CN114853709A - Method for enriching daidzein in soy sauce residues and application thereof - Google Patents
Method for enriching daidzein in soy sauce residues and application thereof Download PDFInfo
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- CN114853709A CN114853709A CN202210230853.9A CN202210230853A CN114853709A CN 114853709 A CN114853709 A CN 114853709A CN 202210230853 A CN202210230853 A CN 202210230853A CN 114853709 A CN114853709 A CN 114853709A
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- soy sauce
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- ZQSIJRDFPHDXIC-UHFFFAOYSA-N daidzein Chemical compound C1=CC(O)=CC=C1C1=COC2=CC(O)=CC=C2C1=O ZQSIJRDFPHDXIC-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 235000013555 soy sauce Nutrition 0.000 title claims abstract description 61
- 235000007240 daidzein Nutrition 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000012986 modification Methods 0.000 claims abstract description 22
- 230000004048 modification Effects 0.000 claims abstract description 22
- 239000000284 extract Substances 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000003795 desorption Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- KFCUTDKSFNXVKD-UHFFFAOYSA-N 2,2,8,8,8-pentafluorooctanoyl chloride Chemical compound FC(F)(F)CCCCCC(F)(F)C(Cl)=O KFCUTDKSFNXVKD-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 235000010469 Glycine max Nutrition 0.000 claims description 8
- 244000068988 Glycine max Species 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- 235000020712 soy bean extract Nutrition 0.000 claims 7
- 230000010355 oscillation Effects 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 238000005576 amination reaction Methods 0.000 abstract description 2
- 238000003682 fluorination reaction Methods 0.000 abstract description 2
- 239000000287 crude extract Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- GOMNOOKGLZYEJT-UHFFFAOYSA-N isoflavone Chemical compound C=1OC2=CC=CC=C2C(=O)C=1C1=CC=CC=C1 GOMNOOKGLZYEJT-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- 235000008696 isoflavones Nutrition 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000010262 high-speed countercurrent chromatography Methods 0.000 description 3
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 235000003687 soy isoflavones Nutrition 0.000 description 2
- DKVBOUDTNWVDEP-NJCHZNEYSA-N teicoplanin aglycone Chemical compound N([C@H](C(N[C@@H](C1=CC(O)=CC(O)=C1C=1C(O)=CC=C2C=1)C(O)=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)OC=1C=C3C=C(C=1O)OC1=CC=C(C=C1Cl)C[C@H](C(=O)N1)NC([C@H](N)C=4C=C(O5)C(O)=CC=4)=O)C(=O)[C@@H]2NC(=O)[C@@H]3NC(=O)[C@@H]1C1=CC5=CC(O)=C1 DKVBOUDTNWVDEP-NJCHZNEYSA-N 0.000 description 2
- SHMNLEQWIMKCQA-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(Cl)=O SHMNLEQWIMKCQA-UHFFFAOYSA-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
- 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
- 239000004952 Polyamide Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000006539 genistein Nutrition 0.000 description 1
- TZBJGXHYKVUXJN-UHFFFAOYSA-N genistein Natural products C1=CC(O)=CC=C1C1=COC2=CC(O)=CC(O)=C2C1=O TZBJGXHYKVUXJN-UHFFFAOYSA-N 0.000 description 1
- 229940045109 genistein Drugs 0.000 description 1
- 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 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000000899 pressurised-fluid extraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/34—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only
- C07D311/36—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only not hydrogenated in the hetero ring, e.g. isoflavones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/40—Separation, e.g. from natural material; Purification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Soy Sauces And Products Related Thereto (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for enriching daidzein in soy sauce residue and application thereof, wherein the method specifically comprises the steps of mixing MOF-808-F prepared by two-step modification of a metal organic framework material MOF-808 with a primary extract of soy sauce residue, desorbing the MOF-808-F adsorbed with daidzein with methanol, and finally concentrating and drying. According to the invention, through two-step modification of amination and fluorination on MOF-808, the hydrophobic property of the prepared MOF-808-F material is greatly improved, the adsorption property of the material on daidzein is improved, and the effect of enriching and purifying the daidzein in soy sauce residues is achieved; the invention skillfully utilizes the hydrophobic effect, the chelating effect and the surface adsorption effect of the MOF-808-F material to selectively adsorb the daidzein, and effectively adsorbs the daidzein so as to achieve the purpose of enriching the daidzein in the soy sauce residue.
