CN116158509A - Preparation method of instant brown rice flour - Google Patents
Preparation method of instant brown rice flour Download PDFInfo
- Publication number
- CN116158509A CN116158509A CN202310270498.2A CN202310270498A CN116158509A CN 116158509 A CN116158509 A CN 116158509A CN 202310270498 A CN202310270498 A CN 202310270498A CN 116158509 A CN116158509 A CN 116158509A
- Authority
- CN
- China
- Prior art keywords
- brown rice
- temperature
- extrusion
- starch
- amylase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 235000021329 brown rice Nutrition 0.000 title claims abstract description 86
- 235000013312 flour Nutrition 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 4
- 238000001125 extrusion Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229920002472 Starch Polymers 0.000 claims abstract description 27
- 239000008107 starch Substances 0.000 claims abstract description 27
- 235000019698 starch Nutrition 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004382 Amylase Substances 0.000 claims abstract description 22
- 108010059892 Cellulase Proteins 0.000 claims abstract description 22
- 229940106157 cellulase Drugs 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000007873 sieving Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000007710 freezing Methods 0.000 claims abstract description 13
- 230000008014 freezing Effects 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims description 29
- 229940088598 enzyme Drugs 0.000 claims description 17
- 102000004190 Enzymes Human genes 0.000 claims description 16
- 108090000790 Enzymes Proteins 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 102000004139 alpha-Amylases Human genes 0.000 claims description 9
- 108090000637 alpha-Amylases Proteins 0.000 claims description 9
- 229940024171 alpha-amylase Drugs 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000010668 complexation reaction Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 102000013142 Amylases Human genes 0.000 abstract description 11
- 108010065511 Amylases Proteins 0.000 abstract description 11
- 235000019418 amylase Nutrition 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 229920002678 cellulose Polymers 0.000 abstract description 6
- 239000001913 cellulose Substances 0.000 abstract description 6
- 235000013339 cereals Nutrition 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 230000000975 bioactive effect Effects 0.000 abstract description 5
- 238000001953 recrystallisation Methods 0.000 abstract description 5
- 229940100486 rice starch Drugs 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 4
- 150000007965 phenolic acids Chemical class 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 238000005549 size reduction Methods 0.000 abstract description 2
- 235000013824 polyphenols Nutrition 0.000 description 43
- 150000008442 polyphenolic compounds Chemical class 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 12
- 238000000605 extraction Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 235000016709 nutrition Nutrition 0.000 description 7
- 230000001007 puffing effect Effects 0.000 description 7
- OHCQJHSOBUTRHG-KGGHGJDLSA-N FORSKOLIN Chemical compound O=C([C@@]12O)C[C@](C)(C=C)O[C@]1(C)[C@@H](OC(=O)C)[C@@H](O)[C@@H]1[C@]2(C)[C@@H](O)CCC1(C)C OHCQJHSOBUTRHG-KGGHGJDLSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229940074391 gallic acid Drugs 0.000 description 6
- 235000004515 gallic acid Nutrition 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 230000035764 nutrition Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- SUZLHDUTVMZSEV-UHFFFAOYSA-N Deoxycoleonol Natural products C12C(=O)CC(C)(C=C)OC2(C)C(OC(=O)C)C(O)C2C1(C)C(O)CCC2(C)C SUZLHDUTVMZSEV-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- OHCQJHSOBUTRHG-UHFFFAOYSA-N colforsin Natural products OC12C(=O)CC(C)(C=C)OC1(C)C(OC(=O)C)C(O)C1C2(C)C(O)CCC1(C)C OHCQJHSOBUTRHG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920000856 Amylose Polymers 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229920000945 Amylopectin Polymers 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008618 cell wall macromolecule catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- -1 dietary fiber Chemical class 0.000 description 1
- 235000013325 dietary fiber Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 230000035553 feeding performance Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229940068065 phytosterols Drugs 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000020985 whole grains Nutrition 0.000 description 1
Images
Classifications
-
- 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
- A23L7/00—Cereal-derived products; Malt products; Preparation or treatment thereof
- A23L7/10—Cereal-derived products
- A23L7/104—Fermentation of farinaceous cereal or cereal material; Addition of enzymes or microorganisms
- A23L7/107—Addition or treatment with enzymes not combined with fermentation with microorganisms
-
- 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
-
- 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
- A23L7/00—Cereal-derived products; Malt products; Preparation or treatment thereof
- A23L7/10—Cereal-derived products
- A23L7/115—Cereal fibre products, e.g. bran, husk
-
- 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
- A23L7/00—Cereal-derived products; Malt products; Preparation or treatment thereof
- A23L7/10—Cereal-derived products
- A23L7/117—Flakes or other shapes of ready-to-eat type; Semi-finished or partly-finished products therefor
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P30/00—Shaping or working of foodstuffs characterised by the process or apparatus
- A23P30/20—Extruding
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Manufacturing & Machinery (AREA)
- Cereal-Derived Products (AREA)
Abstract
The instant brown rice flour is produced through the synergistic action of medium temperature amylase and cellulase in gradient temperature controlling and high solid state extrusion reaction, the grain size reduction of starch and cellulose as main components, the fast liquid nitrogen freezing of the extrudate, the inhibition of slow retrogradation to form insoluble molecular chain, re-crystallization, drying, crushing and sieving. The method can effectively reduce the particle size of the brown rice, weaken the cooling regeneration of the brown rice starch to generate recrystallization, thereby greatly improving the water solubility index and gelatinization degree of the product, being easy to be mixed by adding water, reducing the density of the starch particles to smooth starch, reducing the loss of natural phenolic acid in the brown rice and retaining the bioactive substances in the brown rice.
