CN1055931C - 富含糖苷配基异黄酮植物蛋白浓缩物及其制备方法 - Google Patents
富含糖苷配基异黄酮植物蛋白浓缩物及其制备方法 Download PDFInfo
- Publication number
- CN1055931C CN1055931C CN94194200A CN94194200A CN1055931C CN 1055931 C CN1055931 C CN 1055931C CN 94194200 A CN94194200 A CN 94194200A CN 94194200 A CN94194200 A CN 94194200A CN 1055931 C CN1055931 C CN 1055931C
- Authority
- CN
- China
- Prior art keywords
- isoflavones
- enzyme
- glucoside
- isoflavone
- protein
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 108010082495 Dietary Plant Proteins Proteins 0.000 title claims abstract description 39
- 239000012141 concentrate Substances 0.000 title claims abstract description 24
- CJWQYWQDLBZGPD-UHFFFAOYSA-N isoflavone Natural products C1=C(OC)C(OC)=CC(OC)=C1C1=COC2=C(C=CC(C)(C)O3)C3=C(OC)C=C2C1=O CJWQYWQDLBZGPD-UHFFFAOYSA-N 0.000 claims abstract description 118
- 235000008696 isoflavones Nutrition 0.000 claims abstract description 118
- 239000000463 material Substances 0.000 claims abstract description 77
- 150000002515 isoflavone derivatives Chemical class 0.000 claims abstract description 70
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 24
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 24
- GOMNOOKGLZYEJT-UHFFFAOYSA-N isoflavone Chemical compound C=1OC2=CC=CC=C2C(=O)C=1C1=CC=CC=C1 GOMNOOKGLZYEJT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 102000006995 beta-Glucosidase Human genes 0.000 claims abstract description 19
- 108010047754 beta-Glucosidase Proteins 0.000 claims abstract description 19
- 108090000371 Esterases Proteins 0.000 claims abstract description 8
- TWCMVXMQHSVIOJ-UHFFFAOYSA-N Aglycone of yadanzioside D Natural products COC(=O)C12OCC34C(CC5C(=CC(O)C(O)C5(C)C3C(O)C1O)C)OC(=O)C(OC(=O)C)C24 TWCMVXMQHSVIOJ-UHFFFAOYSA-N 0.000 claims description 40
- PLMKQQMDOMTZGG-UHFFFAOYSA-N Astrantiagenin E-methylester Natural products CC12CCC(O)C(C)(CO)C1CCC1(C)C2CC=C2C3CC(C)(C)CCC3(C(=O)OC)CCC21C PLMKQQMDOMTZGG-UHFFFAOYSA-N 0.000 claims description 40
- PFOARMALXZGCHY-UHFFFAOYSA-N homoegonol Natural products C1=C(OC)C(OC)=CC=C1C1=CC2=CC(CCCO)=CC(OC)=C2O1 PFOARMALXZGCHY-UHFFFAOYSA-N 0.000 claims description 40
- 229930182478 glucoside Natural products 0.000 claims description 38
- 102000004190 Enzymes Human genes 0.000 claims description 35
- 108090000790 Enzymes Proteins 0.000 claims description 34
- 235000010469 Glycine max Nutrition 0.000 claims description 30
- ZQSIJRDFPHDXIC-UHFFFAOYSA-N daidzein Chemical compound C1=CC(O)=CC=C1C1=COC2=CC(O)=CC=C2C1=O ZQSIJRDFPHDXIC-UHFFFAOYSA-N 0.000 claims description 30
- 244000068988 Glycine max Species 0.000 claims description 28
- -1 glucoside isoflavones Chemical class 0.000 claims description 28
- ZCOLJUOHXJRHDI-CMWLGVBASA-N genistein 7-O-beta-D-glucoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=C2C(=O)C(C=3C=CC(O)=CC=3)=COC2=C1 ZCOLJUOHXJRHDI-CMWLGVBASA-N 0.000 claims description 25
- ZCOLJUOHXJRHDI-FZHKGVQDSA-N Genistein 7-O-glucoside Natural products O([C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O1)c1cc(O)c2C(=O)C(c3ccc(O)cc3)=COc2c1 ZCOLJUOHXJRHDI-FZHKGVQDSA-N 0.000 claims description 22
- 235000018102 proteins Nutrition 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 14
- 235000007240 daidzein Nutrition 0.000 claims description 13
- 150000008131 glucosides Chemical class 0.000 claims description 13
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 9
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003125 aqueous solvent Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 108010064851 Plant Proteins Proteins 0.000 claims description 3
- 235000021118 plant-derived protein Nutrition 0.000 claims description 3
- 235000021374 legumes Nutrition 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- GMTUGPYJRUMVTC-UHFFFAOYSA-N Daidzin Natural products OC(COc1ccc2C(=O)C(=COc2c1)c3ccc(O)cc3)C(O)C(O)C(O)C=O GMTUGPYJRUMVTC-UHFFFAOYSA-N 0.000 description 6
- KYQZWONCHDNPDP-UHFFFAOYSA-N Daidzoside Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=C2C(=O)C(C=3C=CC(O)=CC=3)=COC2=C1 KYQZWONCHDNPDP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 108010059820 Polygalacturonase Proteins 0.000 description 5
- KYQZWONCHDNPDP-QNDFHXLGSA-N daidzein 7-O-beta-D-glucoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=C2C(=O)C(C=3C=CC(O)=CC=3)=COC2=C1 KYQZWONCHDNPDP-QNDFHXLGSA-N 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WUADCCWRTIWANL-UHFFFAOYSA-N biochanin A Chemical compound C1=CC(OC)=CC=C1C1=COC2=CC(O)=CC(O)=C2C1=O WUADCCWRTIWANL-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 206010006187 Breast cancer Diseases 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 108010073771 Soybean Proteins Proteins 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000019710 soybean protein Nutrition 0.000 description 3
