CN112715917A - Preparation method of soy sauce rich in active selenium - Google Patents
Preparation method of soy sauce rich in active selenium Download PDFInfo
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/50—Soya sauce
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/015—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/30—Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation
- A23L5/32—Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation using phonon wave energy, e.g. sound or ultrasonic waves
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Nutrition Science (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Soy Sauces And Products Related Thereto (AREA)
Abstract
The invention discloses a preparation method of soy sauce rich in active selenium, belonging to the technical field of food processing. The method comprises the following steps: the soy sauce is prepared by using soybean or soybean meal or black soybean, flour or crushed fried wheat and salt as main raw materials, adding an active nano selenium-chitosan compound into the raw soy sauce to enable the content of the active nano selenium-chitosan compound to reach 1-300 mu M/L, and then carrying out ultrasonic treatment to promote the active nano selenium to be crosslinked and combined with amino acid, polypeptide and polysaccharide in the soy sauce to further stabilize the nano selenium. After the active nano-selenium soy sauce is subjected to ultrasonic treatment, diatomite filtration, sterilization and filling are carried out, and the high-stability active nano-selenium-rich soy sauce is obtained. Compared with the conventional soy sauce and the contrast selenium-rich soy sauce, the active-rich nano-selenium soy sauce produced by the method has the outstanding advantages of high safety, stability, high organic selenium content and the like, and the added value of the product is high.
Description
Technical Field
The invention relates to a preparation method of soy sauce rich in active selenium, in particular to a preparation method of high-stability soy sauce rich in active selenium, belonging to the technical field of food processing.
Background
The soy sauce originates from China and is an essential seasoning in daily cooking, catering industry and food industry of people. Currently, the annual yield of Chinese soy sauce is over 50% of the total world production, and the annual yield is about 1000 ten thousand tons (Yangmingquan, et al. domestic soy sauce secondary sedimentation research progress and prospect [ J ] food and fermentation industry, 2019, 45(10), 250-. The current high-end market for soy sauce is almost occupied by Japanese soy sauce, and the average price of Chinese soy sauce is less than 1/12 for Japanese soy sauce (Yangmingquan, et al. domestic soy sauce secondary sedimentation research progress and prospect [ J ] food and fermentation industry, 2019, 45(10), 250-. Therefore, how to improve the quality of the Chinese soy sauce and further improve the competitiveness of the Chinese soy sauce in domestic and foreign markets becomes a bottleneck problem of the development of the Chinese soy sauce industry.
Selenium is a fourth-cycle group-six transition element and plays an important role in maintaining human health, and the occurrence of more than 40 diseases (e.g., keshan disease, Kashin-Kaschin-Beck disease, cardiovascular disease, etc.) is highly correlated with selenium deficiency (Miguel Navarro-Alarcon and Carmen Cabrera-viqu. Selenium in food and the human body: a review [ J ] Science of the Total Environment,2008,400, 115-141.). The main routes for selenium to be available to humans are soil → plants → animals → food → humans, while more than 72% of the land in china (especially the densely populated areas in the middle east) is areas with or severe selenium deficiency, which results in more than one third of the people in china being in a state of selenium deficiency or severe selenium deficiency (hanging Dawei et a. selenium supplement, free quality and yield of computer jujube as infected by side addition of sodium selenium [ J ]. scientific horticulture, 2017,225, 1-5.). At present, the selenium intake of adults in China is only 26-32 micrograms per day, and the minimum intake of adults recommended by the world health organization is 55 micrograms per day (Diaphana. preparation of chitosan nano-smashing system and research on physicochemical properties and biological activity thereof [ D ]. Beijing: China university of agriculture, 2017.).
Inorganic selenium mainly exists in the forms of selenite and selenate, and both are highly toxic compounds to human beings. Selenite and selenate are absorbed by biological plants and mainly expressed by Se6+And Se4+The selenium is in a form that can be partially converted into organic selenium after being absorbed by microorganisms. The toxicity of nano-selenium and organic selenium (especially nano-selenium) is far lower than that of inorganic selenium, while the biological activity (such as oxidation resistance, immunocompetence, selenium-containing enzyme activity and the like) is far higher than that of inorganic selenium, so that the nano-selenium and organic selenium is an ideal state for supplementing selenium for human bodies; preparation of Wangting, glutathione nano selenium compound and its characteristic research [ D]Guangzhou: river university, 2010; diagnna Dianthi, preparation of chitosan nano-smashing system and research on physicochemical characteristics and biological activity of chitosan nano-smashing system [ D]Beijing: university of agriculture, china, 2017). Therefore, the intake of nano and organic active selenium is significant for improving the intake of selenium。
At present, the domestic selenium supplement product mainly supplements sodium selenite or sodium selenate, and the supplement of inorganic selenium has low biotransformation rate or the risk of chronic poisoning caused by the accumulation of inorganic selenium. Research has proved that the nano-selenium not only has low toxicity, but also has high bioavailability and bioactivity. The preparation of nano-selenium generally adopts VC, VE, VA, glutathione, amino acid and the like as reducing agents, and adopts protein and polysaccharide as nano-selenium adsorbents and stabilizers, but nano-selenium-protein/polysaccharide complexes are easy to flocculate and precipitate (generally about 30 days), have poor stability, and cause the prepared active nano-selenium complexes to lose commercial value (Song Xiaooxinao, et al. physiochemical and functional properties of chemical-stabilized selected selenium nanoparticles complex under the condition of differential processing treatment of microorganisms [ J ]. Food Chemistry 331 (127378)).