Description
Technical Field
The invention belongs to the field of deep processing of grains, and in particular relates to a method for preparing instant brown rice powder by utilizing gradient temperature control of medium-temperature amylase and cellulase through an extrusion process and a time-space synergistic effect.
Background
Brown rice refers to whole, crushed, or flaked rice caryopsis, and the outer bran contains a variety of potential bioactive compounds including dietary fiber, minerals, vitamins, phytosterols, and phenolics, which have a variety of benefits to human health. However, the whole grain has a coarse and compact texture and is not easy to digest and absorb due to the large amount of bran wax and fiber substances contained in the cortex, and the traditional processing methods such as steaming, boiling, baking and the like can cause the loss of heat-sensitive bioactive phenolic compounds by pre-curing starch food raw materials at high temperature, and have the defects of incapability of continuous production and the like.
At present, many researches are carried out on treating brown rice through additional processes and equipment such as germination, ultrahigh pressure, ultrasound, microwaves and the like, and the treatment capacity is limited by the equipment; the processed brown rice cannot be boiled in one step without interval, and the time is long, or a great amount of energy is consumed due to the intermediate drying step and the like. Importantly, the taste of the cooked rice is not improved greatly, the cooked rice is still hard, and the required chewing time is long. Along with the acceleration of the life rhythm of people and the change of the working environment, the instant food is more and more favored by consumers, the instant cereal brewing meal replacement powder is one of the instant cereal brewing meal replacement powder, and the instant cereal meal replacement powder can be eaten after being mixed with hot water, and is simple and convenient to process. The existing processing modes of instant powder comprise extrusion puffing, roller drying, high Wen Fensui, spray drying and the like. These treatments have some promotion effect on the solubility of the brown rice flour, but have limitations, and it is difficult to ensure that nutrients in the brown rice are retained while the solubility of the brown rice flour is enhanced.
Disclosure of Invention
The invention aims to improve the solubility of the brown rice powder by optimizing the processing technology, ensure the nutrition characteristics of the brown rice and avoid pursuing one-sided effect. According to the invention, the multidirectional shearing force provided by the traditional extrusion cavity or screw configuration is coordinated with the targeted enzymolysis in a time-space manner, the retrogradation kinetics is changed through temperature control crystallization after extrusion, and the obtained brown rice powder is rich in bioactive substances, has high water solubility and gelatinization degree, and is convenient to brew. The brown rice processing machine meets the market demand, can retain the nutritional value of brown rice to a large extent, and improves the deep processing utilization degree of brown rice.
Specifically, the method utilizes the multi-physical field processing environment coupled in the extrusion cavity and amylase enzymolysis to promote hydrolysis and gelatinization of starch chains in the first half of processing by regulating and controlling the moisture content of brown rice powder, the gradient temperature of the processing environment and the cooperative mode of medium-temperature amylase/cellulase, so that a mild processing environment is formed, the retention of polyphenol substances in the second half is promoted, and the cellulase is added in the second half of processing to act on cell walls and the like to release part of combined polyphenol, so that the functional nutrition characteristics of the brown rice powder are enhanced. The extrudate is immediately put into liquid nitrogen for freezing, and crystallization is avoided by controlling the temperature to avoid brown rice starch cooling retrogradation, so that the gelatinization degree and the water absorption index of the extrudate are improved, and the brown rice starch instant freezing instant drink has the characteristic of being convenient to brew.