- 208000026310 Breast neoplasm Diseases 0.000 description 2
- 241001232809 Chorista Species 0.000 description 2
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 206010060862 Prostate cancer Diseases 0.000 description 2
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 2
- 101000693619 Starmerella bombicola Lactone esterase Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005862 Whey Substances 0.000 description 2
- 102000007544 Whey Proteins Human genes 0.000 description 2
- 108010046377 Whey Proteins Proteins 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- ZZIALNLLNHEQPJ-UHFFFAOYSA-N coumestrol Chemical compound C1=C(O)C=CC2=C1OC(=O)C1=C2OC2=CC(O)=CC=C12 ZZIALNLLNHEQPJ-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006911 enzymatic reaction Methods 0.000 description 2
- TZBJGXHYKVUXJN-UHFFFAOYSA-N genistein Natural products C1=CC(O)=CC=C1C1=COC2=CC(O)=CC(O)=C2C1=O TZBJGXHYKVUXJN-UHFFFAOYSA-N 0.000 description 2
- 235000006539 genistein Nutrition 0.000 description 2
- 229940045109 genistein Drugs 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000014347 soups Nutrition 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- 101800000263 Acidic protein Proteins 0.000 description 1
- 102000001301 EGF receptor Human genes 0.000 description 1
- 108060006698 EGF receptor Proteins 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 108700041567 MDR Genes Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- DCTLJGWMHPGCOS-UHFFFAOYSA-N Osajin Chemical compound C1=2C=CC(C)(C)OC=2C(CC=C(C)C)=C(O)C(C2=O)=C1OC=C2C1=CC=C(O)C=C1 DCTLJGWMHPGCOS-UHFFFAOYSA-N 0.000 description 1
- OUZCFMSJGDEXRT-UHFFFAOYSA-N Scandinone Natural products O=C1C=2C(OC)=C(CC=C(C)C)C=3OC(C)(C)C=CC=3C=2OC=C1C1=CC=C(O)C=C1 OUZCFMSJGDEXRT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010936 aqueous wash Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 102000015694 estrogen receptors Human genes 0.000 description 1
- 108010038795 estrogen receptors Proteins 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930003944 flavone Natural products 0.000 description 1
- 235000011949 flavones Nutrition 0.000 description 1
- 150000002213 flavones Chemical class 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- HKQYGTCOTHHOMP-UHFFFAOYSA-N formononetin Chemical compound C1=CC(OC)=CC=C1C1=COC2=CC(O)=CC=C2C1=O HKQYGTCOTHHOMP-UHFFFAOYSA-N 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229930013032 isoflavonoid Natural products 0.000 description 1
- 150000003817 isoflavonoid derivatives Chemical class 0.000 description 1
- 235000012891 isoflavonoids Nutrition 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000011340 peptidyl-tyrosine autophosphorylation Effects 0.000 description 1
- 230000006920 protein precipitation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 210000001541 thymus gland Anatomy 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/415—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from plants
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
- C12P17/02—Oxygen as only ring hetero atoms
- C12P17/06—Oxygen as only ring hetero atoms containing a six-membered hetero ring, e.g. fluorescein
Abstract
本文揭示了富含糖苷配基异黄酮强化蛋白浓缩物及其生产方法和其回收。该方法包括等电位下洗涤植物蛋白物质使之形成蛋白浓缩物,将其匀浆并与足量的β-葡糖苷酶或酯酶在足够时间范围、温度、pH值下充分反应,使浓缩物中至少大部分葡糖苷配糖基异黄酮转化为糖苷配基异黄酮。
Description
此发明涉及糖苷配基异黄酮富含植物蛋白浓缩物的生产。通过洗涤植物蛋白物质产生植物蛋白浓缩物,利用一种或几种β-葡糖苷酶大多数葡糖苷配基异黄酮转化成可保留在富含蛋白浓缩物中的糖苷配基异黄酮。此项专利申请是1993.10.12提交的美国专利申请序号No.08/135,194,的部分继续申请。
异黄酮存在于包括植物蛋白物质例如大豆的各种豆科植物中,这些化合物包括黄豆苷,6″-OAc黄豆苷,6″-OMal黄豆苷,黄豆苷原,染料木苷,6″-OAc染料木苷,6″-OMal染料木苷,染料木苷原,大豆异黄酮,6″-OAc大豆异黄酮,6″-OMal大豆异黄酮,大豆异黄酮原,鹰嘴豆芽素A7-羟基-4’-甲氧异黄酮和拟雌内酯。通常上述化合物天然存在于苦味的大豆,及商业产品的生产过程中(如分离或浓缩)。问题焦点是除去这些物质。例如在传统的制备大豆蛋白分离方法中,豆片在碱性水溶液介质中被萃取,大部分异黄酮溶于萃取液,而其余溶于乳清中,乳清经蛋白酸沉淀形成分离体。留在于酸性蛋白沉淀分离体中的残余异黄酮经彻底冲洗而分离。
近期发现在植物蛋白(如大豆)中的异黄酮可抑制人体癌细胞的生长,例如胸腺及前列腺的癌细胞,其记载在如下文献中:″Genistein Inhibition of the Growth of Human Breast Cancer Cells,Independencefrom Estrogen Receptors and the Multi-Drug Resistance Gene″by Peterson andBarnes,Biochemical and Biophvsical Research.Communications,Vol.179,No.1,pp.661-667,August 30.1991;″Genistein and Biochanin A Inhibit theGrowth of Human Prostate Cancer Cells but not Epidermal Growth FactorReceptor Tyrosine Auto-phosphorylation″by Peterson and Barnes.The Protate.Vol.22,pp.335-345(1993);and ″Soybeans Inhibit Mammary Tumors in Modelsof Breast Cancer″ by Barnes,et al. Mutagens and Carcinogens in the Diet.pp.239-253(1990).