Description
Technical Field
The invention relates to the technical field of food deep processing, in particular to a method for enriching daidzein in soy sauce residues and application thereof.
Background
Soy sauce, a commonly used traditional seasoning, has an increasing yield year by year and results in an increase in the yield of soy sauce residues, a by-product thereof; it still contains many reusable bioactive components such as soy isoflavones. During the fermentation process, the glucoside isoflavone can be converted into aglycon isoflavone (genistein, daidzein and daidzein) with bioactivity, and the content of the aglycon isoflavone in the soy sauce residue is higher than that in the soybeans, so the soy sauce residue is a good and rich source for separating and purifying the soy isoflavone.
In the prior art, the extraction method of aglycone isoflavone daidzein comprises auxiliary solvent extraction (heating reflux method, ultrasonic auxiliary extraction method, microwave auxiliary extraction method), and pressure fluid extraction (supercritical CO extraction method) 2 Extraction, pressurized liquid extraction, subcritical fluid extraction), and solid phase extraction. Wherein: the auxiliary solvent extraction method destroys a sample by means of heating, ultrasound and microwave, enhances the leaching and permeation of effective components in the sample by a solvent, and achieves the effect of improving the extraction efficiency; the pressure fluid extraction method and the solid phase extraction method utilize high pressure to carry out green extraction on the sample, and can shorten the extraction time; the solid adsorbent adsorbs active ingredients in the liquid sample, and then the active ingredients are eluted by eluent or desorbed by heating, so that the aim of separating and enriching target compounds is fulfilled, and the method is also commonly used as a refining and purifying method.
In terms of purification, commonly used methods include column chromatography (silica gel column chromatography, polyamide column chromatography, macroporous adsorbent resin column chromatography, etc.) and high-speed counter-current chromatography. The column chromatography can separate the daidzein from the sample solution by molecular sieve action and intermolecular force (hydrogen bond or van der waals force), so that a high-purity daidzein product can be obtained; the high-speed counter-current chromatography is a liquid-liquid partition chromatography technology without a solid carrier, and the separation and purification are carried out by utilizing the solubility difference among compounds, so that the denaturation and decomposition of analytes are not caused, the product recovery rate is high, the purification effect is good, and the separation can be continuously carried out with high efficiency.
Although column chromatography is widely applied to separation and purification, the separation and purification steps are complicated, the single treatment capacity is small, and the column chromatography is difficult to apply to industrial production; the high-speed counter-current chromatography also has the defects of higher cost and suitability for separating and purifying a small amount of products, and the method is not specific and only depends on the difference of the solubility of the substances for separation. In solid phase extraction processes, the choice of adsorbent material directly affects separation parameters such as selectivity, selectivity and adsorption capacity. Common natural adsorption materials such as activated carbon, zeolite, clay, and resin, most of which have a low surface area and few functional groups on the surface, are difficult to provide effective adsorption force, resulting in limited adsorption capacity.
Metal organic framework Materials (MOFs) are widely used for removing and separating various substances (such as heavy metal ions, harmful substances, gases, bioactive components) due to the advantages of large specific surface area, porous surface, abundant active sites, strong designability and the like. Because daidzein is difficult to dissolve in water and has high hydrophobicity, according to the characteristic of high hydrophobicity, the MOFs material can improve the hydrophobicity of the MOFs material after being modified by modification after being fluorinated, and the adsorption performance of the MOFs material on daidzein is improved through the hydrophobic effect. So far, reports on how to modify MOFs materials to separate and purify soybean isoflavone and apply the soybean isoflavone to the field of food have not been found.
In view of this, the invention is particularly proposed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for enriching daidzein in soy sauce residue and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for enriching daidzein in soy sauce residue, comprising:
mixing MOF-808-F prepared by two-step modification of metal organic framework material MOF-808 with a primary extract of soy sauce residue, desorbing MOF-808-F adsorbed with daidzein with methanol, and finally concentrating and drying.