The soy sauce is a liquid seasoning prepared by fermenting soybean/soybean meal, flour and salt serving as main raw materials by using microorganisms such as aspergillus oryzae and the like. At present, the production of the selenium-rich soy sauce mainly adopts the method of (1) directly adding inorganic selenium (CN101584454, CN104431947A) into salt water at the early stage of fermentation or (2) directly adding a mixture of selenium, VA and VE (CN101176546A) into the soy sauce obtained by filtering at the later stage of fermentation or (3) adding selenium-rich yeast (CN 102524741A). However, in the method (1), inorganic selenium has high toxicity, and the safety problem exists when the inorganic selenium is directly added; in addition, inorganic selenium added at the early stage is absorbed and utilized by microorganisms such as yeast and lactic acid bacteria existing in the mash during the fermentation process, and the microorganisms are filtered and removed at the later stage, so that selenium remaining in the soy sauce is greatly reduced, and the method (3) has the same problem. In the method (2), the effect of protecting and reducing the nano-selenium by adopting VA and VE is poor, because the soy sauce is a water-soluble colloid and VA and VE are fat-soluble vitamins, the nano-selenium system constructed by the method is unstable.
Disclosure of Invention
[ problem ] to
On one hand, inorganic selenium is toxic to human bodies when being supplemented, and on the other hand, when the soy sauce is prepared by fermenting the selenium-rich raw materials, selenium can be absorbed and utilized by microorganisms such as saccharomycetes, lactic acid bacteria and the like existing in mash in the fermentation process, and the microorganisms can be filtered and removed in the later period, so that the selenium left in the soy sauce can be greatly reduced. In addition, soy sauce is a water-soluble colloid, and it is difficult to form a stable homogeneous system when nano-selenium prepared by the method of the patent (CN101176546A) is added.
[ solution ]
The invention aims to develop a preparation method of soy sauce rich in active selenium with high stability. Specifically, the invention provides a method for preparing high-stability soy sauce rich in active selenium by using an active nano selenium-chitosan compound prepared by using soybean or soybean meal or black soybean, flour or crushed parched wheat as a main raw material, Aspergillus oryzae (Aspergillus oryzae) or Aspergillus sojae as a fermentation strain and using chitosan, selenious acid or sodium selenate, VC and glacial acetic acid or sulfuric acid as raw materials and using an ultrasonic stabilization technology.
The method comprises the following specific steps:
(1) preparation of active nano selenium-chitosan compound
1) Adding 0.1-5g of chitosan (deacetylation degree is 70-98%) into 100mL of water, adding 0.1-10mL of glacial acetic acid or hydrochloric acid or sulfuric acid while stirring, and stirring uniformly to obtain a chitosan solution;
2) slowly adding sodium selenite or sodium selenate into the chitosan solution in the step 1), adjusting the concentration of the sodium selenite or sodium selenate in the solution to be 1-500mM/L, and uniformly stirring;
3) slowly adding VC into the sodium selenite or sodium selenate-chitosan solution, adjusting the molar ratio of the sodium selenite or sodium selenate to the VC to be 1 (1-10), and uniformly stirring to obtain an active nano selenium-chitosan compound;
(2) preparation of high-stability soy sauce rich in active selenium
1) Raw material selection and proportioning: protein raw material (soybean or soybean meal or black bean): flour or pulverized parched wheat at a ratio of 100:10-50 (calculated on dry matter);
2) pretreatment of raw materials: cleaning semen glycines or semen Sojae Atricolor, soaking at normal temperature for 4-16h, moistening bean cake and 0.7-1.0 times (preferably 0.8 times) of water for 10-30min, and steaming and boiling the above protein materials at 140 deg.C for 5-180min under 100-;
3) preparing the yeast for making hard liquor: mixing Aspergillus oryzae (Asperg)Bacillus oryzae) or Aspergillus sojae spore (Aspergillus sojae) is premixed with flour or pulverized parched wheat, and the inoculation amount is 1 × 105-1×107CFU/g raw material flour or pulverized parched wheat, cooling the protein material cooked in step 2) to about 40 deg.C, mixing with the above flour inoculated with Aspergillus spore or pulverized parched wheat, and culturing the mixture at 20-32 deg.C for 36-60 hr to obtain Daqu;
4) preparing mash and adding active nano selenium: preparing saline water with the concentration of 5-25% (w/w), adding the active nano selenium-chitosan compound into the saline water, mixing the solution with a ratio of Daqu to the saline water of 1kg (0.8-4) L to prepare mash, and uniformly mixing the mash until the selenium content in the mash reaches 1-300 mu M/L;
5) and (3) stabilizing active selenium: fermenting the soy sauce mash obtained in the step 4) at the temperature of 10-60 ℃ for 15 days to 2 years, and carrying out ultrasonic treatment on the soy sauce mash when the soy sauce mash is fermented for 1-180 days to promote crosslinking and combination of the active nano selenium and protein, amino acid, polypeptide and polysaccharide in fermentation liquor to further stabilize the active selenium, wherein the ultrasonic conditions are as follows: the frequency is 18-100kHz, the ultrasonic intensity is 1-100W/L, and the ultrasonic time is 30S-60 min;
6) squeezing or oil spraying: squeezing or spraying oil on the sauce mash after fermentation to obtain raw soy sauce;
7) filtering, sterilizing and filling: filtering the raw soy sauce with diatomite, sterilizing (60-140 deg.C/10S-60 min), and packaging to obtain high-stability soy sauce rich in active selenium.
In one embodiment of the invention, in the step (1), 0.5-3g of chitosan (deacetylation degree 85-95%) is added into 100mL of water, 1-6mL of glacial acetic acid, hydrochloric acid or sulfuric acid is further added, and the mixture is uniformly stirred; then slowly adding sodium selenite or sodium selenate into the chitosan solution, adjusting the concentration of the sodium selenite or sodium selenate solution to 10-100mM/L, and uniformly stirring; finally, VC is slowly added into the sodium selenite or sodium selenate-chitosan solution, the molar ratio of the sodium selenite or sodium selenate to the VC is adjusted to 1 (3-5), and the active nano selenium-chitosan compound is obtained after even stirring.
