CN102210786A - Method for extracting natural antioxidant from shells of camellia oleifera - Google Patents
Method for extracting natural antioxidant from shells of camellia oleifera Download PDFInfo
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- CN102210786A CN102210786A CN201110151448XA CN201110151448A CN102210786A CN 102210786 A CN102210786 A CN 102210786A CN 201110151448X A CN201110151448X A CN 201110151448XA CN 201110151448 A CN201110151448 A CN 201110151448A CN 102210786 A CN102210786 A CN 102210786A
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- camellia oleifera
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- antioxidant substances
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- 241000526900 Camellia oleifera Species 0.000 title claims abstract description 55
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- JPFCOVZKLAXXOE-XBNSMERZSA-N (3r)-2-(3,5-dihydroxy-4-methoxyphenyl)-8-[(2r,3r,4r)-3,5,7-trihydroxy-2-(4-hydroxyphenyl)-3,4-dihydro-2h-chromen-4-yl]-3,4-dihydro-2h-chromene-3,5,7-triol Chemical group C1=C(O)C(OC)=C(O)C=C1C1[C@H](O)CC(C(O)=CC(O)=C2[C@H]3C4=C(O)C=C(O)C=C4O[C@@H]([C@@H]3O)C=3C=CC(O)=CC=3)=C2O1 JPFCOVZKLAXXOE-XBNSMERZSA-N 0.000 claims abstract description 24
- 229920001991 Proanthocyanidin Polymers 0.000 claims abstract description 24
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- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
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- 238000000874 microwave-assisted extraction Methods 0.000 claims abstract description 7
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- 239000000463 material Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- CWEZAWNPTYBADX-UHFFFAOYSA-N Procyanidin Natural products OC1C(OC2C(O)C(Oc3c2c(O)cc(O)c3C4C(O)C(Oc5cc(O)cc(O)c45)c6ccc(O)c(O)c6)c7ccc(O)c(O)c7)c8c(O)cc(O)cc8OC1c9ccc(O)c(O)c9 CWEZAWNPTYBADX-UHFFFAOYSA-N 0.000 description 8
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- GCPYCNBGGPHOBD-UHFFFAOYSA-N Delphinidin Natural products OC1=Cc2c(O)cc(O)cc2OC1=C3C=C(O)C(=O)C(=C3)O GCPYCNBGGPHOBD-UHFFFAOYSA-N 0.000 description 7
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- 235000007242 delphinidin Nutrition 0.000 description 7
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- HGVVOUNEGQIPMS-UHFFFAOYSA-N procyanidin Chemical compound O1C2=CC(O)=CC(O)=C2C(O)C(O)C1(C=1C=C(O)C(O)=CC=1)OC1CC2=C(O)C=C(O)C=C2OC1C1=CC=C(O)C(O)=C1 HGVVOUNEGQIPMS-UHFFFAOYSA-N 0.000 description 7
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- KMVWNDHKTPHDMT-UHFFFAOYSA-N 2,4,6-tripyridin-2-yl-1,3,5-triazine Chemical compound N1=CC=CC=C1C1=NC(C=2N=CC=CC=2)=NC(C=2N=CC=CC=2)=N1 KMVWNDHKTPHDMT-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
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- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 2
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 1
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- 240000001548 Camellia japonica Species 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
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- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- Medicines Containing Plant Substances (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
本发明涉及一种从油茶壳中提取天然抗氧化物质的方法，以粉碎后的油茶壳为原料，以水为溶剂，采用微波辅助提取法浸提得到提取液，提取液离心分离后得到的上清液使用非极性或低极性大孔吸附树脂分离，乙醇水溶液进行洗脱，洗脱液蒸馏出乙醇后得到主要成分为油茶壳原花色素的液体状天然抗氧化物质。经冷冻干燥后得粉状天然抗氧化物质。由本发明制得的目标产物具有更强的抗氧化生物活性功能。
The invention relates to a method for extracting natural antioxidant substances from camellia oleifera husk. The crushed camellia oleifera husk is used as raw material, water is used as solvent, and an extract is extracted by microwave-assisted extraction method. The supernatant is separated by non-polar or low-polar macroporous adsorption resin, eluted with ethanol aqueous solution, and the eluent is distilled to obtain a liquid natural antioxidant substance whose main component is proanthocyanidin from camellia oleifera husk. After freeze-drying, a powdery natural antioxidant substance is obtained. The target product prepared by the present invention has stronger antioxidant biological activity.