In order to realize the above summary, the technical scheme of the present application is as follows:
a method for preparing instant brown rice flour comprises the following steps: and co-extruding the medium-temperature alpha-amylase and the brown rice powder for 2.7-3 min, and adding a proper amount of cellulase in the half process of extrusion to perform co-extrusion for 1.3-1.5 min. Immediately after extrusion, the mixture is frozen in liquid nitrogen to inhibit starch retrogradation and complexation of phenolic substances and enzymes. And then the mixture is put into a freeze dryer for freeze drying for 48 hours, and the instant brown rice flour is obtained after grinding and sieving.
After Wen-amylase is added into the brown rice powder in a quantitative manner, the brown rice powder is processed and modified by utilizing a plurality of physical fields such as an amylase enzymolysis synergistic extrusion shearing field, a temperature field and the like, so that the hydrolysis and gelatinization of starch amylose and partial branched chains are promoted, the ordered structure of starch chains is destroyed, the water solubility index of starch crystallinity is reduced, the water solubility index is increased, the materials tend to be in a mixed flow state, and a mild extrusion environment is created; and then the cell wall degradation part of the combined phenolic substances are converted into free phenolic substances under the synergistic effect of the cellulase, and the diffusion and interaction of the free polyphenol in the starch matrix are enhanced on the basis of the action result of the first half Cheng Zhongwen amylase, so that the stable retention of the free polyphenol in the processing process is realized. Immediately after extrusion, liquid nitrogen is put into the mixture for low-temperature freezing, so that the movement speed of a starch chain can be slowed down, the crystallization retrogradation process of the starch chain is inhibited, the high water solubility of the starch is kept, and meanwhile, the complexation of free polyphenol and enzyme is inhibited, so that the nutrition characteristic of the starch is kept.
Wherein, the enzyme activity range of the intermediate Wen-amylase is as follows: 500-1500U/g; the enzyme activity range of the cellulase is as follows: 5-50U/g, the enzyme activity being defined as the amount of enzyme activity (U) added per gram of starch dry basis.
The co-extrusion treatment of the Wen-amylase and the brown rice flour at least comprises three temperature areas, wherein the treatment temperature of the three temperature areas is 60-70 ℃ and is increased one by one;
the co-extrusion after adding the cellulase at least comprises three temperature areas, the treatment temperature of the three temperature areas is 60-40 ℃, and the treatment temperature is reduced one by one.
In certain embodiments of the invention, the screw speed is set at 50 to 150r/min.
In certain embodiments of the present invention, the brown rice is ground and crushed prior to extrusion and sieved through a 60 mesh screen.
In certain embodiments of the invention, the moisture content of the mixed material of the complex enzyme and starch is adjusted to 15-45% before extrusion.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the traditional brown rice extrusion process, the method adopts a biological enzyme-extrusion combined means and a complex enzyme synergistic extrusion mode, and shear stress and mechanical energy input in a first stage are assisted by moderate temperature amylase to destroy the ordering of starch chains, so that starch is highly gelatinized and degraded in the extrusion process, the transition of material matrixes from solid state to fluid state is realized, starch is converted into thermoplastic starch in a uniform state, the surfaces of starch particles tend to be round and smooth, the molecular density of the starch is reduced, a flexible protection layer for functional small molecules is further formed, and a mild extrusion environment is created.
2. And in the second stage, cellulase is added to carry out enzymolysis on hard cellulose with rough texture, so that the conversion and degradation of part of insoluble macromolecular cellulose into soluble small-scale cellulose molecules are realized. On the basis, active small molecules such as antioxidant phenolic acid and the like are released, so that the conversion and stable retention of phenolic substances from a combined state to a free state are realized; meanwhile, the cellulose is introduced in the latter half of extrusion, so that the complexation of phenolic substances and enzymes can be effectively reduced, the combination of the phenolic substances and enzyme molecules is reduced, and the nutrition characteristics of the extruded product are maintained.
3. After the double-enzyme co-extrusion processing, the liquid nitrogen is utilized to carry out quick freezing, so as to slow down the rearrangement process of starch molecules (amylose and amylopectin), inhibit the cooling regeneration recrystallization of the brown rice starch after extrusion, and ensure that the processed product keeps high gelatinization degree and water absorption; meanwhile, the complexing action of the micromolecular phenols and the enzyme is inhibited, and the nutrition characteristic is maintained. The processing method provided by the invention is simple to operate, has high production capacity and good feeding performance, can be continuously operated, has higher retention rate of phenolic substances of the obtained brown rice flour on one hand and good nutritional functional characteristics, and has higher water solubility and gelatinization degree on the other hand, and is convenient to be used as an instant product for brewing. Has better application prospect in further developing deep processing products.