In one embodiment of the present invention, in the step (2), the protein raw material (soybean or soybean meal or black soybean): flour or pulverized parched wheat100:15-30 (dry basis); cleaning semen glycines or semen Sojae Atricolor, soaking at normal temperature for 8-12h, moistening bean cake with 0.8 times of water for 30min, and steaming and boiling the above protein materials at 135 deg.C for 120-; premixing Aspergillus oryzae (Aspergillus oryzae) or Aspergillus sojae (Aspergillus sojae) with flour or pulverized parched semen Tritici Aestivi in an inoculation amount of 5 × 105-5×106CFU/g raw material, cooling the above cooked protein material to about 40 deg.C, mixing with the above flour inoculated with Aspergillus spore or pulverized parched wheat, and culturing the mixture at 28-30 deg.C for 40-48h to obtain Daqu; preparing saline water with concentration of 8-22% (w/w), adding active nano selenium-chitosan compound into the saline water, and mixing the yeast and the saline water at a ratio of 1:1-2.5(w/v) to prepare mash so that the selenium content reaches 10-100 mu M/L of the sauce mash; fermenting the prepared soy sauce mash at 30-45 ℃ for 30-180 days, and carrying out ultrasonic treatment on the soy sauce mash when the soy sauce mash is fermented for 5-90 days so as to promote the active selenium to be crosslinked and combined with protein, amino acid, polypeptide and polysaccharide in the soy sauce to further stabilize the active selenium, wherein the ultrasonic conditions are as follows: the frequency is 20-70kHz, the ultrasonic intensity is 10-80W/L, and the ultrasonic time is 60S-20 min; squeezing or spraying oil on the sauce mash after fermentation to obtain raw soy sauce; filtering the raw soy sauce with diatomite, sterilizing (85-130 deg.C/30S-30 min), and packaging to obtain high-stability soy sauce rich in active selenium.
[ advantageous effects ]
Compared with the conventional soy sauce and the selenium-rich soy sauce, the invention has the following advantages and beneficial effects:
(1) the selenium-rich soy sauce produced by the method has outstanding safety and stability, and does not have selenium precipitation or color change in the quality guarantee period of 180 days.
(2) The ultrasonic wave has the effects of mechanical stirring, perturbation, reduction of chemical reaction activation energy, cavitation, heat and the like, and under the conditions of proper frequency, power density, action time and the like, the ultrasonic wave can desorb the active nano selenium from the original template with weaker binding force, so as to promote the active nano selenium to be combined with the template which is easier to adsorb or react, and finally achieve the purpose of stabilization. The ultrasonic technology is utilized to remarkably promote the crosslinking and combination of the active nano selenium and amino acid, peptide and polysaccharide in the soy sauce, remarkably improve the content and conversion rate of organic selenium in the soy sauce, and further improve the safety and bioavailability of the selenium-enriched soy sauce.
(3) The invention discloses a preparation method of high-stability active selenium soy sauce by taking soy sauce which is an essential seasoning for the public as a carrier, reasonably selecting the adding time of active nano selenium and combining an active nano selenium-chitosan compound preparation technology and an ultrasonic technology. The invention can provide powerful support for improving the quality and efficiency of soy enterprises, improving the market competitiveness of products and improving the health level of Chinese people.
(4) The invention develops a preparation method of soy sauce rich in active nano-selenium with high stability by combining chemical reduction and ultrasonic treatment, the soy sauce produced by the method has obviously improved safety, stability and organic selenium content, and has important significance for preventing diseases related to selenium deficiency. The high-stability soy sauce produced by the technology of the invention does not increase the production cost (0.2 yuan/L soy sauce) obviously, but increases the added value of the product obviously, thus having good market prospect. Therefore, the invention has important economic value and social significance.
Drawings
FIG. 1 shows the turbidity change of nano selenium soy sauce produced by adding the technology of the invention and the technology of the prior invention patent.
Note: (1) comparison: the commercially available soy sauce without exogenous selenium is added with the patent nano selenium: the soy sauce with the nano-selenium added in the amount of 2000 mug/L prepared by the method of example 1 is added with the nano-selenium: the soy sauce prepared by adopting the technology disclosed by CN101176546A and with the nano-selenium addition amount of 2000 mug/L; (2) the OD value was obtained by diluting the soy sauce sample 10 times.
Detailed Description
The invention relates to a method for measuring the content of total Selenium, organic Selenium and inorganic Selenium, which refers to the methods of GB 5009.93-2017 and JingDawei et al (Selenium encirclement, front quality and yield of inorganic jujube as infected by the addition of sodium selenite [ J ]. Scientia Horticulturae,2017,225, 1-5).
Example 1 production of high-stability active-enriched Nano-selenium Soy sauce Using Soybean meal as protein Material
(1) Preparing an active nano selenium-chitosan compound: 0.1g of chitosan (degree of deacetylation: 70%) is added to 100mL of water, 0.1mL of glacial acetic acid is added while stirring, and the mixture is stirred uniformly to obtain a chitosan solution. Slowly adding sodium selenite into the chitosan solution, adjusting the concentration of the sodium selenite solution to 1mM/L, and stirring uniformly. And (3) slowly adding VC into the sodium selenite-chitosan solution, adjusting the molar ratio of the sodium selenite to the VC to be 1:1, and uniformly stirring to obtain the active nano selenium-chitosan compound.