In a specific embodiment of the present invention, the method for enriching daidzein in soy sauce residue comprises the following steps:
s1, crude extraction of soy sauce residues: mixing the soy sauce residues with an ethanol water solution as a solvent, and adjusting the concentration of ethanol in an extracting solution after extraction to obtain an initial extracting solution of the soy sauce residues;
s2, preparation and modification of MOF-808: preparing metal organic framework material MOF-808 by a hydrothermal method, and modifying by 5-amino isophthalic acid to obtain MOF-808-NH 2 Finally, modifying by pentafluorooctanoyl chloride to prepare MOF-808-F;
s3, uniformly mixing the MOF-808-F obtained in the step S2 and the primary extract obtained in the step S1 according to the solid-liquid ratio of 0.8-1.25 mg: 1mL, oscillating for adsorption, removing supernatant, ultrasonically desorbing by using pure methanol, performing solid-liquid separation, collecting desorption solution, concentrating and drying to obtain the soyabean essence;
wherein, the step S1 and the step S2 can be switched in order.
In the above technical solution, in step S2, a hydrothermal preparation process of the metal-organic framework material MOF-808 includes:
ultrasonically mixing zirconium salt, trimesic acid, N-dimethylformamide and formic acid according to a proportion, carrying out hydrothermal reaction at the temperature of 120-145 ℃ after sealing, centrifugally collecting a reaction product, and then sequentially carrying out soaking washing and high-temperature activation to obtain the MOF-808.
Specifically, in the above technical solution, in step S2, in the hydrothermal preparation process of the metal-organic framework material MOF-808, the hydrothermal reaction time is 45-50 h.
Specifically, in the above technical solution, in step S2, in the hydrothermal preparation process of the metal-organic framework material MOF-808, the soaking and washing is specifically to sequentially soak and wash the product with N, N-dimethylformamide and methanol for 2 to 4 times.
Specifically, in the above technical solution, in step S2, during the hydrothermal preparation process of the metal-organic framework material MOF-808, the temperature and time for the high-temperature activation are 140-160 ℃ and 18-24h, respectively.
In the above technical solution, in step S2, the process of modifying the MOF-808 with 5-aminoisophthalic acid includes:
dispersing the prepared powdered MOF-808 in an acetone solution of 5-amino isophthalic acid, soaking and washing a product after an activation reaction, and drying to obtain the MOF-808-NH 2 。
Specifically, in the above technical solution, in step S2, in the process of modifying 5-amino isophthalic acid in the metal organic framework material MOF-808, the concentration of the acetone solution of 5-amino isophthalic acid is 30 to 60 mmol/L.
Specifically, in the above technical solution, in step S2, in the process of modifying 5-amino isophthalic acid in the metal organic framework material MOF-808, the amount of acetone solution of 5-amino isophthalic acid added is 0.08-0.12mL, corresponding to 1mg of powdered MOF-808.
Specifically, in the above technical solution, in step S2, in the modification process of 5-aminoisophthalic acid of the metal organic framework material MOF-808, the temperature and time of the activation reaction are 10-40 ℃ and 18-26h, respectively.
Specifically, in the above technical solution, in step S2, in the process of modifying the 5-aminoisophthalic acid of the metal-organic framework material MOF-808, the soaking and washing specifically is to sequentially soak and wash the product with N, N-dimethylformamide and acetone for 2 to 4 times.
Specifically, in the above technical solution, in the step S2, in the modification process of the 5-aminoisophthalic acid of the metal organic framework material MOF-808, the drying includes vacuum drying at room temperature for 15-40h, and then drying at 155-180 ℃ for 18-35 h.
In the technical scheme, in step S2, the MOF-808-NH is modified by pentafluorooctanoyl chloride 2 The process comprises the following steps:
MOF-808-NH 2 Dispersing in pentafluorooctanoyl chloride, stirring at 25-55 deg.C for reaction, condensing and refluxing, centrifuging to collect the reacted product, washing, and drying to obtain MOF-808-F.
Specifically, in the above technical solution, in step S2, MOF-808-NH is formed in the metal-organic framework material 2 During the modification process of the pentafluorooctanoyl chloride, the content of the corresponding 1mg of MOF-808-NH is 2 The adding amount of the pentafluorooctanoyl chloride is 0.015-0.024 mL.
Specifically, in the above technical solution, in step S2, MOF-808-NH is formed in the metal-organic framework material 2 In the modification process of the pentafluorooctanoyl chloride, the reaction time is 20-26 h.
Specifically, in the above technical solution, in step S2, MOF-808-NH is formed in the metal-organic framework material 2 In the modification process of the pentafluorooctanoyl chloride, the washing is specifically carried out by washing with acetone for three times.
Specifically, in the above technical solution, in step S2, MOF-808-NH is formed in the metal-organic framework material 2 In the modification process of the pentafluorooctanoyl chloride, the drying temperature and the drying time are respectively 25-40 ℃ and 10-15 h.
Further, in the above technical scheme, in the step S1, in the course of crude extraction of the soy sauce residues, the soy sauce residues and 70% ethanol water solution are mixed according to a material-to-liquid ratio of 1: 10-15, extracted at 65-78 ℃ for 3-6h, and then diluted with water until the ethanol concentration in the extract is 24-26%, so as to obtain a primary extract of the soy sauce residues.
Further, in the above technical solution, in step S3, the time of the oscillating adsorption is 1.5 to 3 hours, and the ultrasonic desorption includes ultrasonic treatment for 15 to 30min and oscillating for 45 to 90 min.
The invention also provides the application of the method in recovering the daidzein in the soy sauce residue.
Compared with the prior art, the invention has the following advantages:
(1) the MOF-808-F material is prepared, and soyabean elements in the soy sauce residues are enriched and refined by utilizing the characteristics of porous surface, abundant metal center and high hydrophobicity;
(2) compared with an unmodified MOF-808 material, the MOF-808-F material adopted by the invention is subjected to two-step modification of amination and fluorination on the MOF-808, so that the hydrophobic property of the prepared MOF-808-F material is greatly improved, the adsorption property of the material on daidzein is improved, and the effect of enriching and purifying the daidzein in soy sauce residues is achieved;
(3) the method skillfully utilizes the hydrophobic effect, the chelation effect and the surface adsorption effect of the MOF-808-F material to selectively adsorb the daidzein, and effectively adsorbs the daidzein so as to achieve the purpose of enriching the daidzein in the soy sauce residue.
Drawings
FIG. 1 is a schematic flow chart of the process for enriching daidzein in soy sauce residue according to an embodiment of the present invention;
FIG. 2 is a graph showing the comparison of the measurement results of the water contact angle of MOF-808 in step S2 and MOF-808-F obtained by two-step modification in example 1 of the present invention
Fig. 3 is a graph comparing the results of the contents of daidzein in the soy sauce residue and the crude extract in step S1 of example 1 of the present invention, the content of daidzein in the desorption solution in step S3 of example 1, and the content of daidzein in the desorption solution in step S3 of comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the means used are conventional in the art unless otherwise specified.
The terms "comprises," "comprising," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental raw materials used in the examples of the invention are all commercially available products.
The soy sauce residue used in the embodiment of the invention is fresh soy sauce residue discarded after soy sauce production.
The preparation process of the metal organic framework material MOF-808 used in the embodiment of the invention comprises the following steps:
(1) accurately weigh 483.6mg ZrOCl 2 ·8H 2 Adding O and 314.4mg of trimesic acid into an inner container of a reaction kettle with a polytetrafluoroethylene lining, then adding 60mL of N, N-dimethylformamide and 60mL of formic acid, uniformly mixing, and covering a cover;
(2) putting the inner container into an ultrasonic cleaner, performing ultrasonic treatment for 10min until the mixture is dissolved, then putting the inner container of the reaction kettle into a high-pressure reaction kettle, screwing down a cover, putting the sealed high-pressure kettle into an electric heating constant-temperature air-blowing drying box, heating for 48h at 130 ℃, after heating and cooling, centrifugally collecting the obtained white material, soaking and washing for 3 times by using N, N-dimethylformamide and methanol respectively, and finally heating the powder for 20h at 150 ℃ to activate.
Example 1
The embodiment of the invention provides a method for enriching daidzein in soy sauce residues, which specifically comprises the following steps as shown in figure 1:
s1, uniformly mixing soy sauce residue (100g) with the content of daidzein detected and 70 wt% of ethanol water solution according to the material-to-liquid ratio of 1: 12, stirring and extracting at 70 ℃ for 4h to obtain a crude extract, measuring the content of daidzein in the crude extract, and adding water to dilute until the content of ethanol in the crude extract is 25 wt% to obtain a primary extract of soy sauce residue for later use;
s2 two-step modification of metal organic framework material MOF-808
(1) Dispersing a 300mg MOF-808 powder sample in 30mL of 50 mmol/L5-amino isophthalic acid acetone solution, violently stirring for 24h at room temperature, centrifugally collecting materials after reaction, respectively soaking and washing the materials with N, N-dimethylformamide and acetone for three times, vacuum drying the washed materials for 24h at room temperature, and drying for 24h at 160 ℃ to obtain an activated product MOF-808-NH 2 ；
(2) Weighing 300mg of MOF-808-NH 2 Dispersing in a three-neck flask filled with 5mL of pentafluorooctanoyl chloride, heating the mixture at 40 ℃, magnetically stirring for 24 hours, centrifugally collecting materials after the reaction is finished, washing the materials with acetone for three times, and drying the materials at 30 ℃ for 12 hours to obtain MOF-808-F;
s3, MOF-808-F material static adsorption desorption
(1) Adsorption experiments
Accurately weighing 30mg of MOF-808-F material, placing the MOF-808-F material in a 50mL centrifuge tube, adding 30mL of soy sauce residue primary extract, placing the centrifuge tube on a shaking table after ultrasonic treatment for 20min, oscillating for 2h, centrifuging at 7000r/min for 10min, taking supernatant, diluting to 2 times with ethanol, and determining the concentration of daidzein in the diluent by high performance liquid chromatography;
(2) desorption experiment
Transferring the supernatant, keeping the MOF-808-F material in a centrifuge tube, adding 40mL of pure methanol for desorption, carrying out ultrasonic treatment for 20min, standing for 1h, centrifuging at 7000r/min for 15min, collecting desorption liquid, carrying out volume and concentration determination on the desorption liquid, carrying out rotary evaporation to obtain extract, and carrying out drying treatment to obtain a refined product of the purified soyabean essence.
Example 2
The embodiment of the invention provides a method for enriching daidzein in soy sauce residues, which specifically comprises the following steps:
s1, uniformly mixing soy sauce residues (100g) with the content of daidzein detected with 70 wt% of ethanol water solution according to the material-liquid ratio of 1: 12, stirring and extracting at 70 ℃ for 4h to obtain a crude extract, measuring the content of daidzein in the crude extract, and adding water to dilute until the content of ethanol in the crude extract is 25 wt% to obtain a primary extract of soy sauce residues for later use;
s2 two-step modification of metal organic framework material MOF-808
(1) Dispersing a 300mg MOF-808 powder sample in 35mL of 40 mmol/L5-amino isophthalic acid acetone solution, violently stirring for 24h at room temperature, centrifugally collecting materials after reaction, respectively soaking and washing the materials with N, N-dimethylformamide and acetone for three times, vacuum drying the washed materials for 24h at room temperature, and drying for 24h at 180 ℃ to obtain an activated product MOF-808-NH 2 ；
(2) Weighing 300mg of MOF-808-NH 2 Dispersing in a conical flask filled with 4mL of pentafluoropropionyl chloride, heating the mixture at 40 ℃, performing magnetic stirring, condensing and refluxing for 24h, centrifugally collecting the material after the reaction is finished, washing with acetone for three times, and drying at 30 ℃ for 10h to obtain MOF-808-F;
s3, MOF-808-F material static adsorption desorption
(1) Adsorption experiments
Accurately weighing 30mg of MOF-808-F material, placing the MOF-808-F material in a 50mL centrifuge tube, adding 30mL of soy sauce residue primary extract, placing the centrifuge tube on a shaking table after ultrasonic treatment for 20min, oscillating for 2h, centrifuging at 7000r/min for 10min, taking supernatant, diluting to 2 times with ethanol, and determining the concentration of daidzein in the diluent by high performance liquid chromatography;
(2) desorption experiment
Transferring the supernatant, keeping the MOF-808-F material in a centrifuge tube, adding 40mL of pure methanol for desorption, carrying out ultrasonic treatment for 20min, standing for 1h, centrifuging at 7000r/min for 15min, collecting desorption liquid, carrying out volume and concentration determination on the desorption liquid, carrying out rotary evaporation to obtain extract, and carrying out drying treatment to obtain a refined product of the purified soyabean essence.
Through detection, the content of daidzein in the desorption solution after MOF-808-F enrichment in example 1 and example 2 is 115.32mg/g and 94.63mg/g respectively.
Comparative example 1
The invention provides a method for enriching daidzein in soy sauce residue, which comprises the following steps:
s1, uniformly mixing soy sauce residue (100g) with the content of daidzein detected and 70 wt% of ethanol water solution according to the material-to-liquid ratio of 1: 12, stirring and extracting at 70 ℃ for 4h to obtain a crude extract, measuring the content of daidzein in the crude extract, and adding water to dilute until the content of ethanol in the crude extract is 25 wt% to obtain a primary extract of soy sauce residue for later use;
s2 synthesis of metal organic framework material MOF-808
483.6mg of ZrOCl were weighed 2 ·8H 2 O, 314.4mg of trimesic acid, which is added into the inner container of a reaction kettle with a polytetrafluoroethylene lining, then 60mL of N, N-dimethylformamide and 60mL of formic acid are added, mixed evenly and covered with a cover. Putting the inner container into an ultrasonic cleaner, and performing ultrasonic treatment for 10min until the mixture is dissolved. The inner container of the reaction kettle is placed into a high-pressure reaction kettle, the cover is screwed down, and the sealed high-pressure kettle is placed into an electric heating constant-temperature blast drying box to be heated for 48 hours at 130 ℃. After completion of heating and cooling, the obtained white material was collected by centrifugation and washed by immersion in N, N-dimethylformamide and methanol each three times. Finally, the powder is heated at 150 ℃ for 20h to activate;
s3, MOF-808 material static adsorption desorption
(1) Adsorption experiments
Accurately weighing 30mg of MOF-808 material, placing the MOF-808 material in a 50mL centrifuge tube, adding 30mL of soy sauce residue primary extract, carrying out ultrasonic treatment for 20min, placing the centrifuge tube on a shaking table, oscillating for 2h, centrifuging at 7000r/min for 10min, taking supernatant, diluting to 2 times with ethanol, and determining the concentration of daidzein in the diluent by high performance liquid chromatography;
(2) desorption experiment
Transferring the supernatant, keeping the MOF-808 material in a centrifuge tube, adding 40mL of pure methanol for desorption, performing ultrasonic treatment for 20min, standing for 1h, centrifuging at 7000r/min for 15min, collecting desorption solution, determining the volume and the concentration of daidzein in the desorption solution, performing rotary evaporation to obtain extract, and drying to obtain a purified refined daidzein product.
FIG. 2 is a graph showing the comparison of the measurement results of the water contact angle of MOF-808 in step S2 and MOF-808-F obtained by two-step modification in example 1 of the present invention; as can be seen from the figure: the water contact angle of the MOF-808 is 30.14 degrees, the water contact angle of the MOF-808-F is 40.29 degrees, and the water contact angle of the MOFs material is increased after two-step modification, which shows that the hydrophobicity of the material is enhanced.
FIG. 3 is a graph showing the comparison of the content of daidzein in the soy sauce residue and the crude extract in step S1 of example 1 of the present invention, the content of daidzein in the desorption solution in step S3 of example 1, and the content of daidzein in the desorption solution in step S3 of comparative example 1.
As can be seen from the figure: the content of daidzein in the soy sauce residue and the crude extract is extremely low, and is respectively 1.45mg/g and 5.06 mg/g; after MOF-808 and MOF-808-F enrichment, the content of daidzein in the purified product is greatly improved to 53.64mg/g and 115.32mg/g respectively, which shows that after the material is modified and the hydrophobicity is improved, the enrichment of daidzein is remarkably improved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention.
It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for enriching daidzein in soy sauce residue is characterized in that,
the MOF-808-F prepared by two-step modification of a metal organic framework material MOF-808 is mixed with a primary extract of soy sauce residues, then the MOF-808-F with absorbed daidzein is desorbed by methanol, and finally, the mixture is concentrated and dried.
2. The method of enriching soy bean extract in soy sauce residues as claimed in claim 1,
the method comprises the following steps:
s1, crude extraction of soy sauce residues: mixing the soy sauce residues with an ethanol water solution as a solvent, and adjusting the concentration of ethanol in an extracting solution after extraction to obtain an initial extracting solution of the soy sauce residues;
s2, preparation and modification of MOF-808: preparing metal organic framework material MOF-808 by a hydrothermal method, and modifying by 5-amino isophthalic acid to obtain MOF-808-NH 2 Finally, modifying by pentafluorooctanoyl chloride to prepare MOF-808-F;
s3, uniformly mixing the MOF-808-F obtained in the step S2 and the primary extract obtained in the step S1 according to the solid-liquid ratio of 0.8-1.25 mg: 1mL, oscillating for adsorption, removing supernatant, ultrasonically desorbing by using pure methanol, performing solid-liquid separation, collecting desorption solution, concentrating and drying to obtain the soyabean essence;
wherein, the step S1 and the step S2 can be switched in order.
3. The method of enriching soy bean extract in soy sauce residues as claimed in claim 2,
in step S2, the hydrothermal preparation process of the metal-organic framework material MOF-808 includes:
ultrasonically mixing zirconium salt, trimesic acid, N-dimethylformamide and formic acid according to a proportion, carrying out hydrothermal reaction at the temperature of 120-145 ℃ after sealing, centrifugally collecting a reaction product, and then sequentially carrying out soaking washing and high-temperature activation to obtain the MOF-808.
4. The method of enriching soy bean extract in soy sauce residues as claimed in claim 3,
in step S2, in the hydrothermal preparation process of the metal-organic framework material MOF-808:
the time of the hydrothermal reaction is 45-50 h;
and/or, the soaking and washing is specifically that the product is sequentially soaked and washed for 2-4 times by using N, N-dimethylformamide and methanol respectively;
and/or the temperature and the time of the high-temperature activation are respectively 140-160 ℃ and 18-24 h.
5. The method of enriching soy bean extract in soy sauce residues as claimed in claim 2,
in step S2, the process of modifying the MOF-808 with 5-aminoisophthalic acid comprises:
dispersing the prepared powdered MOF-808 in an acetone solution of 5-amino isophthalic acid, soaking and washing a product after an activation reaction, and drying to obtain the MOF-808-NH 2 。
6. The method of enriching soy bean extract in soy sauce residues as claimed in claim 5,
in step S2, in the 5-aminoisophthalic acid modification process of the metal-organic framework material MOF-808:
the concentration of the acetone solution of the 5-amino isophthalic acid is 30-60 mmol/L;
and/or, the amount of the acetone solution of 5-amino isophthalic acid added is 0.08-0.12mL corresponding to 1mg of powdered MOF-808;
and/or the temperature and the time of the activation reaction are respectively 10-40 ℃ and 18-26 h;
and/or, the soaking and washing is specifically that the product is sequentially soaked and washed for 2-4 times by N, N-dimethylformamide and acetone respectively;
and/or the drying comprises vacuum drying at room temperature for 15-40h, and then drying at high temperature of 155-180 ℃ for 18-35 h.
7. The method of enriching soy bean extract in soy sauce residues as claimed in claim 2,
in step S2, modifying the MOF-808-NH with pentafluorooctanoyl chloride 2 The process of (2) comprises:
MOF-808-NH 2 Dispersing in pentafluorooctanoyl chloride, stirring at 25-55 deg.C for reaction, condensing and refluxing, centrifuging to collect the reacted product, washing, and drying to obtain MOF-808-F.
8. The method of enriching daidzein in soy sauce residue according to claim 7,
in step S2, MOF-808-NH is formed in the metal-organic framework material 2 In the modification process of the pentafluorooctanoyl chloride:
corresponding to 1mg of MOF-808-NH 2 The adding amount of the pentafluorooctanoyl chloride is 0.015-0.024 mL;
and/or the reaction time is 20-26 h;
and/or, the washing is specifically washing with acetone for three times;
and/or the drying temperature and time are respectively 25-40 ℃ and 10-15 h.
9. The method for enriching soy bean extract in soy sauce lees according to any one of claims 2 to 8,
in the step S1, in the crude extraction process of the soy sauce residues, mixing the soy sauce residues and 70% ethanol water according to the material-liquid ratio of 1: 10-15, extracting at 65-78 ℃ for 3-6h, and then adding water to dilute until the ethanol concentration in the extracting solution is 24-26% to obtain a primary extracting solution of the soy sauce residues;
and/or in step S3, the oscillation adsorption time is 1.5-3h, and the ultrasonic desorption comprises ultrasonic treatment for 15-30min and oscillation for 45-90 min.
10. Use of the method of any one of claims 1 to 9 for recovering daidzein from soy sauce residues.
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