CN111850062A - 一种超高静压结合转化液辅助水解芥子中硫代葡萄糖苷为异硫氰酸酯的方法 - Google Patents
一种超高静压结合转化液辅助水解芥子中硫代葡萄糖苷为异硫氰酸酯的方法 Download PDFInfo
- Publication number
- CN111850062A CN111850062A CN202010637958.7A CN202010637958A CN111850062A CN 111850062 A CN111850062 A CN 111850062A CN 202010637958 A CN202010637958 A CN 202010637958A CN 111850062 A CN111850062 A CN 111850062A
- Authority
- CN
- China
- Prior art keywords
- mustard
- isothiocyanate
- static pressure
- isothiocyanates
- hydrolyzing
- 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.)
- Pending
Links
- 150000002540 isothiocyanates Chemical class 0.000 title claims abstract description 51
- 241000219198 Brassica Species 0.000 title claims abstract description 44
- 235000003351 Brassica cretica Nutrition 0.000 title claims abstract description 43
- 235000003343 Brassica rupestris Nutrition 0.000 title claims abstract description 43
- 235000010460 mustard Nutrition 0.000 title claims abstract description 43
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 23
- 125000004383 glucosinolate group Chemical group 0.000 title claims abstract description 23
- 230000003068 static effect Effects 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 title claims abstract description 10
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000011282 treatment Methods 0.000 claims abstract description 7
- 239000000084 colloidal system Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 235000019508 mustard seed Nutrition 0.000 claims description 8
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 8
- 239000008158 vegetable oil Substances 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 235000019198 oils Nutrition 0.000 claims description 5
- 244000140786 Brassica hirta Species 0.000 claims description 4
- 235000011371 Brassica hirta Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 235000006463 Brassica alba Nutrition 0.000 claims description 3
- 244000180419 Brassica nigra Species 0.000 claims description 3
- 235000011291 Brassica nigra Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001412 brassica hirta moench. Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 5
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical class S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 235000016720 allyl isothiocyanate Nutrition 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- -1 Isothiocyanate compounds Chemical class 0.000 description 10
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 108090000790 Enzymes Proteins 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 238000004885 tandem mass spectrometry Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000005687 corn oil Nutrition 0.000 description 5