(2) Preparing the soy sauce rich in active selenium with high stability: raw material selection and proportioning: bean pulp: flour 100:10 (dry matter basis). Moistening bean cake with 0.8 times of water for 30min, and steaming at 100 deg.C for 180 min. Premixing Aspergillus oryzae (Aspergillus oryzae) spore with flour at an inoculation amount of 1 × 105And (3) cooling the steamed soybean meal to about 40 ℃ by CFU/g raw material, fully mixing the cooked soybean meal with the flour inoculated with aspergillus oryzae, and culturing the mixture at 20 ℃ for 60 hours to obtain the yeast. Preparing 5% (w/w) saline water, adding active nano selenium-chitosan compound into the saline water, and mixing the Daqu and the saline water according to the ratio of 1:0.8(w/v) to prepare fermented liquor so that the selenium content reaches 1 mu M/L; the prepared soy sauce mash is fermented for 15 days at the temperature of 60 ℃, and is subjected to ultrasonic treatment when the soy sauce mash is fermented for 1 day so as to promote the crosslinking and combination of the active nano selenium and protein, amino acid, polypeptide and polysaccharide in the soy sauce to further stabilize the active selenium, wherein the ultrasonic conditions are as follows: the frequency is 18kHz, the ultrasonic intensity is 1W/L, and the ultrasonic time is 60 min. And squeezing the soy sauce mash after the fermentation is finished to obtain the raw soy sauce. Filtering the raw soy sauce with diatomite, sterilizing (60 ℃/60min) and filling to obtain the soy sauce rich in active selenium with high stability.
After the high-stability active selenium-rich soy sauce is placed at normal temperature for 180 days, no selenium crystal and color change are seen. The total selenium content is 9.3 mug/100 mL, wherein, the organic selenium content and the inorganic selenium content are respectively 7.1 mug/100 mL and 2.2 mug/100 mL.
Comparative example 1 preparation of Soy sauce without addition of active Nano selenium-Chitosan Complex
The preparation of soy sauce without adding active nano selenium-chitosan complex is carried out according to the following steps:
1) raw material selection and proportioning:
bean pulp: flour 100:10 (dry matter basis). Pretreatment of soybean meal: moistening bean cake with 0.8 times of water for 30min, and steaming at 100 deg.C for 180 min.
2) Premixing Aspergillus oryzae (Aspergillus oryzae) spore with flour at an inoculation amount of 1 × 105CFU/g raw material; cooling the soybean meal cooked in the step 1) to about 40 ℃, fully mixing the soybean meal with the flour inoculated with aspergillus oryzae, and culturing the mixture at 20 ℃ for 60 hours to obtain the yeast for making hard liquor.
3) Preparing 5% (w/w) saline water, mixing Daqu and saline water at a ratio of 1:0.8(w/v), making mash, and fermenting the prepared sauce mash at 60 deg.C for 15 days. Performing ultrasonic treatment on the raw soy sauce in the first day of fermentation, wherein the ultrasonic conditions are as follows: the frequency is 18kHz, the ultrasonic intensity is 1W/L, and the ultrasonic time is 60 min.
4) And squeezing the soy sauce mash after the fermentation is finished to obtain the raw soy sauce.
5) Filtering with diatomite, sterilizing (60 deg.C/60 min), and packaging to obtain soy sauce without active nanometer selenium-chitosan complex.
Control example 2 preparation of Soy sauce containing active Nano selenium-Chitosan Complex without ultrasonic treatment
The preparation of soy sauce containing active nano-selenium-chitosan complex without ultrasonic treatment was carried out according to the following steps:
1) raw material selection and proportioning: bean pulp: flour 100:10 (dry matter basis). Bean pulp pretreatment: moistening bean cake with 0.8 times of water for 30min, and steaming at 100 deg.C for 180 min.
2) Premixing Aspergillus oryzae (Aspergillus oryzae) spore with flour at an inoculation amount of 1 × 105CFU/g raw material, fully mixing the soybean meal cooked in the step 1) with flour inoculated with aspergillus oryzae when the temperature of the soybean meal is reduced to about 40 ℃, and culturing the mixture at 20 ℃ for 60 hours to obtain the yeast for making hard liquor.
3) Preparing 5% (w/w) saline water, adding active nano selenium-chitosan compound into the saline water, mixing the yeast and the saline water in a ratio of 1:0.8(kg/L) to prepare mash, enabling the selenium content in the mash to reach 1 mu M/L sauce mash, uniformly mixing, and fermenting at 60 ℃ for 15 days.
4) And squeezing the soy sauce mash after the fermentation is finished to obtain the raw soy sauce.
5) Filtering with diatomite, sterilizing (60 deg.C/60 min), and packaging to obtain selenium-rich soy sauce without stabilization.
Compared with the soy sauce of the comparative example 1 (without adding exogenous selenium), the total selenium, organic selenium and inorganic selenium contents of the soy sauce rich in active selenium in example 1 are respectively increased by 5.2 times, 5.8 times and 3.9 times, and the proportion of the organic selenium in the total selenium is increased by 6.1 percent.
After the selenium-enriched soy sauce of the comparative example 2 was left for 180 days, no gray to black selenium crystals appeared on the bottom of the bottle, and the total selenium content was the same as that of the selenium-enriched soy sauce of the above example 1, but the organic selenium content in the active selenium-enriched soy sauce of the example 1 was increased by 9.6% compared to the selenium-enriched soy sauce of the comparative example 2. The above analysis shows that the soy sauce rich in active selenium of example 1 has high stability, organic selenium content and conversion rate, and has higher nutritive value and health care function than the common soy sauce and the soy sauce rich in selenium produced by the conventional process.