Description
Technical field
The present invention relates to a kind of method, relate in particular to a kind of method of from shell of Camelliaoleifera Abel, extracting the natural anti-oxidation material from vegetable material extraction natural anti-oxidation active substance.
Background technology
Tea oil tree is the distinctive woody edible oil materials seeds of China, also is and one of Elaeis guineensis Jacq., Fructus Canarii albi, the Cortex cocois radicis world four big woody edible oil sources seeds equally celebrated for their achievements.In nearly 5,000 ten thousand mu of state-owned camellia oleifera lam, produce about 1,000,000 tons of Semen Camelliae per year, but the abundant edible camellia oil of production nutritive value.Shell of Camelliaoleifera Abel (also claiming shell of Camellia oleifera Abel, the peel of oil tea fruit) accounts for 60% of whole oil tea fruit weight, is the residue of oil tea secondary industry, and according to measuring and calculating, its annual growing amount has 1,600,000 tons approximately.Shell of Camelliaoleifera Abel is rich in plant polyphenol, and its main component is proanthocyanidin (procyanidins) class.Proanthocyanidin has very strong antioxidation biology activity, can remove harmful free radicals in the human body, improve the immunity of human body, can be used as the main effective ingredient of anti-cancer, mutation, control cardiovascular disease medicine and as the new type natural antioxidant of safety non-toxic, become the important additives of the important source material of medicine, health product and food, cosmetics.
Abroad to the bioactive research of proanthocyanidin (mainly being procyanidin) existing decades of history, particularly since the eighties, European countries such as Germany, France reach countries such as Japan, India, Korea S and have carried out number of research projects.China since the eighties development and use research of proanthocyanidin.
Nineteen fifty-one, France Jacques Masquelier found the antioxygenic property of procyanidin first, and successfully extracted procyanidin from the maritime pine bark.U.S. Joslyn in 1967 etc. isolate the proanthocyanidin polyphenolic substance from Pericarpium Vitis viniferae and Semen Vitis viniferae.Bombardelli had invented the method for extracting the high assay proto cyaniding mixture from Semen Vitis viniferae in 1976.Jacques Masquelier in 1979 further studies and extracts procyanidin and realized industrialization from Semen Vitis viniferae.
Abroad mainly contain about the patent of extracting proanthocyanidin: French Jacques Masquellier in 1969 from the maritime pine bark with boiling water extraction, ethyl acetate extraction crude extract, chloroform precipitated product.Japan in 1989 have He Minming with
Aesculus hippocastanumBark is a raw material, uses water extraction, petroleum ether, resin absorption product.U.S. Tochiakl Ariga from Cortex Pini with methanol extraction, petroleum ether, ethyl acetate extraction, liquid-phase chromatographic column separate and to obtain product.Polish Oszmianski Jan in 1996 is a solvent with acetone, adopts ultrasound wave to extract procyanidin from Semen Vitis viniferae, ethyl acetate extraction, chloroform precipitated product.U.S. Henkel company extracted procyanidin from Semen Vitis viniferae in 1997, with boiling water extraction, and ethyl acetate extraction crude extract, chloroform precipitation product.