Drawings
FIG. 1 is a flow chart of the instant brown rice powder with small-scale particle size having antioxidant effect according to the present invention.
Fig. 2 is a 1000-fold Scanning Electron Microscope (SEM) micrograph of brown rice flour prepared according to the present invention. Wherein A is an untreated brown rice sample; and B, extruding the processed brown rice sample (5U/g of cellulase and 1000U/g of medium-temperature alpha-amylase).
Detailed Description
The instant brown rice flour is produced through the synergistic action of medium temperature amylase and cellulase in gradient temperature controlling and high solid state extrusion reaction, the grain size reduction of starch and cellulose as main components, the fast liquid nitrogen freezing of the extrudate, the inhibition of slow retrogradation to form insoluble molecular chain, re-crystallization, drying, crushing and sieving. The method can effectively reduce the particle size of the brown rice, weaken the cooling regeneration of the brown rice starch to generate recrystallization, thereby greatly improving the water solubility index and gelatinization degree of the product, being easy to be mixed by adding water, reducing the density of the starch particles to smooth starch, reducing the loss of natural phenolic acid in the brown rice and retaining the bioactive substances in the brown rice.
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The brown rice material used in the following examples was Ningjing No. 43. Wen-amylase from DEKE, CAS number 9000-92-4, or from Soy Bao, CATA8752; cellulases were purchased from creditor or microphone.
Example 1
(1) Crushing: pulverizing brown rice raw material with pulverizer, and sieving with 60 mesh sieve to obtain brown rice powder;
(2) And (3) batching: weighing a proper amount of medium Wen-amylase, adding into brown rice powder to make the medium-temperature alpha-amylase activity 1000U/g, and uniformly mixing; adding a proper amount of water to regulate the water content of the material to 30%, and homogenizing;
(3) Extruding and puffing, wherein the rotating speed of a screw is 100rpm, and the feeding speed is 4rpm;
(3.1) placing the brown rice flour treated in the step (2) into a feeding container of an extruder, setting the temperature of the first region to 60 ℃, the temperature of the second region to 65 ℃ and the temperature of the third region to 70 ℃, and extruding for 2.7min from the feeding to the third region.
(3.2) mixing 10U/g cellulase by setting the feed inlet, setting the temperature of four zones at 60 ℃, the temperature of five zones at 50 ℃ and the die temperature at 40 ℃, and extruding from four zones into six zones for 1.3min.
(4) Drying and crushing: and (3) immediately freezing the extrudate obtained in the step (4) in liquid nitrogen, transferring the frozen extrudate into a freeze dryer, freeze-drying the frozen extrudate at-48 ℃, crushing and sieving the frozen extrudate.
(5) And (3) measuring polyphenol content: sample 2g was taken, 20mL of 80% methanol solution was added, and shaking was performed for 10min, followed by centrifugation at 4000g for 5min. Repeating the extraction for 3 times, collecting supernatant, evaporating at 45deg.C under vacuum, and adding 80% methanol solution to constant volume to obtain free polyphenol. The residue after extraction of the free polyphenols was hydrolyzed at room temperature with 2m naoh under shaking for 3h. Then, the pH was adjusted to 1.5-2.0 with 6M hydrochloric acid, and extraction was performed three times with ethyl acetate. Ethyl acetate was collected, rotary evaporated to dryness and 80% methanol solution was added to fix the volume to give the bound polyphenol. Taking 0.5mL of polyphenol extract, adding 1mL of forskolin reagent for reaction for 6min, and adding 2mL of 15% Na 2 CO 3 The solution was reacted at room temperature in the absence of light for 2 hours, and then absorbance was measured at 760 nm. The results were compared to a standard curve of gallic acid solution and expressed as microgram gallic acid equivalent per gram dry weight sample (mgGAE/gDW).