- 239000002285 corn oil Substances 0.000 description 5
- 108010058651 thioglucosidase Proteins 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- HUJXHFRXWWGYQH-UHFFFAOYSA-O sinapine Chemical compound COC1=CC(\C=C\C(=O)OCC[N+](C)(C)C)=CC(OC)=C1O HUJXHFRXWWGYQH-UHFFFAOYSA-O 0.000 description 4
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007857 degradation product Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000009461 vacuum packaging Methods 0.000 description 3
- PHZOWSSBXJXFOR-UHFFFAOYSA-N 2-Propenyl glucosinolate Natural products OCC1OC(SC(CC=C)=NOS(O)(=O)=O)C(O)C(O)C1O PHZOWSSBXJXFOR-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 238000010268 HPLC based assay Methods 0.000 description 2
- 229920002774 Maltodextrin Polymers 0.000 description 2
- 239000005913 Maltodextrin Substances 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- WWBNBPSEKLOHJU-CEOIDQJPSA-N Sinalbin Natural products S(=O)(=O)(O/N=C(\S[C@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1)/Cc1ccc(O)cc1)O WWBNBPSEKLOHJU-CEOIDQJPSA-N 0.000 description 2
- PHZOWSSBXJXFOR-MYMDCHNCSA-N Sinigrin Natural products S(=O)(=O)(O/N=C(\S[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@H](CO)O1)/CC=C)O PHZOWSSBXJXFOR-MYMDCHNCSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000002706 hydrostatic effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229940035034 maltodextrin Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 229940117953 phenylisothiocyanate Drugs 0.000 description 2
- QKFAFSGJTMHRRY-OCFLFPRFSA-M potassium;[(e)-1-[(2s,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]sulfanylbut-3-enylideneamino] sulfate Chemical compound [K+].OC[C@H]1O[C@@H](S\C(CC=C)=N\OS([O-])(=O)=O)[C@H](O)[C@@H](O)[C@@H]1O QKFAFSGJTMHRRY-OCFLFPRFSA-M 0.000 description 2
- 235000019633 pungent taste Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WWBNBPSEKLOHJU-RFEZBLSLSA-N sinalbin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1S\C(=N/OS(O)(=O)=O)CC1=CC=C(O)C=C1 WWBNBPSEKLOHJU-RFEZBLSLSA-N 0.000 description 2
- 235000017291 sinigrin Nutrition 0.000 description 2
- 235000019654 spicy taste Nutrition 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- JUSMHIGDXPKSID-DVKNGEFBSA-N 1-thio-beta-D-glucopyranose Chemical compound OC[C@H]1O[C@@H](S)[C@H](O)[C@@H](O)[C@@H]1O JUSMHIGDXPKSID-DVKNGEFBSA-N 0.000 description 1
- 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 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 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 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 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 1
- 241000238631 Hexapoda Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 206010034203 Pectus Carinatum Diseases 0.000 description 1
- 125000003275 alpha amino acid group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000507 anthelmentic effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- PFOARMALXZGCHY-UHFFFAOYSA-N homoegonol Natural products C1=C(OC)C(OC)=CC=C1C1=CC2=CC(CCCO)=CC(OC)=C2O1 PFOARMALXZGCHY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 208000015122 neurodegenerative disease Diseases 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000009931 pascalization Methods 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- 230000004614 tumor growth Effects 0.000 description 1
Images
Classifications
-
- 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
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/002—Nitriles (-CN)
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/007—Other edible oils or fats, e.g. shortenings, cooking oils characterised by ingredients other than fatty acid triglycerides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/02—Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
- A23D9/04—Working-up
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Polymers & Plastics (AREA)
- Food Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biotechnology (AREA)
- Seasonings (AREA)
Abstract
本发明公开了一种超高静压结合转化液辅助水解芥子中硫代葡萄糖苷为异硫氰酸酯的方法,包括以下步骤:将芥子或芥子粉与转化液按照1:1~1:5的固液比例混合,胶体磨充分磨成浆,然后在压力为200~600MPa下保压处理5~30min后泄压取出即得异硫氰酸酯。胶体磨成浆的平均粒径应该在50‑315μm范围内。异硫氰酸酯主要指烯丙基异硫氰酸酯和苯基异硫氰酸酯。本发明通过超高静压技术结合转化液辅助水解硫代葡萄糖苷为异硫氰酸酯,水解效率高,30分钟内可以可全部水解,而传统工业上则需要2~3天的时间;本发明生产的异硫氰酸酯产率高,稳定性高。本发明的工艺简单、效果显著、且是一种绿色物理加工技术,加工过程无加热、无添加任何添加剂。
Description
技术领域
本发明涉及异硫氰酸酯产品技术领域,具体地说,涉及一种水解芥子中硫代葡萄糖苷为异硫氰酸酯的方法。
背景技术
异硫氰酸酯类的化合物具有很多生物活性,其中最重要的包括通过调节Phase I和Phase II代谢酶的活性,抑制肿瘤的发生、通过凋亡抑制肿瘤生长、预防某些退化性疾病。另外异硫氰酸酯具有广谱抗菌性能和驱虫的作用,已作为天然抗菌剂,应用于各类食品中,包括牛肉、鸡胸肉、香肠、面包和花生,以延长食品货架期。还有报道异硫氰酸酯在杂草、昆虫和真菌防治方面具有替代合成农药的潜力。因此,从芥子中高效地制备高含量的异硫氰酸酯并发挥其在工业上的应用是非常重要的。
异硫氰酸酯是芥子中硫代葡萄糖苷的水解产物。芥子是芸苔属植物,包括白芥子、黄芥子和黑芥子等,有独特的刺激性和辛香辣味,被广泛种植用于天然调味料。事实上,完整的、干燥的芥子并无辣味,只有在其破碎水解后才有辣味产生。这是由于芥子中存在着硫代葡萄糖苷(黑芥子苷,sinigrin;和白芥子甘,sinalbin)。硫代葡萄糖苷类化合物的核心结构,由一个β-D-硫代葡萄糖连接一个磺酸盐醛肟基团和一个来源于氨基酸侧链组成,它被内源性芥子酶水解产生异硫氰酸酯类化合物才产生的辛辣味。芥子酶 (EC 3.2.1.147)与硫代葡萄糖苷共存,但在芥子细胞的胞质中分离。植物完整的组织受损时,硫代葡萄糖苷和芥子酶结合反应生成葡萄糖和一个不稳定的糖苷配基中间体,然后自发地转化为以异硫氰酸酯为最主要成分的混合降解产物。其中黑芥子苷(sinigrin)的主要降解产物为烯丙基异硫氰酸酯,而白芥子苷(sinalbin)的主要降解产物为苯基异硫氰酸酯。芥子苷转化为异硫氰酸酯的效率受多种因素的影响包括芥子酶辅酶因子、pH值、温度、络合剂、颗粒大小和其他因素。在传统的工业生产上,芥子苷完全转化为异硫氰酸酯大多需要2~3天的时间,生产效率非常低。
超高静压技术是一种新型非热加工技术,是指将原料放入密封的、高强度的压力容器中,以水或矿物油作为传压介质,施加压力100-1000MPa,在常温或较低温下维持一段时间后,达到杀菌、钝酶和改善食品品质的一种加工方法。超高静压具有节能、省时、不破坏食品活性成分等优点。一方面在超高静压作用下,提取液渗入固体原料内部,使有效成分溶解,在有效成分达到溶解平衡后迅速卸压,在细胞内外渗透压的作用下,有效成分迅速扩散到组织周围的提取液中。另一方面,在超高压的作用下,胞内酶被释放出来并在超高静压作用下被激活(超高静压通过改变酶的三四级构象而提高酶的活性),与底物的相互作用加强,这种利用超高静压破坏隔离,使酶和基质相互接触的作用称为“凝聚作用”。超高压能够对非共价键产生影响,而共价键无影响,会使生物大分子成分变性,而不破坏药物中的小分子有效成分的生理活性,可以达到提取和灭菌的目的。基于上述超高静压的特点,将超高静压作用于芥子,通过调整转化液的组成,可以将芥子中的内源芥子酶激活,从而达到高效地将硫代葡萄糖苷转化为高活性的异硫氰酸酯类化合物的目的。