Shell of Camelliaoleifera Abel is as the by-product of oil tea processing, acts as a fuel usually to use or go out of use in actual production, caused the pollution of environment and the waste of resource.In recent years, some studies show that shell of Camelliaoleifera Abel has stronger antioxidant activity.Lin Shen living (1997) studies show that the acetone-water extract of shell of Camelliaoleifera Abel has very strong non-oxidizability, and its antioxidant content is mainly gallic acid and catechin.Chen Yue (2008) has set up the process of enriching of polyphenol in the shell of Camelliaoleifera Abel, adopts 60% acetone-water to extract, ethyl acetate extraction, and D101 type macroporous resin adsorption, behind 30% ethanol elution, the content of polyphenol has reached 45%.Shen Jianfu (2008) studies the ethanol extraction technology of total flavonoids substance in the shell of Camelliaoleifera Abel, it studies show that at 30 times after 60% heavy soak with ethanol of sample, 40 ℃ of following ultrasound wave auxiliary extraction 45 min, extract 2 times continuously, total leaching rate of flavone can reach 97.34%, and the flavone stripping quantity in the shell of Camelliaoleifera Abel is 1.709%
The inventor's seminar has carried out the method research of extracting the proanthocyanidin antioxidant from plant parts such as hair Cortex Myricae Rubrae, Cortex Phyllanthis in recent years, has obtained relevant national inventing patent.But Shang Weijian extracts the method based on the natural anti-oxidation material of proanthocyanidin from shell of Camelliaoleifera Abel.
Summary of the invention
Low for the utilization rate that solves the shell of Camelliaoleifera Abel that prior art exists, proanthocyanidin can be with extracting the limited shortcoming of raw material type, the invention provides a kind of method of from shell of Camelliaoleifera Abel, extracting the natural anti-oxidation material, can improve the added value of shell of Camelliaoleifera Abel, enlarge the raw material sources of proanthocyanidin.
Technical scheme of the present invention is: a kind of method of extracting the natural anti-oxidation material from shell of Camelliaoleifera Abel, with the shell of Camelliaoleifera Abel after pulverizing is raw material, with water is solvent, adopt the lixiviate of microwave-assisted extraction method to obtain extracting solution, the supernatant that obtains after the extracting solution centrifugalize uses nonpolar or low polar macroporous adsorption resin to separate, ethanol water carries out eluting, and eluent obtains the liquid natural anti-oxidation material that main component is the shell of Camelliaoleifera Abel proanthocyanidin after distilling out ethanol.
The granularity that described shell of Camelliaoleifera Abel is pulverized is 2～4mm.
Described microwave exposure temperature is 60～80 ℃, and exposure time is 15～35min, and the mass volume ratio of shell of Camelliaoleifera Abel and water is 1:15～25g/ml.
Described nonpolar or low polar macroporous adsorption resin is AB-8, D101, D4006, H103.
Macroporous adsorbent resin control upper prop liquid and eluent flow rate are 1.4～1.7 Bv/h.
Described ethanol water is that the volume ratio of second alcohol and water is 60%～70% solution.
Liquid natural anti-reflecting oxide plasmogamy obtains powdery natural anti-oxidation material through after the vacuum lyophilization after being made as aqueous solution again.
Described vacuum is≤0.01MPa.
Beneficial effect:
1. the current research relevant with proanthocyanidin both at home and abroad mainly concentrates on extraction separation natural anti-oxidation active substance from Semen Vitis viniferae, skin and Cortex Pini raw material, and the present invention extracts the natural anti-oxidation active substance from shell of Camelliaoleifera Abel.Oil tea has wide resource distribution in areas such as China Fujian, Guangxi, Jiangxi, Hunan, Zhejiang and Anhui.The annual shell of Camelliaoleifera Abel stock number that produces of China is huge, is rich in proanthocyanidin in the shell of Camelliaoleifera Abel, and therefore target product raw material sources of the present invention are abundant.At present shell of Camelliaoleifera Abel is as the forest products industrial wood waste, thereby is dropped contaminated environment usually.The present invention can further develop the new type natural antioxidant of high added value, realizes the efficient utilization of the forest reserves.
2. the present invention is solvent with water, adopts microwave-assisted to extract, and separates preparation shell of Camelliaoleifera Abel proanthocyanidin through macroporous resin adsorption, and easy and simple to handle, extraction time is short, only needs 15～35 min, and gained proanthocyanidin product oxidation resistance is strong.
Description of drawings
Fig. 1 is the HPLC chromatogram of shell of Camelliaoleifera Abel proanthocyanidin acid degradation product;
524 nm wavelength detect down, and 1, delphinidin (delphinidin), 2, anthocyanidin (cyanidin).
Fig. 2 is the positive ion mode ESI-MS collection of illustrative plates of shell of Camelliaoleifera Abel proanthocyanidin acid degradation product.