Example 2 production of high-stability active-enriched Nano-selenium Soy sauce from Soy bean
(1) Preparing an active nano selenium-chitosan compound: 5g of chitosan (degree of deacetylation: 98%) is added to 100mL of water, 10mL of hydrochloric acid is added while stirring, and the mixture is stirred uniformly to obtain a chitosan solution. Slowly adding sodium selenate into the chitosan solution, adjusting the concentration of sodium selenate to 500mM/L, and uniformly stirring. And (3) slowly adding VC into the sodium selenate-chitosan solution, adjusting the molar ratio of the sodium selenate to the VC to be 1:10, and uniformly stirring to obtain the active nano selenium-chitosan compound.
(2) Preparing the soy sauce rich in active selenium with high stability: raw material selection and proportioning: soybean: crushed roasted wheat at 100:50 (calculated as dry matter). Cleaning semen glycines, soaking at normal temperature for 16 hr, and steaming at 140 deg.C for 5 min. Premixing Aspergillus sojae (Aspergillus sojae) with pulverized parched semen Tritici Aestivi in an inoculation amount of 1 × 107Cooling the above cooked soybean to about 40 deg.C, mixing with the above pulverized parched wheat inoculated with Aspergillus sojae, and culturing the mixture at 32 deg.C for 36 hr to obtain Daqu. Preparing 25% (w/w) saline water, adding active nano selenium-chitosan composite into the saline waterMixing Daqu and saline water at a ratio of 1:4(w/v) to prepare mash, so that the selenium content reaches 300 μ M/L of the sauce mash; the prepared soy sauce mash is fermented for 2 years at 10 ℃, and is subjected to ultrasonic treatment when the soy sauce mash is fermented for 90 days so as to promote the active nano selenium to be crosslinked and combined with protein, amino acid, polypeptide and polysaccharide in the soy sauce to further stabilize the active selenium, wherein the ultrasonic conditions are as follows: frequency 100kHz, ultrasonic intensity 100W/L and ultrasonic time 30S. And squeezing the soy sauce mash after the fermentation is finished to obtain the raw soy sauce. Filtering the raw soy sauce with diatomite, sterilizing (140 ℃/10S) and filling to obtain the soy sauce rich in active selenium with high stability.
After the soy sauce rich in active selenium with high stability is placed for 180 days at normal temperature, no selenium crystal and no color change are seen. The total selenium content is 2343.6 μ g/100mL, wherein the organic selenium content and the inorganic selenium content are 2050.7 μ g/100mL and 292.9 μ g/100mL respectively.
Comparative example 3 preparation of Soy sauce without addition of active Nano selenium-Chitosan Complex
The preparation of soy sauce without adding active nano selenium-chitosan complex is carried out according to the following steps:
1) raw material selection and proportioning:
soybean: crushed roasted wheat at 100:50 (calculated as dry matter). Pretreatment of soybeans: cleaning semen glycines, soaking at normal temperature for 16 hr, and steaming at 140 deg.C for 5 min.
2) Premixing Aspergillus sojae (Aspergillus sojae) spore with pulverized parched semen Tritici Aestivi, with inoculation amount of 1 × 107CFU/g raw material; cooling the cooked soybean in the step 1) to about 40 ℃, fully mixing the soybean with the fried wheat inoculated with the aspergillus sojae spores, and culturing the mixture at 20 ℃ for 36 hours to obtain the yeast.
3) Preparing 25% (w/w) saline water, mixing Daqu and saline water at a ratio of 1:4(w/v), making into mash, and fermenting the prepared sauce mash at 10 deg.C for 2 years. And (3) performing ultrasonic treatment on the raw soy sauce at the 90 th day of fermentation, wherein the ultrasonic conditions are as follows: frequency 100kHz, ultrasonic intensity 100W/L and ultrasonic time 30 s.
4) And squeezing the soy sauce mash after the fermentation is finished to obtain the raw soy sauce.
5) Filtering with diatomite, sterilizing (140 deg.C/10S), and packaging to obtain soy sauce without active nanometer selenium-chitosan complex.
Comparative example 4 preparation of Soy sauce containing active Nano selenium-Chitosan Complex without ultrasonic treatment
The preparation of soy sauce containing active nano-selenium-chitosan complex without ultrasonic treatment was carried out according to the following steps:
1) raw material selection and proportioning:
soybean: crushed roasted wheat at 100:50 (calculated as dry matter). Pretreatment of soybeans: cleaning semen glycines, soaking at normal temperature for 16 hr, and steaming at 140 deg.C for 5 min.
2) Premixing Aspergillus sojae (Aspergillus sojae) spore with pulverized parched semen Tritici Aestivi, with inoculation amount of 1 × 107CFU/g raw material; cooling the cooked soybean in the step 1) to about 40 ℃, fully mixing the soybean with the fried wheat inoculated with the aspergillus sojae spores, and culturing the mixture at 20 ℃ for 36 hours to obtain the yeast.
3) Preparing 25% (w/w) saline water, adding active nano selenium-chitosan compound into the saline water, mixing the yeast and the saline water at a ratio of 1:4(w/v) to prepare a moromi, enabling the selenium content to reach 300 mu M/L, and fermenting the prepared moromi at 10 ℃ for 2 years.
4) And squeezing the soy sauce mash after the fermentation is finished to obtain the raw soy sauce.
5) Filtering with diatomite, sterilizing (140 deg.C/10S), and packaging to obtain soy sauce without active nanometer selenium-chitosan complex.
Compared with the soy sauce of the comparison example 3 (without adding exogenous selenium), the total selenium, organic selenium and inorganic selenium contents of the soy sauce rich in active selenium in the example 2 are respectively increased by 1561.4, 1952.0 and 649.9 times, and the proportion of the organic selenium in the total selenium is increased by 17.3 percent.