发明内容
针对现有技术转化芥子中硫代葡萄糖苷为异硫氰酸酯效率极低的问题(通常需要2~3天的时间),本发明的目的在于提供一项高效、绿色的超高静压结合转化液制备富含异硫氰酸酯的芥子提取物的技术,所制备的提取物进一步采用植物油萃取,得到富含异硫氰酸酯的芥子植物油。
本发明的目的通过下述技术方案实现:
一种超高静压结合转化液辅助水解芥子中硫代葡萄糖苷为异硫氰酸酯的方法,包括以下步骤:
将芥子或芥子粉与转化液混合,胶体磨充分磨成浆,然后在超高静压为200~600MPa下保压处理5~30min后泄压取出。
作为优选的,在上述的制备方法中,步骤(1)所述的芥子或芥子粉为白芥子、黑芥子、黄芥子或灰芥子。
作为优选的,在上述的制备方法中,所述芥子或芥子粉与转化液按照1:1~1:5的固液比例混合。
作为优选的,在上述的制备方法中,步骤(2)所述转化液含有抗坏血酸4.5-18mM和EDTA 15-30mM,温度为30-70℃,pH=6-9。
一种富含异硫氰酸酯的芥子植物油的制备方法,包括如下步骤:
将上述所得异硫氰酸酯与植物油按照1:5的重量比充分搅拌15分钟后,将固体与水溶液/油脂进行过滤分离,回收油脂,得到富含异硫氰酸酯的芥子植物油。与现有的技术相比,本发明具有如下有益效果:
1、本发明通过超高静压技术结合转化液辅助水解硫代葡萄糖苷为异硫氰酸酯,水解效率高,30分钟内可以可全部水解,而传统工业上则需要2~3天的时间;
2、本发明生产的异硫氰酸酯产率高(产率提高45~53%),稳定性高。
3、本发明的工艺简单、效果显著、且是一种绿色物理加工技术,加工过程无加热、无添加任何添加剂。
附图说明
图1为实施例1芥子中的白芥子苷物质的液相色谱图;其中,a为标准品,b为样品;
图2为实施例1芥子中的异硫氰酸酯的液相色谱图,其中,a为标准品,b为样品。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
以下实施例中,相关指标测定方法附后。
测定方法:
(1)采用HPLC法测定芥子苷的含量:
称取0.1 g样品,用6 mL 80% (v/v)甲醇煮沸10 min,冷却离心,回收上清液,再次提取,将上清液加入80%甲醇至25mL,提取通过0.22 μm聚四氟乙烯过滤器进高效液相色谱瓶。采用Waters HPLC测定提取物,进行定量。定性则采用UHPLC/MS/MS法。
HPLC条件:Waters HPLC高效液相色谱;色谱柱:XTerra C18;柱温:40℃;二元梯度:(A) 0.1% TFA水溶液,(B) 0.1% TFA乙腈溶液;流速:1mL /min;初始条件为5%B 3min然后线性增加到10%B 4min,40%B 12min,95%B 13min,然后在5%B平衡3min。
UHPLC/MS/MS条件:Agilent 1290UHPLC/6460 MS/MS;扫描质谱:100-800 m/z;时间:200 s;碰撞电压:135 V;碰撞能量:15 eV;电池加速器电压:3V。
(2)采用HPLC法测定苯基异硫氰酸酯的含量
0.25g芥子与5mL水和10mL二氯甲烷(DCM)混合,离心5分钟,除去水层,再次提取,用DCM将溶液定容至25ml。以3:1体积加入共轭试剂(DCM中20mM三乙胺和200mM 2-巯基乙醇),于30℃水浴保温60min,氮吹干燥,将提取物混于水:乙腈(v/v)为1:1的溶液,离心,通过0.45μm尼龙过滤器进高效液相色谱瓶。采用Waters HPLC测定提取物,进行定量。定性则采用UHPLC/MS/MS法。
HPLC条件:Waters HPLC高效液相色谱;色谱柱:XTerra C18;柱温:40℃;二元梯度:(A) 0.1%甲酸水溶液,(B) 0.1%甲酸乙腈溶液;流速:1ml /min;初始条件为5% B,15分钟后增加到50% B,波长设置为270 nm。
UHPLC/MS/MS条件:Agilent 1290UHPLC/6460 MS/MS;扫描质谱:100-800 m/z;时间:200 s;碰撞电压:135 V;碰撞能量:15 eV;电池加速器电压:3V。
实施例1
白芥子中的硫代葡萄糖苷转化为异硫氰酸酯包括如下步骤:
(1)将样品称重50g;
(2)按照1:5(g/ml)的比例与转化液混合(pH=7,含抗坏血酸18mM,EDTA15mM,温度为50℃);
(3)胶体磨中磨浆,达到平均粒径62μm;
(4)装入PET真空包装袋;
(5)进行超高静压处理,600MPa压力下保留20min后泄压取出。30分钟内全部水解,硫代葡萄糖苷转化为异硫氰酸酯。
对比例1
白芥子中的硫代葡萄糖苷转化为异硫氰酸酯包括如下步骤:
(1)将样品称重50g;
(2)按照1:5(g/ml)的比例与转化液混合(pH=7,含抗坏血酸18mM,EDTA15mM,温度为50℃);
(3)胶体磨中磨浆,达到平均粒径62μm;
(4)装入PET真空包装袋;
(5)置于50℃的水浴锅中保温48个小时。
对实施例1和对比例1进行检测异硫氰酸酯和硫代葡萄糖苷:实施例1经过超高静压处理的样品中总异硫氰酸酯的含量达到20.4毫克/克芥子,而未经过高压处理的对比例1样品中异硫氰酸酯的含量为13.4毫克/克芥子,两种处理后白芥子苷的浓度已经检测不到。超高压处理显著提高了异硫氰酸酯的含量。可见长时间水浴保温,可以全部将芥子苷转化为异硫氰酸酯,但是转化后的异硫氰酸酯可能挥发或者氧化成其他物质,造成了损失。通过结果分析,传统方法获取的异硫氰酸酯只有本发明超高压的66%。
富含异硫氰酸酯的芥子玉米油的制备:将实施例1所得的芥子与玉米油按照1:5的比例充分搅拌15分钟后,将固体、水溶液、油脂进行过滤分离,回收油脂,得到富含异硫氰酸酯的芥子玉米油。将含有异硫氰酸酯的油脂按照1:8的比例与麦芽糊精和变性淀粉(麦芽糊精与变性淀粉的质量比为1:2)混合,高压均质后(压力为5000 psi),进行喷雾干燥,得到含有异硫氰酸酯的微胶囊粉末。异硫氰酸酯类的化合物是脂溶性的,具有强刺激性气味和强挥发性,在空气中易氧化变质,导致其失去活性。而微胶囊技术对其进行包埋可以显著提高异硫氰酸酯的稳定性,降低其挥发性,并且可以在应用中进行控释和缓释,更好的发挥异硫氰酸酯在食品工业上作为天然抑菌剂的应用。
实施例2
白芥子中的硫代葡萄糖苷转化为异硫氰酸酯包括如下步骤:
(1)将样品称重50g;
(2)按照1:1(g/ml)的比例与转化液混合(pH=9,含抗坏血酸4.5mM,EDTA30 mM,温度为40℃);
(3)胶体磨中磨浆,达到平均粒径315μm;
(4)装入PET真空包装袋;
(5)进行超高静压处理,450MPa压力下保留15min后泄压取出;30分钟内全部水解,硫代葡萄糖苷转化为异硫氰酸酯;
(6)检测异硫氰酸酯和硫代葡萄糖苷:经过超高静压处理的样品中总异硫氰酸酯的含量达到19.6毫克/克芥子。
(7)将处理的芥子与玉米油按照1:5的比例充分搅拌15分钟后,将固体、水溶液、油脂进行过滤分离,回收油脂,得到富含异硫氰酸酯的芥子玉米油,可以作为调味料应用于食品中。
Claims (5)
1.一种超高静压结合转化液辅助水解芥子中硫代葡萄糖苷为异硫氰酸酯的方法,其特征在于包括以下步骤:
将芥子或芥子粉与转化液混合,胶体磨充分磨成浆,然后在超高静压为200~600MPa下保压处理5~30min后泄压取出。
2.如权利要求1所述的制备方法,其特征在于:步骤(1)所述的芥子或芥子粉为白芥子、黑芥子、黄芥子或灰芥子。
3.如权利要求1所述的制备方法,其特征在于:所述芥子或芥子粉与转化液按照1:1~1:5的固液比例混合。
4.如权利要求1所述的制备方法,其特征在于:步骤(2)所述转化液含有抗坏血酸4.5-18mM和EDTA 15-30mM,温度为30-70℃,pH=6-9。
5.一种富含异硫氰酸酯的芥子植物油的制备方法,其特征在于包括如下步骤:
将权利要求1所得产物与植物油按照1:5的重量比充分搅拌15分钟后,将固体与水溶液/油脂进行过滤分离,回收油脂,得到富含异硫氰酸酯的芥子植物油。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010637958.7A CN111850062A (zh) | 2020-07-06 | 2020-07-06 | 一种超高静压结合转化液辅助水解芥子中硫代葡萄糖苷为异硫氰酸酯的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010637958.7A CN111850062A (zh) | 2020-07-06 | 2020-07-06 | 一种超高静压结合转化液辅助水解芥子中硫代葡萄糖苷为异硫氰酸酯的方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111850062A true CN111850062A (zh) | 2020-10-30 |
Family
ID=73151894
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010637958.7A Pending CN111850062A (zh) | 2020-07-06 | 2020-07-06 | 一种超高静压结合转化液辅助水解芥子中硫代葡萄糖苷为异硫氰酸酯的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111850062A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115769885A (zh) * | 2022-11-22 | 2023-03-10 | 珠海天禾食品有限公司 | 一种异硫氰酸烯丙酯含量高的芥末调味酱及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1579222A (zh) * | 2003-08-07 | 2005-02-16 | 酒井四郎 | 由芥子分馏异硫氰酸烯丙酯、异硫氰酸对羟基苄酯、蛋白和纤维 |
CN101440054A (zh) * | 2008-12-02 | 2009-05-27 | 中国林业科学研究院林产化学工业研究所 | 从辣根中制备苯乙基异硫氰酸酯的方法 |
CN102811727A (zh) * | 2010-03-31 | 2012-12-05 | 宝洁公司 | 提取异硫氰酸酯的方法 |
CN108624575A (zh) * | 2018-05-21 | 2018-10-09 | 北京化工大学 | 黑芥子酶纯化耦合固定化的方法 |
-
2020
- 2020-07-06 CN CN202010637958.7A patent/CN111850062A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1579222A (zh) * | 2003-08-07 | 2005-02-16 | 酒井四郎 | 由芥子分馏异硫氰酸烯丙酯、异硫氰酸对羟基苄酯、蛋白和纤维 |
CN101440054A (zh) * | 2008-12-02 | 2009-05-27 | 中国林业科学研究院林产化学工业研究所 | 从辣根中制备苯乙基异硫氰酸酯的方法 |
CN102811727A (zh) * | 2010-03-31 | 2012-12-05 | 宝洁公司 | 提取异硫氰酸酯的方法 |
CN108624575A (zh) * | 2018-05-21 | 2018-10-09 | 北京化工大学 | 黑芥子酶纯化耦合固定化的方法 |
Non-Patent Citations (7)
Title |
---|
VAN EYLEN, DAVID等: "《Behavior of mustard seed (Sinapis alba L.) myrosinase during temperature/pressure treatments: a case study on enzyme activity and stability》", 《EUROPEAN FOOD RESEARCH AND TECHNOLOGY》 * |
VAN EYLEN, DAVID等: "《Effects of pressure/temperature treatments on stability and activity of endogenous broccoli (Brassica oleracea L. cv. Italica) myrosinase and on cell permeability》", 《JOURNAL OF FOOD ENGINEERING》 * |
丁瑞霞等: "《异硫氰酸烯丙酯酶解转化工艺的优化》", 《食品安全质量检测学报》 * |
丁轲等: "响应面优化辣根中总异硫氰酸酯及异硫氰酸烯丙酯水解制备工艺", 《中国食品学报》 * |
姜子涛: "《芥末中硫甙的最佳水解工艺及辛辣成份的研究》", 《中国机械工程学会包装与食品工程分会第四届学术年会工程科技Ⅰ辑》 * |
孙艳伟: "黄芥籽中活性成分的制备及其抗氧化活性评价", 《中国优秀硕士学位论文全文数据库(电子期刊)》 * |
罗爽妍: "《超高静压对白芥子中芥子酶催化反应的影响机制研究》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115769885A (zh) * | 2022-11-22 | 2023-03-10 | 珠海天禾食品有限公司 | 一种异硫氰酸烯丙酯含量高的芥末调味酱及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Anal | Food processing by‐products and their utilization: Introduction | |
Chamorro et al. | Valorization of kiwi agricultural waste and industry by-products by recovering bioactive compounds and applications as food additives: A circular economy model | |
Pathak et al. | Waste to wealth: a case study of papaya peel | |
Um et al. | Ultrasound-assisted extraction and antioxidant activity of phenolic and flavonoid compounds and ascorbic acid from rugosa rose (Rosa rugosa Thunb.) fruit | |
CN102018263B (zh) | 一种用于保鲜的全天然精油组合物、制备方法及其使用方法 | |
US9017666B2 (en) | Broccoli based nutritional supplements | |
Galali et al. | Biologically active components in by‐products of food processing | |
CN102196733A (zh) | 脂质的浓缩方法 | |
CN106615073A (zh) | 一种微胶囊蔬菜保鲜剂及制备方法 | |
Secco et al. | Valorization of blueberry by-products (Vaccinium spp.): antioxidants by pressurized liquid extraction (PLE) and kinetics models | |
CN111850062A (zh) | 一种超高静压结合转化液辅助水解芥子中硫代葡萄糖苷为异硫氰酸酯的方法 | |
KR101471450B1 (ko) | 뽕나무를 이용한 훈제 오리고기, 훈제 닭고기 또는 이의 제조방법 | |
FR2663204A1 (fr) | Procede et production d'une huile alimentaire grasse contenant des algues chlorella. | |
Sharma et al. | Utilization of waste from tropical fruits | |
Bekhit et al. | Technological aspects of by-product utilization | |
CA2330383A1 (en) | Carotenoid and other anti-oxidants extraction | |
KR102565191B1 (ko) | 장수풍뎅이 유충 추출물 함유 조성물의 제조방법, 이에 의해 제조된 곤충 추출물 함유 조성물 및 이를 포함하는 식품 | |
CN104997017A (zh) | 一种香蕉植物酵素及其制作方法 | |
CN102805288A (zh) | 一种米糠营养素的提取方法 | |
CN104782754A (zh) | 含牡丹籽粕水提物的果蔬保鲜剂及生产方法及应用 | |
KR102432923B1 (ko) | 파인애플 농축액을 이용한 치킨무 조미액 | |
Oboh et al. | The Effect of Syrup Prepared from Elaeis guineensis jacq.(African Oil Palm) Sap and Honey on the Oxidation of Cooked Ground Beef during Short Term Storage | |
KR20190138910A (ko) | 비타민 c를 이용하여 항산화효과를 높이는 파인애플 발효물의 제조방법 | |
CN107751619A (zh) | 一种宠物猫的专用日粮 | |
KR102671355B1 (ko) | 항산화 활성을 갖는 들깨박 효소분해물 및 그 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201030 |
|
RJ01 | Rejection of invention patent application after publication |