(6) Water solubility index determination: take 2g of sample (W 0 ) Put into centrifuge tubes of known mass (W 1 ) Adding 25mL distilled water, shaking until the substances are completely dispersed, holding in water bath at 30deg.C for 30min, stirring for 30s at intervals of 10min, centrifuging at 4000r/min for 15min, and pouring the supernatant into a 500mL beaker (W 2 ) In which the mixture is baked at 105 ℃ to constant mass (W 3 ) Centrifugal tube (W) 4 )。
The brown rice flour prepared in this example contains 1.492 mg GAE/gDW, 0.731 mg GAE/gDW, and 2.224mg GAE/gDW, respectively, of free polyphenol, bound polyphenol and total phenol, which are significantly higher than the polyphenol content of the sample obtained by the conventional extrusion method. Samples WSI and WAI were 42.8% and 171.8%, respectively, with greatly improved quick solubility compared to the brown rice material and conventional extruded samples.
Example 2
(1) Crushing: pulverizing brown rice raw material with pulverizer, and sieving with 60 mesh sieve to obtain brown rice powder;
(2) And (3) batching: weighing a proper amount of medium Wen-amylase, adding into brown rice powder to make the medium-temperature alpha-amylase activity be 500U/g, and uniformly mixing; adding a proper amount of water to regulate the water content of the material to 20%, and homogenizing;
(3) Extrusion puffing: the screw speed was 150rpm and the feed rate was 4rpm;
(3.1) placing the brown rice flour treated in the step (2) into a feeding container of an extruder, setting the temperature of the first region to 60 ℃, the temperature of the second region to 65 ℃ and the temperature of the third region to 70 ℃, and extruding for 3min from the feeding to the third region.
(3.2) mixing 5U/g cellulase by setting the feed inlet, setting the temperature of four zones at 60 ℃, the temperature of five zones at 50 ℃ and the die temperature at 40 ℃, and extruding from four zones into six zones for 1.5min.
(4) Drying and crushing: and (3) immediately freezing the extrudate obtained in the step (4) in liquid nitrogen, transferring the frozen extrudate into a freeze dryer, freeze-drying the frozen extrudate at-48 ℃, crushing and sieving the frozen extrudate.
(5) And (3) measuring polyphenol content: sample 2g was taken, 20mL of 80% methanol solution was added, and shaking was performed for 10min, followed by centrifugation at 4000g for 5min. Repeating the extraction for 3 times, collecting supernatant, evaporating at 45deg.C under vacuum, and adding 80% methanol solution to constant volume to obtain free polyphenol. The residue after extraction of the free polyphenols was hydrolyzed at room temperature with 2m naoh under shaking for 3h. Then, the pH was adjusted to 1.5-2.0 with 6M hydrochloric acid, and extraction was performed three times with ethyl acetate. Ethyl acetate was collected, rotary evaporated to dryness and 80% methanol solution was added to fix the volume to give the bound polyphenol. Taking 0.5mL of polyphenol extract, adding 1mL of forskolin reagent for reaction for 6min, and adding 2mL of 15% Na 2 CO 3 The solution was reacted at room temperature in the absence of light for 2 hours, and then absorbance was measured at 760 nm. The results were compared to a standard curve of gallic acid solution and expressed as microgram gallic acid equivalent per gram dry weight sample (mgGAE/gDW).
(6) Water solubility index determination: take 2g of sample (W 0 ) Put into centrifuge tubes of known mass (W 1 ) In, add 25mL of distilled water, shaking until the material was completely dispersed, holding in a water bath at 30deg.C for 30min, stirring for 30s at intervals of 10min, centrifuging at 4000r/min for 15min, pouring the supernatant into a 500mL beaker (W 2 ) In which the mixture is baked at 105 ℃ to constant mass (W 3 ) Centrifugal tube (W) 4 )。
The brown rice flour prepared in the embodiment contains 1.5632, 0.523 and 2.0856mgGAE/gDW of free polyphenol, combined polyphenol and total phenol, which are remarkably higher than the polyphenol content reserved in the sample obtained by the traditional extrusion method. Samples WSI and WAI were 45.2% and 170.04%, respectively, with greatly improved quick solubility compared to the brown rice material and conventional extruded samples.
Example 3
(1) Crushing: pulverizing brown rice raw material with pulverizer, and sieving with 60 mesh sieve to obtain brown rice powder;
(2) And (3) batching: weighing a proper amount of medium Wen-amylase and cellulase, adding into brown rice powder, enabling the medium-temperature alpha-amylase activity to be 1500U/g, and uniformly mixing; adding a proper amount of water to regulate the water content of the material to 40%, and homogenizing;
(3) Extrusion puffing: the screw speed was 50rpm and the feed rate was 4rpm;
(3.1) placing the brown rice flour treated in the step (2) into a feeding container of an extruder, setting the temperature of the first region to 60 ℃, the temperature of the second region to 65 ℃ and the temperature of the third region to 70 ℃, and extruding for 2.7min from the feeding to the third region.