上述异黄酮是以在下式7位上连带有葡萄糖分子的葡糖苷或糖苷形式存在的。一些葡糖苷,如6″-OAc染料木苷含一个与葡萄糖分子六位相连的乙酸酯基。而包括葡糖苷所有异黄酮苷令人感觉趣之处是其医药价值,最有价值的异黄酮是不带葡萄糖分子的糖苷配基。这些异黄酮的水溶性与糖苷或葡糖苷不同。从分类上看这些异黄酮是黄豆苷原,染料木苷原,大豆异黄酮原。这些糖苷配基具有如下通式:
其中R1,R2,R3和R4选自H,OH和OCH3。因此本发明涉及的是含有这些物质的糖苷配基物和植物蛋白浓缩物。
在本领域中已有许多将葡糖苷异黄酮转化成糖苷配基异黄酮的方法,例如日本专利申请258,669,Obata et al中记载该方法仅能达到中等转化,因而不十分理想,特别是在大规模商业生产中。另外,许多已知方法(如669申请)只讲到了如何从蛋白物质中除去异黄酮类物质,而未描述如何制备糖苷配基异黄酮富含蛋白浓缩物。因此需要一种方法使绝大多数葡糖苷异黄酮并优选实质上将所有葡糖苷异黄酮转化成糖苷配基异黄酮,并生产一糖苷配基异黄酮富含植物蛋白浓缩物。
因此发明的目的在于提供一种糖苷配基异黄酮富含植物蛋白浓缩物及其生产过程。本发明其它的目的如下详述。
本发明提供了一种富含糖苷配基异黄酮植物蛋白浓缩物及其生产方法。该方法包括用在植物蛋白等电位点的PH水溶液中洗涤含有葡糖苷的植物蛋白物质,从而产生植物蛋白浓缩物。该浓缩物与足够量的一种或多种β-葡糖苷酶,在足够的时间、温度、PH值下反应,使浓缩物中的至少大部分葡糖苷配转化为糖苷配基异黄酮,从而产生一种富含糖苷配基异黄酮蛋白浓缩物。本发明也提供了生产该浓缩物的方法,其中在洗涤或浓缩中补加β-葡糖苷酶。所得富含糖苷配基浓缩物然后可分离并脱水。另外,本发明也提供了以相对高的比例从植物蛋白物质回收蛋白浓缩物中异黄酮类物质的方法。
虽然本发明是针对大豆产品且方法具体适用于生产富含糖苷配基异黄酮浓缩大豆物料,但是对于含有异黄酮的各类植物蛋白资源都可利用此方法。例如适宜的蛋白材料是豆类物质,大豆物质或含大豆的植物蛋白物质。术语“大豆物质”在这里指大豆类及大豆类衍生物。
按优选具体实施的浓缩物,起始物是大豆片,其油已通过萃取去掉。豆蛋白浓缩物典型是用PH44至46这一蛋白等电位点的水溶性溶剂洗涤大豆片而制备的。一种可食酸加入水中提供豆蛋白物质的等电位洗涤。等电位洗涤去除了大量溶于水的碳水化合物及其它成份,但不去除蛋白质,由此得到了蛋白浓缩物,其通常是干品重量时的60-75%。在植物蛋白或豆类物质中的葡糖苷异黄酮通过等电位洗涤而去除。但在PH值相对较低时,所除去的量少于高PH值萃取时的量。因此从优选实施方案和最大限度回收异黄酮目的出发,优选等电点洗涤限定在一步或最多加一步额外洗涤。还优选洗涤蛋白物质的水性溶剂与蛋白物质的重量比大约是5∶1至10∶1。
所得浓缩物以约10-约15重量%的固体浓度悬浮于水中,然后与一种或多种β-葡糖苷酶反应,使浓缩物中至少大部分并优选实质上全部葡糖苷异黄酮转化成糖苷配基异黄酮。β-葡糖苷酶的最佳PH值范围依赖于具体使用的β-葡糖苷酶,通常为4至8这间。萃取时的PH一般被调节到这样的PH范围,即在与酶反应前,所用的具体酶活性最大。该PH一般通过加可食用酸来调节,如醋酸、硫酸、磷酸,盐酸或任何其它适用的试剂。
β-葡糖苷酶可天然存在于大豆类物质或微生物生长过程中,这里称为“残留”酶,或被加到浓缩物之中。加入的酶,在这指“补充酶”。一般情况下如果浓缩物中“残留”酶的量不足以使异黄酮的葡糖苷转化成糖苷配基。则应加入补充酶。异黄酮转化所需酶的量是由多种因素决定的,其包括酶的种类、酶浓度分布、PH值系统及酶的活性。只要足够浓度的酶存在,无论是“残留酶”还是“补充酶”或二者兼有,浓缩物在足够时间温度及PH条件下与β-葡糖苷酶反应都可使大多数并优选实质上全部葡糖苷异黄酮转化成糖苷配基异黄酮。
较好的“补充酶”(β-葡糖苷酶类)包括生物果胶酶100L和300L,生物果胶酶OK70L,乳糖酶F,内酯酶。乳糖酶F可由Amano Intemational Enzyme Co.,Inc,P.O.Box 1000,Troy,UA22974提供,其最佳的PH范围为4-6;内酯酶(Lctozyme)可由Novo Industries,Enzyme division,Novo Alle,DK-2880Bagsvaerd.,Denmart提供,其最佳的PH为7左右。生物果胶酶100L和300L以及OK70L可由Quest International SarasotaFlorda提供。补充酶的足量加入可使大部分并优选实质上全部葡糖苷异黄酮转化成糖苷异黄酮。因此加入“补充酶”是十分必要的,其加入量应为干品蛋白浓缩物重量的0.5%至5%。
另一类可作为“补充酶”的是酯酶,这些酯酶适于这里所述的优选实施方法,它通过从异黄酮共轭体中除去乙酸酯基和丙二酸酯基团使乙酸酯和丙二酸酯的共轭体转变为葡糖苷配糖基异黄酮。大多数优选具体实施方案中,使用这两种酶,即β-葡糖苷酶和酯酶。
较好的具体方法是一步法并具有非常高的转化率(从葡糖苷异黄酮转化成糖苷配基异黄酮),且用时短并操作容易,经济易行。术语“一步”在此表示在反应过程中的参数保持不变,这些参数包括PH值和温度。
非常高的转化率是指蛋白浓缩物中至少大部分并优选实质上全部的葡糖苷异黄酮转化成糖苷配基异黄酮。术语“大部分”指转化率至少为50%,术语“实质上全部”指至少为80%,最好的指至少90%。
虽然不洗涤可能受到特殊理论的束缚,但它确实表明这里所述的令人惊奇且出人意料的高转化率来自一步反应过程中所用的参数组合。优选反应系统的PH值保持稳定且大约从4至8。最优选的PH值是在一步法中,与异黄酮共轭体反应前,酶最具活性时PH值。优选在一步法中反应系统的温度保持稳定,大约从40度到60度,最佳温度为60度。一般通过一步法将实质上所有葡糖苷异黄酮转成糖苷配基物所需的反应时间大约从2小时到24小时。
提供富含糖苷配基浓缩物的另一替代步骤是:将等电点洗涤和与β-葡糖苷酶的反应结合到单一步骤中,其中豆类起始物质悬浮于等电点洗涤液中,并将在该等电点具有最佳PH的一种或几种β-葡糖苷酶如乳糖酶下直接加入到浆液中。然后反应按上述反应条件进行,从而将至少大部分和优选实质上全部葡糖苷异黄酮转化为糖苷配基物。这一步骤代表了优选且简单的方法,并不必首先在等电点洗涤物质以去除可溶性碳水化合物,从而避免了通过洗涤使异黄酮损失的可能性。
蛋白浓缩物可利用常规的方法脱水、包括离心与干燥技术从而得到染料木苷原浓度为1.0至2.0毫克/克(干品),黄豆苷原为0.7至1.5毫克/克(干品)的浓缩物。
本发明还提供了以非常高比例,从植物蛋白材料如大豆材料回收蛋白浓缩物中黄酮的方法。基于植物蛋白起始物中各类异黄酮总量,通过这里所述方法得到的回收率至少为50%,较好为65%,最好为80%。虽然不希望受具体理论的束缚,但确信由这里所述反应得到的高回收率与所述各种加工手段有关。在具体阶段,通过将相对可溶的葡糖苷异黄酮转化为不溶的糖苷配基异黄酮,可从进料物质中将高百分比异黄酮回收在所得产物中。