In the selenium-enriched soy sauce of comparative example 4 (in which sodium selenite was added in the same amount and for the same time without sonication), after standing for 180 days, more gray to black selenium crystals (no activity) appeared on the bottom of the soy sauce bottle, whereas gray to black selenium crystals did not appear on the bottom of the soy sauce bottle of example 2. In addition, the selenium-rich soy sauce of example 2 had an organic selenium content increased by 14.3% over the selenium-rich soy sauce of comparative example 4. The above analysis shows that the soy sauce rich in active selenium of example 2 has high stability, organic selenium content and conversion rate, and has higher nutritive value and health care function than the common soy sauce and the soy sauce rich in selenium produced by the conventional process.
Example 3 production of high-stability active-enriched Nano-selenium Soy sauce from Black Soybean as protein Material
(1) Preparing an active nano selenium-chitosan compound: 1g of chitosan (deacetylation degree 85%) is added into 100mL of water, 1mL of sulfuric acid is added while stirring, and the mixture is stirred uniformly to obtain a chitosan solution. Slowly adding sodium selenite into the chitosan solution, adjusting the concentration of sodium selenite to 50mM/L, and stirring well. And (3) slowly adding VC into the sodium selenite-chitosan solution, adjusting the molar ratio of the sodium selenite to the VC to be 1:3, and uniformly stirring to obtain the active nano-selenium.
(2) Preparing the soy sauce rich in active selenium with high stability: raw material selection and proportioning: black bean: flour 100:30 (dry matter basis). Cleaning semen Sojae Atricolor, soaking at normal temperature for 10 hr, and steaming at 120 deg.C for 30 min. Mixing Aspergillus oryzae (Aspergillus oryzae) with flour, and inoculating at an inoculum size of 1 × 106And (3) cooling the steamed black beans to about 40 ℃ according to the CFU/g raw materials, fully mixing the steamed black beans with the flour inoculated with the aspergillus spores, and culturing the mixture at 28 ℃ for 48 hours to obtain the yeast. Preparing 20% (w/w) saline water, adding active nano selenium-chitosan compound into the saline water, and mixing the Daqu and the saline water according to the ratio of 1:2.5(w/v) to prepare fermented liquor so that the selenium content reaches 50 mu M/L of fermented sauce liquor; the prepared soy sauce mash is fermented for 180 days at the temperature of 30 ℃, and is subjected to ultrasonic treatment when the soy sauce mash is fermented for 10 days so as to promote the crosslinking and combination of the active nano selenium and the protein, amino acid, polypeptide and polysaccharide in the soy sauce to further stabilize the active selenium, wherein the ultrasonic conditions are as follows: frequency of 40kHz, ultrasonic intensity of 50W/L and ultrasonic time of 20 min. And squeezing the soy sauce mash after the fermentation is finished to obtain the raw soy sauce. Filtering the raw soy sauce with diatomite, sterilizing (100 ℃/10min) and filling to obtain the soy sauce rich in active selenium with high stability.
After the soy sauce rich in active selenium with high stability is placed for 180 days at normal temperature, no selenium crystal and no color change are seen. The total selenium content is 392.1 μ g/100mL, wherein the organic selenium content and the inorganic selenium content are 349.4 μ g/100mL and 42.7 μ g/100mL respectively.
Comparative example 5 preparation of Soy sauce without addition of active Nano selenium-Chitosan Complex
The preparation of soy sauce without adding active nano selenium-chitosan complex is carried out according to the following steps:
1) raw material selection and proportioning:
black bean: flour 100:30 (dry matter basis). Pretreatment of black beans: cleaning semen glycines, soaking at normal temperature for 10 hr, and steaming at 120 deg.C for 30 min.
2) Premixing Aspergillus oryzae (Aspergillus oryzae) spore with pulverized flour at an inoculation amount of 1 × 106CFU/g raw material; cooling the cooked soybean in the step 1) to about 40 ℃, fully mixing the soybean with the flour inoculated with the aspergillus oryzae spores, and culturing the mixture at 28 ℃ for 48 hours to obtain the yeast for making hard liquor.
3) Preparing 20% (w/w) saline water, mixing Daqu and saline water at a ratio of 1:2.5(w/v), making mash, and fermenting the prepared sauce mash at 30 deg.C for 180 days. And (3) performing ultrasonic treatment on the raw soy sauce at the 10 th day of fermentation, wherein the ultrasonic conditions are as follows: frequency of 40kHz, ultrasonic intensity of 50W/L and ultrasonic time of 20 min.
4) And squeezing the soy sauce mash after the fermentation is finished to obtain the raw soy sauce.
5) Filtering with diatomite, sterilizing (100 deg.C/10 min), and packaging to obtain soy sauce without active nanometer selenium-chitosan complex.
Control example 6 preparation of Soy sauce containing active Nano selenium-Chitosan Complex without ultrasonic treatment
The preparation of soy sauce containing active nano-selenium-chitosan complex without ultrasonic treatment was carried out according to the following steps:
1) raw material selection and proportioning:
black bean: flour 100:30 (dry matter basis). Pretreatment of black beans: cleaning semen glycines, soaking at normal temperature for 10 hr, and steaming at 120 deg.C for 30 min.
2) Premixing Aspergillus oryzae (Aspergillus oryzae) spore with pulverized flour at an inoculation amount of 1 × 106CFU/g raw material; cooling the soybean steamed in the step 1) toMixing with flour inoculated with Aspergillus oryzae spore at about 40 deg.C, and culturing at 28 deg.C for 48 hr to obtain Daqu.
3) Preparing 20% (w/w) saline water, adding active nano selenium-chitosan compound into the saline water, mixing the yeast and the saline water in a ratio of 1:2.5(w/v) to prepare a moromi, enabling the selenium content to reach 50 mu M/L, and fermenting the prepared moromi for 180 days at 30 ℃.