(3.2) mixing 50U/g cellulase by setting the feed inlet, setting the temperature of four zones at 60 ℃, the temperature of five zones at 50 ℃, the die temperature at 40 ℃, and extruding from four zones into six zones for 1.5min.
(4) Drying and crushing: and (3) immediately freezing the extrudate obtained in the step (4) in liquid nitrogen, transferring the frozen extrudate into a freeze dryer, freeze-drying the frozen extrudate at-48 ℃, crushing and sieving the frozen extrudate.
(5) And (3) measuring polyphenol content: sample 2g was taken, 20mL of 80% methanol solution was added, and shaking was performed for 10min, followed by centrifugation at 4000g for 5min. Repeating the extraction for 3 times, collecting supernatant, evaporating at 45deg.C under vacuum, and adding 80% methanol solution to constant volume to obtain free polyphenol. The residue after extraction of the free polyphenols was hydrolyzed at room temperature with 2m naoh under shaking for 3h. Then, the pH was adjusted to 1.5-2.0 with 6M hydrochloric acid, and extraction was performed three times with ethyl acetate. Ethyl acetate was collected, rotary evaporated to dryness and 80% methanol solution was added to fix the volume to give the bound polyphenol. Taking 0.5mL of polyphenol extract, adding 1mL of forskolin reagent for reaction for 6min, and adding 2mL of 15% Na 2 CO 3 The solution was reacted at room temperature in the absence of light for 2 hours, and then absorbance was measured at 760 nm. The results were compared to a standard curve of gallic acid solution and expressed as microgram gallic acid equivalent per gram dry weight sample (mgGAE/gDW).
(6) Water solubility index determination: take 2g of sample (W 0 ) Put into centrifuge tubes of known mass (W 1 ) Adding 25mL distilled water, shaking until the substances are completely dispersed, holding in water bath at 30deg.C for 30min, stirring for 30s at intervals of 10min, centrifuging at 4000r/min for 15min, and pouring the supernatant into a 500mL beaker (W 2 ) In which the mixture is baked at 105 ℃ to constant mass (W 3 ) Centrifugal tube (W) 4 )。
The brown rice flour prepared in this example contains 1.868, 0.898 and 2.0856mgGAE/gDW of free polyphenol, bonded polyphenol and total phenol, which are significantly higher than the polyphenol content retained in the sample obtained by the conventional extrusion method. Samples WSI and WAI were 40.3% and 178.22%, respectively, with greatly improved quick solubility compared to the brown rice material and conventional extruded samples.
Comparative example 1: the amylase and the cellulase are added simultaneously in the early stage of extrusion
(1) Crushing: pulverizing brown rice raw material with pulverizer, and sieving with 60 mesh sieve to obtain brown rice powder;
(2) And (3) batching: weighing a proper amount of medium Wen-amylase and cellulase, simultaneously adding into brown rice powder, enabling the medium-temperature alpha-amylase activity to be 1000U/g and the cellulase activity to be 10U/g, and uniformly mixing; adding a proper amount of water to regulate the water content of the material to 30%, and homogenizing;
(3) Extrusion puffing: placing the brown rice powder treated in the step (2) into a feeding container of an extruder, and setting the temperature of the first region to 60 ℃, the temperature of the second region to 60 ℃, the temperature of the third region to 65 ℃, the temperature of the fourth region to 65 ℃, the temperature of the fifth region to 70 ℃, the temperature of a die head to 70 ℃, the rotating speed of a screw to 100rpm and the feeding speed to 4rpm;
(4) Drying and crushing: and (3) immediately freezing the extrudate obtained in the step (4) in liquid nitrogen, transferring the frozen extrudate into a freeze dryer, freeze-drying the frozen extrudate at-48 ℃, crushing and sieving the frozen extrudate.
The brown rice flour prepared in this example contains 1.186 mg GAE/gDW, 0.708 mg GAE/gDW, 1.894mg GAE/gDW, 1.708 mg GAE/gDW, 1.894mg GAE/gDW, and 1.894mg GAE/gDW. Samples WSI and WAI were 39.8% and 169.6%, respectively, with greatly improved quick solubility compared to the brown rice material and conventional extruded samples.