A, delphinidin (delphinidin), B, anthocyanidin (cyanidin).
Oil-tea camellia husks tannin component catabolite after the degraded of n-butyl alcohol-hydrochloric acid (95:5) system is analyzed through HPLC, mainly comprises two chromatograph absworption peak (see figure 1)s in the collection of illustrative plates demonstration catabolite.Catabolite shows its molecular ion peak [M] through positive ion mode ESI mass spectral analysis
+Be respectively
M/z303.1 [C
15H
11O
7]
+With 287.1 [C
15H
11O
6]
+(see figure 2) can identify that thus catabolite is respectively delphinidin (delphinidin) and anthocyanidin (cyanidin), can learn thus to have procyanidin and two kinds of structure types of former delphinidin in the shell of Camelliaoleifera Abel proanthocyanidin.
The specific embodiment
A kind of concrete grammar that extracts the natural anti-oxidation material from shell of Camelliaoleifera Abel is as follows:
(1) pulverize: the shell of Camelliaoleifera Abel raw material after will purifying is pulverized with the plant pulverizer, sieve aperture Φ=2～4 mm;
(2) extract: with water is solvent, adopts microwave extraction, and the solid-liquid mass volume ratio is 1:15～25,60～80 ℃ of controlled microwave irradiation temperatures, and irradiation time 15～35 min get extracting solution;
(3) centrifugalize: extracting solution is isolated supernatant through centrifuge centrifugal 30 min under rotating speed 5000 rpm, and precipitate discards;
(4) resin absorption separates: with on the above-mentioned supernatant in advance through the nonpolar or low polar macroporous adsorption resin of purified treatment, the upper prop flow velocity is 1.4～1.7 Bv/h, absorption is back with pure washing post, the reuse volume ratio is the flow velocity eluting of the ethanol water of 60～70% v/v with 1.4～1.7 Bv/h, collects eluent;
(5) desolventizing: at normal pressure (1.01 * 10
5Pa) steam ethanol under and get liquid natural anti-oxidation material from pure water elution liquid, its main component is the shell of Camelliaoleifera Abel proanthocyanidin.
(6) vacuum lyophilization: use for convenience and transport, can obtain powder by vacuum drying.Liquid natural anti-oxidation material is diluted with pure water, get product water solution; Product water solution carries out dehydrate under the vacuum low-pressure of≤0.01 Mpa after freezing, both got powdery natural anti-oxidation active substance.
Embodiment 1:
A kind of method of from shell of Camelliaoleifera Abel, extracting the natural anti-oxidation material:
(1) pulverize: the shell of Camelliaoleifera Abel raw material after will purifying is pulverized (sieve aperture Φ=2～4 mm) with the plant pulverizer.
(2) extract: with water is solvent, adopts microwave extraction, and the solid-liquid mass volume ratio is 1:15～25,60～80 ℃ of controlled microwave irradiation temperatures, and irradiation time 15～35 min get extracting solution; Wherein temperature can be: 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃.
(3) centrifugalize: extracting solution is isolated supernatant through centrifuge centrifugal 30 min under rotating speed 5000 rpm, and precipitate discards.
(4) resin absorption separates: with on the above-mentioned supernatant in advance through the nonpolar or low polar macroporous adsorption resin of purified treatment, the upper prop flow velocity is 1.4～1.7 Bv/h, absorption is back with pure washing post, the reuse volume ratio is the flow velocity eluting of the ethanol water of 60～70% v/v with 1.4～1.7 Bv/h, collects eluent.
(5) desolventizing: at normal pressure (1.01 * 10
5Pa) steam ethanol under from pure water elution liquid, obtaining main component is the liquid natural anti-oxidation material of shell of Camelliaoleifera Abel proanthocyanidin.
(6) vacuum lyophilization:, get product water solution with the pure water dilution.Product water solution carries out dehydrate under the vacuum low-pressure of 0～0.01 Mpa after freezing, both got powdery natural anti-oxidation active substance.
Embodiment 2:
(1) will through purify, air-dry and pulverize shell of Camelliaoleifera Abel raw material 50 g and pure water 750 mL of (using the plant pulverizer) by Φ 2 mm sieve plates, place 1000 mL there-necked flasks, carry out microwave extraction, 80 ℃ of controlled microwave irradiation temperatures, irradiation time 35 min get extracting solution 620 mL.