下列实例将进一步论述,但其对于本发明具有非限制性。
实例:
取15克大豆粉加入150克水混合,调节PH为7。往该混合物中加入1.5g生物果胶酶100L。混合物在60℃培养2小时同时调节PH至4.5。加入1.0g生物果胶酶100L,再培养2小时。养完毕后,回收所得富含糖苷配基异黄酮蛋白/纤维浓缩物。蛋白/纤维浓缩物中的异黄酮回收率如表1所示:
表1
样品 | 染料木苷% | 6”-OMal-染料木苷% | 6”-OAc-染料木苷% | 染料木苷原% | 黄豆苷% | 6”-OMal1-黄豆苷% | 6”-OAc-黄豆苷% | 黄豆苷原% | 大豆异黄酮% | 6”-OMal-大豆异黄酮% | 大豆异黄酮原% |
-步转化率起始物质蛋白/纤维浓缩物 | 488 | 4927 | 00 | 366 | 477 | 4723 | 10 | 470 | 4350 | 4115 | 1635 |
这些数据表明在“残留”酶与“补充酯”的共同作用下得到的转化率。异黄酮共轭体发生了向转糖苷配基物的明显转化,特别是染料木苷原和黄豆苷原。各类异黄酮的含量是基于异黄酮类的所有形式的总量。
在另一系列实验中研究了来自大豆的蛋白浓缩物中的染料木苷原和黄豆苷原的回收百分比。通过测定分离物中染料木苷原(或黄豆苷原)的量得到回收百分比,其以所含大豆起始物中染料木苷原(或黄豆苷原)的所有形式的总量的百分比来表示。100g去脂豆粉加到1600克用盐酸调节PH至4.5的水中,所得浆状物,被加热到50℃,加入2%凝乳状,具有β-葡糖苷酶活性的乳糖酶F。该浆状物在50℃反应16小时,以保证葡糖苷异黄酮完全转化成糖苷配基异黄酮。蛋白浓缩物通过离心从水溶性溶剂中分离,并形成富含糖苷配基浓缩体,略去了洗涤步骤。分离体中染料木苷原的含量为起始大豆物料(脱脂豆粉)中染料木苷原和染料木苷所有形式的总量的82%。类似地,分离液中黄豆苷原回收率为64%。
定量分析豆类产物中异黄酮的方法如下:通过将0.75g样品(喷雾干燥或碾成细粉)与50ml 80/20甲醇/水溶剂混合提取异黄酮,在室温下用轨道振荡器振摇2小时,进行萃取。2小时后,余下未溶的物料用Whatman No.42滤纸过滤除去。5ml滤液用4ml水和1ml甲醇稀释。
通过高效液相色谱用Beckman C18反相柱对异黄酮类化合物进行分离。将异黄酮注射到该柱上,用溶剂,梯度洗脱,起始:甲醇88%,水10%,冰乙酸2%结束:甲醇98%,冰乙酸2%。流速0.4毫升/分钟,紫外吸收峰为262nm,清楚地拆分出:黄豆苷,6″-氧-乙酰黄豆苷,6″-氧-丙二酰黄豆苷,黄豆苷原,染料木苷,6″-氧-乙酰染料木苷,6″-氧-丙二酰染料木苷,染料木苷原,大豆异黄酮及其衍生物和大豆异黄酮原。峰的鉴定由质谱完成。
定量分析由标准品与样品对照完成。标准品(染料木苷,染料木苷原,黄豆苷,黄豆苷原)由InaofineChemical.Company,Sommerville,NJ.购买。计算每个上述化合物的响应因子(积分面积/浓度),并用于未知样品的定量,对于无标准品提供的共轭体型化合物,其响应因子是由其母体分子的响应因子并根据共轭体的分子量修正而得出的。如大豆异黄酮的响应因子是由染料木苷的响应因子与大豆异黄酮的分子量修正而得出。
此方法提供了每个异黄酮类物质的定量方法。为计算方便,如果所有的共轭形式转化为其对应的非共轭形式,一般依据上述数据和这些化合的聚集重量,分别计算得出染料木苷原,黄豆苷原,大豆异黄酮原的总含量,其总含量也可直接用酸水解转化成共轭形式的方法计算。
当然前述仅是本发明的具体优选方案且在不背离该发明所附权利要求书的精神和范围下可做各种变化与替代。该权利要求书遵循专利法的原则包括相应的条例逐一论述。
Claims (23)
1.从植物蛋白物质生产富含糖苷配基异黄酮蛋白浓缩物的方法,其包括:
(a)用具有植物蛋白物质等电位总的PH值的水性溶剂洗涤含有葡糖苷异黄酮的植物蛋白物质,产生含有葡糖苷异黄酮的植物蛋白浓缩物;和
(b)葡糖苷异黄酮与足量的酶在足够的时间,温度和PH下反应,该酶至少是一种β-葡糖苷酶和酯酶,从而将浓缩物中的至少大部分葡糖苷异黄酮转化成糖苷配基异黄酮,从而生成富含糖苷配基异黄酮的蛋白浓缩物。
2.从权利要求1的方法,其包括:
(a)用具有植物蛋白物质等电点的PH值的水性溶剂洗涤含有葡糖苷异黄酮类物质和足量残留酶的植物蛋白物质,残留酶为至少一种β-葡糖苷酶或酯酶,从而生成含葡糖苷配糖基异黄酮的植物蛋白浓缩物;和
(b)葡糖苷异黄酮与残留酶在足够的时间,温度和PH下反应,将浓缩物至少大部分葡糖苷异黄酮转化成糖苷配基异黄酮,从而制备出富含糖苷配基异黄酮蛋白浓缩物。
3.从植物蛋白物质制备富含糖苷配基异黄酮蛋白浓缩物的方法,其包括:
(a)用具有植物蛋白物质等电位点PH值的水性溶剂洗涤含有葡糖苷异黄酮的植物蛋白物质,生成含有葡糖苷异黄酮的植物蛋白浓缩物;
(b)加入“补充酶”至浓缩物,该酶为至少一种β-葡糖苷酶和酯酶,使浓缩物中酶的总含量充足,以便浓缩物中至少大部分葡糖苷异黄酮被转化为糖苷配基物;和
(c)葡糖苷异黄酮与酶在足够时间,温度和PH下反应,使浓缩物中的至少大部分葡糖苷异黄酮转化为糖苷配基异黄酮,从而制备出富含糖配基异黄酮浓缩物。
4.权利要求1,2或3的方法,其中所述的时间范围为大约2小时至24小时。
5.权利要求4的方法,其中所述的时间范围大约24小时。
6.权利要求1,2或3的方法,其中所述的温度为大约40℃至60℃。
7.权利要求6的方法,其中所述的温度为60℃。
8.权利要求1,2或3的方法,其中所述的PH值大约从4至8。
9.权利要求8的方法,其中所述的PH值大约是4.5。
10.权利要求1,2或3的方法,其中所述的时间范围大约为24小时,温度为大约60℃,PH值大约为4.5。
11.权利要求1,2或3的方法,其中所述的洗涤植物蛋白物质和葡糖苷异黄酮与β-葡糖苷酶的反应步骤是一次操作完成的。
12.权利要求1,2或3的方法,其中所述的糖苷配基异黄酮蛋白浓缩物是由大豆制备的。
13.权利要求1,2或3的方法,其中所述的植物蛋白物质包括大豆类物质。
14.权利要求1,2或3的方法,其中实质上上所有葡糖苷异黄酮类物质转化为糖苷配基异黄酮。
15.权利要求1的方法,其中所述的PH值是使酶或残余酶或补充酶先与异黄酮类物质反应前具有最强活性的PH值。
16.由权利要求1,2或3方法制备富含糖苷配基异黄酮蛋白浓缩物。
17.富含糖苷配基异黄酮强化浓物中染料木苷原的干品含量是1.0至2.0毫克/克,黄豆苷原的含量是0.7至1.5毫克/克。
18.回收至少植物蛋白材料中50%异黄酮的蛋白浓缩物方法,其包括:
(a)用具有植物蛋白物质等电位点PH值的水性溶剂洗涤含有异黄酮类物质的植物蛋白物质,并制备出含有异黄酮类物质的植物蛋白浓缩物,