Comparative example 2 addition of Medium temperature Amylase only
(1) Crushing: pulverizing brown rice raw material with pulverizer, and sieving with 60 mesh sieve to obtain brown rice powder;
(2) And (3) batching: weighing a proper amount of medium Wen-amylase, adding into brown rice powder to make the medium-temperature alpha-amylase activity 1000U/g, and uniformly mixing; adding a proper amount of water to regulate the water content of the material to 30%, and homogenizing;
(3) Extrusion puffing: placing the brown rice powder treated in the step (2) into a feeding container of an extruder, and setting the temperature of the first region to 60 ℃, the temperature of the second region to 60 ℃, the temperature of the third region to 65 ℃, the temperature of the fourth region to 65 ℃, the temperature of the fifth region to 70 ℃, the temperature of a die head to 70 ℃, the rotating speed of a screw to 100rpm and the feeding speed to 4rpm;
(4) Drying and crushing: and (3) immediately freezing the extrudate obtained in the step (4) in liquid nitrogen, transferring the frozen extrudate into a freeze dryer, freeze-drying the frozen extrudate at-48 ℃, crushing and sieving the frozen extrudate.
The brown rice flour prepared in the embodiment contains 1.216 mg GAE/gDW, 0.689 mg GAE/gDW and 1.905mg GAE/gDW, which are respectively higher than the polyphenol content reserved in the samples obtained by the traditional extrusion mode. Samples WSI and WAI were 37.4% and 173.2%, respectively, with greatly improved quick solubility compared to the brown rice material and conventional extruded samples.
Comparative example 3: the brown rice raw material is simply extruded and then subjected to enzymolysis
(1) Crushing: pulverizing brown rice raw material with pulverizer, and sieving with 60 mesh sieve;
(2) And (3) batching: adding proper amount of water to regulate the water content of brown rice material to 30%, and homogenizing;
(3) Extrusion puffing: placing the brown rice powder treated in the step (2) into a feeding container of an extruder, and setting the temperature of the first region to 60 ℃, the temperature of the second region to 60 ℃, the temperature of the third region to 65 ℃, the temperature of the fourth region to 65 ℃, the temperature of the fifth region to 70 ℃, the temperature of a die head to 70 ℃, the rotating speed of a screw to 100rpm and the feeding speed to 4rpm;
(4) Drying and crushing: and (3) immediately freezing the extrudate obtained in the step (4) in liquid nitrogen, transferring the frozen extrudate into a freeze dryer, freeze-drying the frozen extrudate at-48 ℃, crushing and sieving the frozen extrudate.
(5) 10g of extruded brown rice powder is taken, buffer solution is added, and the mixture is stirred into feed liquid with different concentrations.
(6) 1000U/g of medium-temperature amylase is added for water bath enzymolysis for 1h at 60 ℃, and 10U/g of cellulase is added for enzymolysis for 1h at 50 ℃.
The brown rice flour prepared in the embodiment contains free polyphenol, combined polyphenol and total phenol which are respectively 0.863, 0.698 and 1.561mgGAE/gDW, and the content of the free polyphenol, the combined polyphenol and the total phenol is obviously lower than that of the polyphenol reserved in the sample obtained by the enzyme-adding co-extrusion mode.
Claims (5)
1. A preparation method of instant brown rice flour is characterized in that: the method at least comprises the following steps: co-extrusion treatment is carried out on the medium-temperature alpha-amylase and brown rice powder for 2.7-3 min, and then cellulase is added for co-extrusion for 1.3-1.5 min; after extrusion, the mixture is put into liquid nitrogen for freezing, and the starch retrogradation process and the complexation of phenolic substances and enzymes are inhibited; then putting the mixture into a freeze dryer for freeze drying for 48 hours, grinding and sieving the mixture to obtain instant brown rice powder;
the enzyme activity range of the medium Wen-amylase is as follows: 500-1500U/g; the enzyme activity range of the cellulase is as follows: 5-50U/g, wherein the enzyme activity is defined as the enzyme activity amount (U) added into each gram of starch dry basis;
the co-extrusion treatment of the Wen-amylase and the brown rice flour at least comprises three temperature areas, wherein the treatment temperature of the three temperature areas is 60-70 ℃ and is increased one by one;
the co-extrusion after adding the cellulase at least comprises three temperature areas, the treatment temperature of the three temperature areas is 60-40 ℃, and the treatment temperature is reduced one by one.