(2) extracting solution is cooled off after the centrifuge centrifugalize is provided with centrifuge speed 5000 rpm, centrifugal 30 min isolate supernatant 550 mL.
(3) above-mentioned supernatant is added to the flow velocity of 1.4 Bv/h pass through pretreated AB-8 type macroporous resin (Bv=265 cm
3), then using the pure washing post of 2.4 Bv/h, ethanol-water solution 600 mL of reuse 70% merge eluent with the flow velocity eluting of 1.7 Bv/h.
(4) under normal pressure (1.01 * 10
5Pa) steam ethanol (reuse) in the alcohol-water eluent, obtaining main component is the liquid natural anti-oxidation material of shell of Camelliaoleifera Abel proanthocyanidin.
(5) with the pure water dilution, get product water solution.With the vacuum lyophilization at low temperatures of product water solution, obtain natural anti-oxidation active substance powder product 2.50 g, yield 5.47%(shell raw material is by over dry).
Embodiment 3:
(1) will through purify, air-dry and pulverize shell of Camelliaoleifera Abel raw material 30 g and pure water 750 mL of (using the plant pulverizer) by Φ 2 mm sieve plates, place 1000 mL there-necked flasks, carry out microwave extraction, 60 ℃ of controlled microwave irradiation temperatures, irradiation time 35 min get extracting solution 650 mL.
(2) extracting solution is cooled off after the centrifuge centrifugalize is provided with centrifuge speed 5000 rpm, centrifugal 30 min isolate supernatant 580 mL.
(3) above-mentioned supernatant is added to the flow velocity of 1.5 Bv/h pass through pretreated AB-8 type macroporous resin (Bv=265 cm
3), then using the pure washing post of 2.4 Bv/h, ethanol water 500 mL of reuse 70% merge eluent with the flow velocity eluting of 1.5 Bv/h.
(4) under normal pressure (1.01 * 10
5Pa) steam ethanol (reuse) in the ethanol water elution liquid, obtaining main component is the liquid natural anti-oxidation material of shell of Camelliaoleifera Abel proanthocyanidin.
(5) with the pure water dilution, get product water solution.With the vacuum lyophilization at low temperatures of product water solution, obtain natural anti-oxidation active substance powder product 1.60 g, yield 5.83%(shell raw material is by over dry).
The product that above embodiment is made mixes the back as target product, measures oxidation resistance.
Attached 1: target product is measured the removing ability of free radical among the present invention
(DPPH, U.S. Sigman company) is reference material with diphenyl-picryl-diazanyl free radical, with the clearance rate of spectrophotometry target product of the present invention to the DPPH free radical.
Draw methanol solution (concentration is 0.025 mg/mL) 5 mL of DPPH, mix with methanol solution (concentration is 0.1 mg/mL) 1 mL of target product sample.
λ=517 nm places (is reference with methanol) tracking and measuring light absorption value.Absorbance continues to descend, and till maintenance was invariable, timing was also calculated.
Measurement result:
Absorbance drops to the time of steady state value: 12 min
DPPH clearance rate: 84.97%
DPPH clearance rate: 97 mg/gmin
Result data shows that target product has the removing ability to free radical (DPPH).
Attached 2: the target product Total antioxidant capacity is measured among the present invention
(U.S. Sigman company) is tester with ascorbic acid, measures the Total antioxidant capacity of target product of the present invention with iron ion reduction/resistance to oxidation (FRAP) algoscopy.
Get 0.1 mL target product sample methanol solution (concentration is 0.1 mg/mL), with 3.0 mL TPTZ working solutions (by 0.3 mol/L acetate buffer, 25 mL, 10 mmol/L TPTZ solution, 2.5 mL, 20 mmol/L FeCl
3Solution 2.5 mL form) reaction 5 min in 25 ℃ of waters bath with thermostatic control, 593 nm places record absorbance, are reference with the deionized water.Experimental result is represented with the amount (mmol AAE/g) of the ascorbic acid that reaches identical oxidation resistance.
Measurement result:
Total antioxidant capacity: 6.46 mmol AAE/g
Result data shows that target product has stronger oxidation resistance.
Therefore: target product has antioxidant activity among the present invention; Remove free radical ability and iron ion reduction/resistance to oxidation.
Claims (8)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030710A (en) * | 2013-01-05 | 2013-04-10 | 广西大学 | Resource utilization method of camellia oleifera shells |
| CN104072468A (en) * | 2013-03-26 | 2014-10-01 | 宜春元博山茶油科技农业开发有限公司 | Proanthocyanidin extraction process from camellia seed hull |
| CN104789354A (en) * | 2015-03-30 | 2015-07-22 | 浙江大学 | Application of myrica rubra leaf proanthocyanidin to lipid antioxidation |
| CN107198668A (en) * | 2017-05-25 | 2017-09-26 | 中南大学 | Oil tea seed peel moderate resistance oxidizing component extract and its extracting method and application |
| CN110408404A (en) * | 2019-08-26 | 2019-11-05 | 江西农业大学 | Camellia oleifera husk extract and its preparation method and application |
| CN112522341A (en) * | 2020-12-30 | 2021-03-19 | 江西神州通油茶科技有限公司 | Co-production method for extracting xylo-oligosaccharide and procyanidine from camellia oleifera shells |
| CN112618430A (en) * | 2020-12-16 | 2021-04-09 | 湖南林之神生物科技有限公司 | Camellia procyanidine mask and preparation method thereof |
| CN114874173A (en) * | 2022-05-24 | 2022-08-09 | 湖南金昌生物技术有限公司 | Method for extracting procyanidine from fresh oil tea fruit shells |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560265A (en) * | 2009-06-01 | 2009-10-21 | 浙江大学 | Method for preparing oil-tea camellia husk polysaccharide and purifying method |
| CN101744948A (en) * | 2008-12-19 | 2010-06-23 | 浙江大学 | Extract from fruit shell of camellia oleifera abel and preparation method and application thereof |
| CN101885925A (en) * | 2010-07-01 | 2010-11-17 | 韩山师范学院 | A method for extracting brown pigment from camellia oleifera husk |
-
2011
- 2011-06-08 CN CN201110151448A patent/CN102210786B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101744948A (en) * | 2008-12-19 | 2010-06-23 | 浙江大学 | Extract from fruit shell of camellia oleifera abel and preparation method and application thereof |
| CN101560265A (en) * | 2009-06-01 | 2009-10-21 | 浙江大学 | Method for preparing oil-tea camellia husk polysaccharide and purifying method |
| CN101885925A (en) * | 2010-07-01 | 2010-11-17 | 韩山师范学院 | A method for extracting brown pigment from camellia oleifera husk |
Non-Patent Citations (4)
| Title |
|---|
| 董瑞霞等: "茶籽壳原花青素柱分离条件的研究", 《食品与发酵工业》 * |
| 邱贺媛等: "微波辐照提取油茶果壳棕色素及其稳定性研究", 《食品科学》 * |
| 陈亚琪等: "油茶蒲提取物的抗氧化活性", 《林业科学》 * |
| 陈跃龙等: "油茶果皮多元酚富集工艺研究", 《时珍国医国药》 * |
Cited By (13)
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| CN103030710B (en) * | 2013-01-05 | 2015-03-18 | 广西大学 | Resource utilization method of camellia oleifera shells |
| CN104072468A (en) * | 2013-03-26 | 2014-10-01 | 宜春元博山茶油科技农业开发有限公司 | Proanthocyanidin extraction process from camellia seed hull |
| CN104789354A (en) * | 2015-03-30 | 2015-07-22 | 浙江大学 | Application of myrica rubra leaf proanthocyanidin to lipid antioxidation |
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| CN112618430A (en) * | 2020-12-16 | 2021-04-09 | 湖南林之神生物科技有限公司 | Camellia procyanidine mask and preparation method thereof |
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| CN114874173A (en) * | 2022-05-24 | 2022-08-09 | 湖南金昌生物技术有限公司 | Method for extracting procyanidine from fresh oil tea fruit shells |
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