4) And squeezing the soy sauce mash after the fermentation is finished to obtain the raw soy sauce.
5) Filtering with diatomite, sterilizing (100 deg.C/10 min), and packaging to obtain soy sauce without active nanometer selenium-chitosan complex.
Compared with the soy sauce of the comparison example 5 (without adding exogenous selenium), the total selenium, organic selenium and inorganic selenium contents of the soy sauce rich in active selenium in the example 3 are respectively increased by 260.4 times, 331.8 times and 93.9 times, and the proportion of the organic selenium in the total selenium is increased by 18.9 percent.
After the selenium-enriched soy sauce of the comparative example 6 was left for 180 days, a small amount of gray to black selenium crystals appeared on the bottom of the bottle, whereas gray to black selenium crystals did not appear on the bottom of the soy sauce of the example 3. In addition, the organic selenium content of the soy sauce of example 3 was increased by 10.6% compared to the selenium-rich soy sauce of comparative example 6. The above analysis shows that the soy sauce rich in active selenium produced by the method of example 3 has high stability, high organic selenium content and high conversion rate, and has higher nutritional value and health care function than the common soy sauce and the soy sauce rich in selenium produced by the conventional process.
Influence of chitosan concentration and deacetylation degree and molar ratio of selenium to VC on stability of active nano selenium-chitosan compound
Preparing an active nano selenium-chitosan compound: respectively adding 0.1g, 1.0g, 2.5g, 3.5g and 5.0g of chitosan (degree of deacetylation 70%, 80%, 85%, 90% and 98%) into 100mL of water, adding 0.1mL of glacial acetic acid while stirring, and stirring to obtain chitosan solution. Slowly adding sodium selenite into the chitosan solution, adjusting the concentration of the sodium selenite solution to 1mM/L, and stirring uniformly. And (3) slowly adding VC into the sodium selenite-chitosan solution, adjusting the molar ratio of the sodium selenite to the VC to be 1:1, 1:2.5, 1:5, 1:7 and 1:10, and uniformly stirring to obtain the active nano selenium-chitosan compound. The resulting product was allowed to stand at ambient temperature and the time for the first precipitation of the complex was observed and recorded. As a result, as shown in Table 1, the stability of the complex was improved as the chitosan concentration was increased, the degree of deacetylation was increased, and the amount of Vc was increased.
TABLE 1 influence of Chitosan concentration, degree of deacetylation and selenium and Vc molar ratio on the stability of active nano-selenium-chitosan complexes
Note: when the concentration of the chitosan is changed, the deacetylation degree and the molar ratio of selenium to Vc are respectively 85% and 1: 5; when the deacetylation degree of the chitosan is changed, the concentration of the chitosan and the molar ratio of selenium to Vc are respectively 1% and 1: 5; the chitosan concentration and the deacetylation degree sum were 1% and 85%, respectively, when the molar ratio of selenium to Vc was varied.
Influence of ultrasonic conditions (frequency, intensity and time) on quality of selenium-enriched soy sauce
Based on the preparation method of example 1, selenium-rich soy sauce was prepared by adjusting the ultrasonic conditions (frequency, intensity, time), and after standing at room temperature for 180 days, the total selenium, organic selenium and inorganic selenium contents were measured. The results are shown in table 2 below:
TABLE 2 Effect of ultrasound conditions on selenium content in Soy sauce
Note: in table 2, (1) soy sauce was prepared based on the preparation method of example 1, and the influence of ultrasonic conditions on various selenium contents in soy sauce was examined; (2) when the influence of frequency on the content of various selenium in the soy sauce is inspected, the ultrasonic intensity and the ultrasonic time are 1W/L and 60 min; when the influence of the intensity on the contents of various selenium in the soy sauce is inspected, the ultrasonic frequency and the ultrasonic time are 18kHz and 60 min; when the influence of time on the contents of various selenium in the soy sauce is examined, the ultrasonic intensity and frequency are 1W/L and 18 kHz; (3) the experimental data are the average of the results of 3 experiments.
As can be seen from table 2, the ultrasonic frequency, ultrasonic intensity and ultrasonic time have significant effects on the contents of organic selenium and inorganic selenium in the soy sauce, but have no effect on the total selenium content.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A method for preparing soy sauce rich in active selenium is characterized in that the active selenium is nano-selenium, chitosan, selenious acid or sodium selenate, VC and glacial acetic acid or sulfuric acid are utilized to prepare an active nano-selenium-chitosan compound, soybeans or bean pulp or black beans and flour or crushed parched wheat are taken as raw materials, Aspergillus oryzae (Aspergillus oryzae) or Aspergillus sojae is taken as a fermentation strain to prepare the soy sauce by fermentation, the active nano-selenium-chitosan compound is added into soy sauce mash in the fermentation process, and the soy sauce mash is treated by ultrasonic waves, so that the nano-selenium is stably existed in the soy sauce.
2. The method for preparing soy sauce rich in active selenium as claimed in claim 1, wherein the preparation method of active nano selenium-chitosan complex comprises the following steps:
1) adding 0.1-5g of chitosan with deacetylation degree of 70-98% into 100mL of water, adding 0.1-10mL of glacial acetic acid or hydrochloric acid or sulfuric acid while stirring, and stirring uniformly to obtain a chitosan solution;
2) slowly adding sodium selenite or sodium selenate into the chitosan solution in the step 1), adjusting the concentration of the sodium selenite or sodium selenate in the solution to be 1-500mM/L, and uniformly stirring;
3) slowly adding vitamin C into the sodium selenite or sodium selenate-chitosan solution, adjusting the molar ratio of the sodium selenite or sodium selenate to the vitamin C to 1 (1-10), and stirring uniformly to obtain the active nano selenium-chitosan compound.