2. The method according to claim 1, wherein the screw rotation speed is set to 50 to 150r/min.
3. The method of manufacturing as claimed in claim 1, wherein the brown rice flour is crushed and sieved through a 60-mesh sieve before extrusion.
4. The preparation method according to claim 1, wherein the water content of the mixture of medium-temperature alpha-amylase and brown rice flour is adjusted to 20-40 wt% before extrusion.
5. The method according to claim 1, wherein the treatment temperature of the freeze dryer is-48 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310270498.2A CN116158509B (en) | 2023-03-20 | 2023-03-20 | Preparation method of instant brown rice flour |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310270498.2A CN116158509B (en) | 2023-03-20 | 2023-03-20 | Preparation method of instant brown rice flour |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116158509A true CN116158509A (en) | 2023-05-26 |
CN116158509B CN116158509B (en) | 2024-05-28 |
Family
ID=86416472
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310270498.2A Active CN116158509B (en) | 2023-03-20 | 2023-03-20 | Preparation method of instant brown rice flour |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116158509B (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20150001057A (en) * | 2013-06-26 | 2015-01-06 | 도울바이오푸드영농조합법인 | Preparation method of puffed rice powder extruded with enzyme for ready-to-eat foods |
CN105755072A (en) * | 2016-04-11 | 2016-07-13 | 淄博汇创生物科技有限公司 | Low temperature extrusion-multienzyme synergistic degradation material pretreatment method |
CN106879945A (en) * | 2015-12-16 | 2017-06-23 | 北京朔方科技发展股份有限公司 | A kind of High Efficiency Solid-State digests the preparation method of coarse rice powder |
CN107212262A (en) * | 2017-04-05 | 2017-09-29 | 广东省农业科学院蚕业与农产品加工研究所 | A kind of brown rice local flavor instant nourishing powder and preparation method thereof |
CN112725312A (en) * | 2021-01-25 | 2021-04-30 | 浙江大学 | Preparation method of complex enzyme and resistant dextrin |
CN112890099A (en) * | 2021-03-05 | 2021-06-04 | 华南农业大学 | Instant purple brown rice powder rich in anthocyanin and preparation method thereof |
-
2023
- 2023-03-20 CN CN202310270498.2A patent/CN116158509B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20150001057A (en) * | 2013-06-26 | 2015-01-06 | 도울바이오푸드영농조합법인 | Preparation method of puffed rice powder extruded with enzyme for ready-to-eat foods |
CN106879945A (en) * | 2015-12-16 | 2017-06-23 | 北京朔方科技发展股份有限公司 | A kind of High Efficiency Solid-State digests the preparation method of coarse rice powder |
CN105755072A (en) * | 2016-04-11 | 2016-07-13 | 淄博汇创生物科技有限公司 | Low temperature extrusion-multienzyme synergistic degradation material pretreatment method |
CN107212262A (en) * | 2017-04-05 | 2017-09-29 | 广东省农业科学院蚕业与农产品加工研究所 | A kind of brown rice local flavor instant nourishing powder and preparation method thereof |
CN112725312A (en) * | 2021-01-25 | 2021-04-30 | 浙江大学 | Preparation method of complex enzyme and resistant dextrin |
CN112890099A (en) * | 2021-03-05 | 2021-06-04 | 华南农业大学 | Instant purple brown rice powder rich in anthocyanin and preparation method thereof |
Non-Patent Citations (3)
Title |
---|
张亮 等: "双酶预酶解协同挤压膨化改善发芽糙米粉冲调性的 工艺优化", 中国食品添加剂, no. 10, 31 December 2018 (2018-12-31), pages 140 - 149 * |
秦文 等: "食品加工原理", vol. 1, 30 June 2011, 中国质检出版社, pages: 95 - 96 * |
马永轩 等: "高温α-淀粉酶- 挤压膨化耦合处理对全谷物 糙米粉品质的影响", 食品科学技术学报, vol. 38, no. 1, 31 January 2020 (2020-01-31), pages 111 - 116 * |
Also Published As
Publication number | Publication date |
---|---|
CN116158509B (en) | 2024-05-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102349622B (en) | Preparation method of nutrition coarse rice powder | |
CN103300287B (en) | Health-care noodles made of mung bean hulls and production method thereof | |
CN105475796B (en) | A kind of preparation method of instant drink powder | |
US6265013B1 (en) | Selective nixtamalization process for the production of fresh whole corn masa, nixtamalized corn flour and derived products | |
JP7545015B2 (en) | How to make high-fiber, low-phytic acid potato oat cake | |
CN105685891A (en) | