bright protective agent.
Description of drawings
Fig. 1 is the electromicroscopic photograph of Powdered DHN-melanin
Fig. 2 is the EPR test pattern of Powdered DHN-melanin
Fig. 3 is the IR test pattern of Powdered DHN-melanin
Fig. 4 is the electromicroscopic photograph of sheet DHN-melanin
Fig. 5 is the ESR test pattern of sheet DHN-melanin
Fig. 6 is the IR test pattern of sheet DHN-melanin.
Embodiment
Can further understand the present invention through specific embodiment given below.But they are not to qualification of the present invention.
Embodiment 1: the preparation method of Powdered DHN-melanin
1) with 1,8-DHN slowly adds Hydrocerol A-Na
2HPO
4In the damping fluid (pH5.0), stir,
2) the continuous NaNO that adds 1M in the whipping process
2Solution is to waiting mole, stirring at room half a hour,
3) reaction product is filtered, insolubles is used ETHYLE ACETATE, methyl alcohol, water rinse twice respectively,
4) the deposition nature dries, and turns out to be powder DHN-melanin through EPR test, IR test, electron microscopic observation.
Embodiment 2: the ammonium sulfate method of enrichment prepares fungi
Daldinia eschscholziiThe outer crude protein of IFB-TL01 born of the same parents
Fungi IFB-TL01 activation on the PDA flat board is inoculated into fresh thalline piece in the 1 L Erlenmeyer flask, every bottle of ME substratum that contains 400 mL; Inoculation 5-6 bottle is on shaking table; After cultivating 4 days under 150-200 rpm, the 28 ℃ of conditions, thalline is filtered, bacterium liquid is at 4 ℃; Centrifugal 20 min of 10,000 rpm go out residual mycelium; Slowly add ammonium sulfate in the bacterium liquid, making its final concentration was 80% (every liter of bacterium liquid adds 516g ammonium sulfate), and 4 ℃ of lower magnetic force whisking appliance stirred overnight fully precipitate albumen; 4 ℃ are descended 10, remove supernatant behind centrifugal 20 min of 000rpm; Deposition is with an amount of Hydrocerol A-Na
2HPO
4Damping fluid dissolving (filter paper filtering is removed insolubles); Place dialysis tubing to dialyse; Afterwards enzyme liquid is lyophilized into brown powder.
Embodiment 3: the outer crude protein enzyme activity determination of fungi IFB-TL01 born of the same parents
With reference to Robort Bourbounais method, be substrate with 3-ethyl benzothiazole-6-sulfonic acid (ABTS), measure the rate of oxidation of enzyme to it.Concrete grammar is: reaction is at room temperature carried out; Total reaction volume is 3 ml; Comprise 0.5 ml, 0.5 mmol/L ABTS and 1.5 ml, 0.1 mmol/L Hydrocerol A, add 1 ml fermented liquid, under 420 nm, measure the variation of its light absorption value; The unit definition of enzyme is PM enzyme liquid light absorption value increasing amount Δ OD420/ (ml.min), proves that the outer crude protein of TL01 born of the same parents has laccase (or oxydase) activity.
Embodiment 4: the preparation method of sheet DHN-melanin
1) ph optimum of the crude protein of the concentrated preparation of ammonium sulfate is 5, at Hydrocerol A-Na of 10ml pH5
2HPO
4Add 5 mg 1 in the damping fluid, the crude protein of 8-DHN, 200 U, 28 ℃, 180 rpm react 8 h,
2) reaction solution is used ethyl acetate extraction; Organic phase/aqueous phase interface has insolubles, and insolubles is collected, and uses twice of methyl alcohol, water rinse respectively; Obtain the sheet black solid after drying, turn out to be sheet DHN-melanin through EPR test, IR test, electron microscopic observation.
The OH free radical scavenging activity of 5: two kinds of melanin of embodiment is measured
1) required solvent: CuSO
4Solution, 1.14 mmol/ L; Benzoic acid solution, 0. 925 mmol/ L; Xitix (AA), 0. 97mmol/ L solution (preparation before using); Phosphate buffer soln, pH7.40.
2) in the test tube of 10mL, add the phosphate buffer soln of 5. 00 mL pH7.4 successively respectively, 0.30 mL, 1.14 mol/ L CuSO
4Solution; 1.20 L 0.925 mmol/ L phenylformic acid and 1.00mL 97 μ mol/ L AA; Being settled to 10 ml shakes up; At room temperature place 90 min, get on 96 orifice plates that 200 μ l are added to black, be respectively at excitation wavelength and emission wavelength then and measure relative intensity of fluorescence under 294 nm and 414 nm.
3) in above system, add a certain amount of melanochrome, the mensuration fluorescence intensity is F
Black, not adding melanic blank system, its fluorescence intensity is F
0Do not add xitix and melanic system, its fluorescence intensity is F, then clearance rate
Clearance rate (%)=(F
0-F
Black)/(F
0-F)
4) clearance rate is calculated
| ? | Three MVs |
| F 0 | 130.5 |
| F | 60.13 |
| F Black powder(×10 - 6g/ mL) | 87.8 |
| F Black-film(×10 - 6g/ mL) | 94.1 |
F
Black powder=60.7%
F
Black-film=51.7%
Above results suggest, two kinds of melanochrome have the ability of stronger removing hydroxyl radical free radical.
Claims (1)
1. melanic preparation method of single type is characterized in that being made up of the following step:
1) the ammonium sulfate method of enrichment prepares fungi
Daldinia eschscholziiThe outer crude protein of IFB-TL01 born of the same parents utilizes the ABTS method to measure the laccase that contains in the crude protein,
2) pH of crude protein is 5, is Hydrocerol A-Na of 5 at 10 ml pH
2HPO
4Add 5 mg 1 in the damping fluid, the crude protein of 8-DHN, 200U, 28 ℃, 180 rpm react 8 h,
3) reaction solution is used ethyl acetate extraction, organic phase/aqueous phase interface has insolubles, and insolubles is collected, and uses methyl alcohol, water rinse twice respectively, and airing promptly obtains the sheet black solid, turns out to be sheet DHN-melanin through ESR test, electron microscopic observation.
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| CN108220258B (en) * | 2016-12-15 | 2023-06-27 | 天津市农业科学院 | Preparation method of stropharia rugoso-annulata active protein with laccase activity |
| CN114671794B (en) * | 2022-04-07 | 2023-11-14 | 江南大学 | Melanin from radiorhizobia and its application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260244A (en) * | 2008-04-18 | 2008-09-10 | 辽宁精化科技有限公司 | Method for reducing medium black P2B residue |
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| CN101260244A (en) * | 2008-04-18 | 2008-09-10 | 辽宁精化科技有限公司 | Method for reducing medium black P2B residue |
Non-Patent Citations (1)
| Title |
|---|
| Mario C. N. Saparrat et al..Pseudocercospora griseola Causing Angular Leaf Spot on Phaseolus vulgaris Produces 1,8-Dihydroxynaphthalene-Melanin..《Mycopathologia》.2009,第168卷(第1期),41-47. * |
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