(b)在足够的时间,温度和PH下,异黄酮与足量的酶充分反应,使浓缩物中至少大部分异黄酮类物质转化为水解性较弱的异黄酮类物质,从而制备出富含异黄酮蛋白浓缩物,其中异黄酮的含量应至少为植物蛋白物质中异黄酮含量的50%。
19.权利要求18的方法,其中所述浓缩物中异黄酮的含量应至少为植物蛋白物质中异黄酮含量的65%。
20.权利要求18的方法,其中所述浓缩物中异黄酮的含量应至少为植物蛋白物质中异黄酮含量的80%。
21.权利要求18所述植物蛋白物质包括大豆类作物。
22.权利要求18的方法,其中所述的酶选自β-葡糖苷酶和酯酶类。
23.浓缩物由权利要求18,19或20的方法制备。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13519493A | 1993-10-12 | 1993-10-12 | |
US08/135,194 | 1993-10-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1135222A CN1135222A (zh) | 1996-11-06 |
CN1055931C true CN1055931C (zh) | 2000-08-30 |
Family
ID=22466963
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94194200A Expired - Fee Related CN1055931C (zh) | 1993-10-12 | 1994-09-21 | 富含糖苷配基异黄酮植物蛋白浓缩物及其制备方法 |
Country Status (12)
Country | Link |
---|---|
US (1) | US5637562A (zh) |
EP (1) | EP0794960B2 (zh) |
JP (1) | JP3777389B2 (zh) |
KR (1) | KR100302695B1 (zh) |
CN (1) | CN1055931C (zh) |
AU (1) | AU696553B2 (zh) |
BR (1) | BR9407820A (zh) |
CA (1) | CA2174120A1 (zh) |
DE (1) | DE69429673T3 (zh) |
RU (1) | RU2151775C1 (zh) |
TW (1) | TW491851B (zh) |
WO (1) | WO1995010529A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112410321A (zh) * | 2020-11-26 | 2021-02-26 | 昆明理工大学 | 一种β-葡萄糖苷酶Ttbgl3及其应用 |
Families Citing this family (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU696574B2 (en) * | 1993-10-12 | 1998-09-10 | Archer-Daniels-Midland Company | An aglucone isoflavone enriched vegetable protein extract and isolate and process for producing |
CN1065864C (zh) * | 1993-10-12 | 2001-05-16 | 蛋白质技术国际公司 | 富含糖苷配基异黄酮植物蛋白乳清, 乳清蛋白及其制备方法 |
US5827682A (en) * | 1995-06-07 | 1998-10-27 | Protein Technologies International, Inc. | Two-step conversion of vegetable protein isoflavone conjugates to aglucones |
US6261565B1 (en) | 1996-03-13 | 2001-07-17 | Archer Daniels Midland Company | Method of preparing and using isoflavones |
US5702752A (en) * | 1996-03-13 | 1997-12-30 | Archer Daniels Midland Company | Production of isoflavone enriched fractions from soy protein extracts |
US5851792A (en) * | 1996-04-03 | 1998-12-22 | Shen; Jerome | Aglucone isoflavone enriched vegetable protein whey whey protein material aglucone isoflavone material high genistein content material and high daidzein content material and process for producing the same from a vegetable protein whey |
US6015785A (en) * | 1996-04-12 | 2000-01-18 | Protein Technologies International, Inc. | Aglucone isofavone enriched vegetable protein extract and isolate and process for producing |
US5821361A (en) * | 1996-06-11 | 1998-10-13 | Protein Technologies International, Inc. | Recovery of isoflavones from soy molasses |
US6579561B2 (en) | 1996-08-09 | 2003-06-17 | Protein Technologies International, Inc. | Aglucone isoflavone enriched vegetable flour and vegetable grit and process for making the same from a vegetable material containing isoflavone |
US6521282B1 (en) | 1996-08-09 | 2003-02-18 | Protein Technologies International, Inc. | Aglucone isoflavone enriched vegetable flour and grit |
US5726034A (en) * | 1996-09-06 | 1998-03-10 | Protein Technologies International, Inc. | Aglucone isoflavone enriched vegetable protein extract and protein material, and high genistein and daidzein content materials and process for producing the same |
AUPO644897A0 (en) * | 1997-04-28 | 1997-05-22 | Novogen Inc | Preparation of isoflavones from legumes |
US5855892A (en) * | 1997-09-19 | 1999-01-05 | Potter; Susan M. | Method for decreasing LDL-cholesterol concentration and increasing HDL-cholesterol concentration in the blood to reduce the risk of atherosclerosis and vascular disease |
US5952374A (en) * | 1997-09-29 | 1999-09-14 | Protein Technologies International, Inc. | Method for inhibiting the development of Alzheimer's disease and related dementias- and for preserving cognitive function |
US6320028B1 (en) | 1997-10-15 | 2001-11-20 | Central Soya Company, Inc. | Soy isoflavone concentrate process and product |
US6369200B2 (en) | 1997-10-15 | 2002-04-09 | Central Soya Company, Inc. | Soy isoflavone concentrate process and product |
US6228993B1 (en) | 1998-10-12 | 2001-05-08 | Central Soya Company, Inc. | Soy isoflavone concentrate process and product |
KR100413025B1 (ko) * | 1997-10-20 | 2004-04-29 | 솔레 엘엘씨 | 아글루콘이소플라본강화식물성단백질유장,유장단백질재료,아글루콘이소플라본재료,제니스테인함량이높은재료및디아드제인함량이높은재료및식물성단백질유장으로부터이들을제조하는방법 |
US5932221A (en) * | 1997-10-30 | 1999-08-03 | Day; Charles E. | Genistin-enriched fraction from soy meal |
US6132795A (en) * | 1998-03-15 | 2000-10-17 | Protein Technologies International, Inc. | Vegetable protein composition containing an isoflavone depleted vegetable protein material with an isoflavone containing material |
US5994508A (en) * | 1998-04-13 | 1999-11-30 | Protein Technologies International, Inc. | Isoflavone rich protein isolate and process for producing |
AU765679B2 (en) * | 1999-11-19 | 2003-09-25 | Archer-Daniels-Midland Company | Isoflavone rich protein isolate and process for producing |
US6083553A (en) * | 1998-06-05 | 2000-07-04 | Protein Technologies International, Inc. | Recovery of isoflavones from soy molasses |
US6013771A (en) * | 1998-06-09 | 2000-01-11 | Protein Technologies International, Inc. | Isoflavone rich protein isolate and process for producing |
US6150399A (en) * | 1998-06-30 | 2000-11-21 | Abbott Laboratories | Soy-based nutritional products |
EP1133307B1 (en) | 1998-11-25 | 2003-06-11 | Nutri Pharma ASA | Use of a composition comprising soy protein, dietary fibres and a phytoestrogen compound in the prevention and/or treatment of pulmonary diseases |
JP2002530347A (ja) | 1998-11-25 | 2002-09-17 | ニュートリ・ファーマ・アルメント・アクシェセルスカブ | 大豆蛋白質、食物繊維およびフィトエストロゲン化合物を含む組成物、および心臓血管疾患の予防および/または治療におけるその使用 |
WO2000032204A1 (en) | 1998-12-02 | 2000-06-08 | Cognis Corporation | Production of a product enriched in isoflavone values from natural sources |
US6544566B1 (en) | 1999-04-23 | 2003-04-08 | Protein Technologies International, Inc. | Composition containing plant sterol, soy protein and isoflavone for reducing LDL cholesterol |