3. The method for preparing soy sauce containing organic selenium as claimed in claim 1, wherein the process of preparing soy sauce by fermentation comprises the steps of:
1) raw material selection and proportioning: the ratio of the protein raw material to the flour or the crushed fried wheat is 100:10-50, and the protein raw material is soybean or soybean meal or black soybean;
2) pretreatment of raw materials: soaking or moistening protein material with water, and steaming;
3) preparing the yeast for making hard liquor: premixing Aspergillus oryzae (Aspergillus oryzae) or Aspergillus sojae (Aspergillus sojae) with flour or crushed fried wheat, inoculating Aspergillus oryzae (Aspergillus oryzae) or Aspergillus sojae (Aspergillus sojae), fully mixing the protein raw material steamed in the step 2) with the flour inoculated with Aspergillus spores or the crushed fried wheat when the temperature is reduced to 38-42 ℃, and culturing the mixture at 20-32 ℃ for 36-60 hours to obtain Daqu;
4) preparing mash and adding active nano selenium: preparing saline water with mass concentration of 5-25%, adding active nano selenium-chitosan compound into the saline water, mixing the active nano selenium-chitosan compound with the ratio of Daqu to the saline water of 1kg (0.8-4) L to prepare mash, enabling the selenium content in the mash to reach 1-300 mu M/L sauce mash, and uniformly mixing;
5) and (3) stabilizing active selenium: fermenting the soy sauce mash obtained in the step 4) at the temperature of 10-60 ℃ for 15 days to 2 years, and carrying out ultrasonic treatment on the soy sauce mash when the soy sauce mash is fermented for 1-180 days to promote crosslinking and combination of the active nano selenium and protein, amino acid, polypeptide and polysaccharide in fermentation liquor to further stabilize the active selenium, wherein the ultrasonic conditions are as follows: the frequency is 18-100kHz, the ultrasonic intensity is 1-100W/L, and the ultrasonic time is 30S-60 min;
6) squeezing or oil spraying: squeezing or spraying oil on the sauce mash after fermentation to obtain raw soy sauce;
7) filtering, sterilizing and filling: filtering the raw soy sauce with diatomite, sterilizing and filling to obtain the soy sauce with high stability and rich active selenium.
4. The method for preparing soy sauce rich in active selenium as claimed in claim 3, wherein the soy bean or black bean is washed and soaked at room temperature for 4-16h, the soybean meal is soaked in 0.7-1.0 times of water for 10-30min, and the protein material is cooked at 140 ℃ for 5-180min under the conditions of 100-.
5. The method of claim 3, wherein the amount of Aspergillus oryzae (Aspergillus oryzae) or Aspergillus sojae (Aspergillus sojae) is 1X 105-1×107CFU/g raw flour or pulverized parched wheat.
6. The method for preparing soy sauce containing organoselenium as claimed in claim 1, wherein 0.5-3g of chitosan with deacetylation degree of 85-95% is added to 100mL of water, 1-6mL of glacial acetic acid or hydrochloric acid or sulfuric acid is further added, and the mixture is stirred uniformly; then slowly adding sodium selenite or sodium selenate into the chitosan solution, adjusting the concentration of the sodium selenite or sodium selenate solution to 10-100mM/L, and uniformly stirring; finally, slowly adding vitamin C into the sodium selenite or sodium selenate-chitosan solution, adjusting the molar ratio of the sodium selenite or sodium selenate to the vitamin C to be 1 (3-5), and uniformly stirring to obtain the active nano selenium-chitosan compound.
7. The method of claim 3, wherein the soy sauce rich in active selenium,
protein raw material (soybean or soybean meal or black bean): flour or crushed fried wheat at a ratio of 100: 15-30; cleaning semen glycines or semen Sojae Atricolor, soaking at normal temperature for 8-12h, moistening bean cake with 0.8 times of water for 30min, and steaming and boiling the above protein materials at 135 deg.C for 120-;
premixing Aspergillus oryzae (Aspergillus oryzae) or Aspergillus sojae (Aspergillus sojae) with flour or pulverized parched semen Tritici Aestivi in an inoculation amount of 5 × 105-5×106CFU/g raw material, cooling the above cooked protein material to 40 deg.C, mixing with the above flour inoculated with Aspergillus spore or pulverized parched wheat, and culturing the mixture at 28-30 deg.C for 40-48 hr to obtain Daqu;
preparing saline water with concentration of 8-22% (w/w), adding active nano selenium-chitosan compound into the saline water, and mixing the yeast and the saline water at a ratio of 1:1-2.5(w/v) to prepare mash so that the selenium content reaches 10-100 mu M/L of the sauce mash; fermenting the prepared soy sauce mash at 30-45 ℃ for 30-180 days, and carrying out ultrasonic treatment on the soy sauce mash when the soy sauce mash is fermented for 5-90 days so as to promote the active selenium to be crosslinked and combined with protein, amino acid, polypeptide and polysaccharide in the soy sauce to further stabilize the active selenium, wherein the ultrasonic conditions are as follows: the frequency is 20-70kHz, the ultrasonic intensity is 10-80W/L, and the ultrasonic time is 60S-20 min;
squeezing or spraying oil on the sauce mash after fermentation to obtain raw soy sauce; filtering the raw soy sauce with diatomite, sterilizing and filling to obtain the soy sauce with high stability and rich active selenium.
8. Soy sauce enriched with active selenium produced by the method of any one of claims 1 to 7.
9. The soy sauce according to claim 8, wherein active selenium is stably present and the content of organic selenium is significantly higher than that of a soy sauce containing no exogenous selenium.
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| CN114128869B (en) * | 2021-11-12 | 2023-07-18 | 江苏大学 | Production method of low-salt soy sauce |
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