US7285297B1 (en) | 1999-04-23 | 2007-10-23 | Archer-Daniels-Midland Company | Method of reducing low density liproprotein cholesterol concentration |
AUPQ504300A0 (en) | 2000-01-11 | 2000-02-03 | Biorex Health Limited | Extraction of flavonoids |
US6811804B2 (en) * | 2001-06-07 | 2004-11-02 | Abbott Laboratories | Juice and soy protein beverage and uses thereof |
AU2002344683B2 (en) * | 2001-06-29 | 2007-08-23 | Maabarot Project Launching And Management Ltd | "Flavonoid concentrates" |
AUPR602201A0 (en) * | 2001-06-29 | 2001-07-26 | Biorex Health Limited | Flavonoid concentrates |
US20040071685A1 (en) * | 2002-10-09 | 2004-04-15 | Devin Houston | Compositions and methods for increasing the bioavailability of plant polyphenols |
WO2005107780A2 (en) * | 2004-05-10 | 2005-11-17 | Instituto Tecnológico Y De Estudios Superiores De Monterrey (Itesm) | Cancer cell growth inhibition by black bean (phaseolus vulgarisl) extracts |
US20090176871A1 (en) * | 2008-01-07 | 2009-07-09 | Schoenwetter Phillip E | Treatments for Domestic Animals Having Sex Hormone Deficiencies Using Soy Germ Isoflavones |
US20100203203A1 (en) * | 2009-02-11 | 2010-08-12 | Segall Kevin I | Preparation of Soy Protein Product Using Water Extraction ("S803") |
US8426189B2 (en) | 2009-04-29 | 2013-04-23 | Fermalogic, Inc. | Soybean-based fermentation media, methods of making and use |
EP4331384A1 (en) * | 2022-08-30 | 2024-03-06 | Takasago International Corporation | Soy-based food, preparation process and use |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01258669A (ja) * | 1988-04-06 | 1989-10-16 | Kikkoman Corp | イソフラボン化合物の製造法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3870805A (en) * | 1970-11-04 | 1975-03-11 | Staley Mfg Co A E | Process for preparing texturized protein compositions and the resulting product |
GB1446965A (en) * | 1974-02-14 | 1976-08-18 | Agricultural Vegetable Prod | Preparation of food products |
JPS5129280A (en) * | 1974-08-12 | 1976-03-12 | Kikkoman Shoyu Co Ltd | Daizuno kakoshorihoho |
US4889921A (en) * | 1987-04-29 | 1989-12-26 | The University Of Toronto Innovations Foundation | Production of rapeseed protein materials |
US5320949A (en) * | 1993-10-12 | 1994-06-14 | Protein Technologies International, Inc. | Process for producing aglucone isoflavone enriched vegetable protein fiber |
AU696574B2 (en) * | 1993-10-12 | 1998-09-10 | Archer-Daniels-Midland Company | An aglucone isoflavone enriched vegetable protein extract and isolate and process for producing |
-
1994
- 1994-09-21 BR BR9407820A patent/BR9407820A/pt not_active Application Discontinuation
- 1994-09-21 KR KR1019960701886A patent/KR100302695B1/ko not_active IP Right Cessation
- 1994-09-21 DE DE69429673T patent/DE69429673T3/de not_active Expired - Fee Related
- 1994-09-21 WO PCT/US1994/010696 patent/WO1995010529A1/en active IP Right Grant
- 1994-09-21 JP JP51181995A patent/JP3777389B2/ja not_active Expired - Fee Related
- 1994-09-21 EP EP94929287A patent/EP0794960B2/en not_active Expired - Lifetime
- 1994-09-21 RU RU96109381/04A patent/RU2151775C1/ru not_active IP Right Cessation
- 1994-09-21 AU AU78399/94A patent/AU696553B2/en not_active Ceased
- 1994-09-21 CN CN94194200A patent/CN1055931C/zh not_active Expired - Fee Related
- 1994-09-21 CA CA002174120A patent/CA2174120A1/en not_active Abandoned
- 1994-09-21 US US08/307,751 patent/US5637562A/en not_active Expired - Lifetime
- 1994-11-23 TW TW083110889A patent/TW491851B/zh not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01258669A (ja) * | 1988-04-06 | 1989-10-16 | Kikkoman Corp | イソフラボン化合物の製造法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112410321A (zh) * | 2020-11-26 | 2021-02-26 | 昆明理工大学 | 一种β-葡萄糖苷酶Ttbgl3及其应用 |
CN112410321B (zh) * | 2020-11-26 | 2022-01-28 | 昆明理工大学 | 一种β-葡萄糖苷酶Ttbgl3及其应用 |
Also Published As
Publication number | Publication date |
---|---|
JP3777389B2 (ja) | 2006-05-24 |
EP0794960B2 (en) | 2006-03-15 |
TW491851B (en) | 2002-06-21 |
WO1995010529A1 (en) | 1995-04-20 |
AU7839994A (en) | 1995-05-04 |
BR9407820A (pt) | 1997-05-06 |
RU2151775C1 (ru) | 2000-06-27 |
CN1135222A (zh) | 1996-11-06 |
EP0794960A4 (en) | 1998-11-25 |
AU696553B2 (en) | 1998-09-10 |
JPH09506076A (ja) | 1997-06-17 |
KR100302695B1 (ko) | 2001-11-30 |
CA2174120A1 (en) | 1995-04-20 |
DE69429673D1 (de) | 2002-02-21 |
US5637562A (en) | 1997-06-10 |
DE69429673T3 (de) | 2007-08-23 |
EP0794960A1 (en) | 1997-09-17 |
EP0794960B1 (en) | 2002-01-16 |
DE69429673T2 (de) | 2002-09-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1055931C (zh) | 富含糖苷配基异黄酮植物蛋白浓缩物及其制备方法 | |
CN1055932C (zh) | 葡糖苷配基异黄酮富集的植物蛋白提取物和分离物及生产方法 | |
CN1065864C (zh) | 富含糖苷配基异黄酮植物蛋白乳清, 乳清蛋白及其制备方法 | |
EP0827698B1 (en) | Aglucone isoflavone enriched vegetable protein extract and protein material, and high genistein and daidzein content materials and process for producing the same | |
US6015785A (en) | Aglucone isofavone enriched vegetable protein extract and isolate and process for producing | |
KR100391231B1 (ko) | 아글루콘이소플라본이농후한식물성단백질추출물과분리물,및이들의제조방법 | |
CN1214871A (zh) | 富含配基异黄酮的植物蛋白乳清及其生产方法 | |
MXPA98003598A (en) | An extract and isolated vegetable protein enriched with aglucone isoflavone, and procedure to produce |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
ASS | Succession or assignment of patent right |
Owner name: ARCHER DANIELS MIDLAND CO Free format text: FORMER OWNER: PROTEIN TECHNOLOGIES INTERNATIONAL, INC. Effective date: 20070302 |
|
C41 | Transfer of patent application or patent right or utility model | ||
TR01 | Transfer of patent right |
Effective date of registration: 20070302 Address after: Illinois Instrunment Patentee after: Ache-Denils-Mildlan Corp. Address before: American Missouri Patentee before: Protein Technologies International |
|
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |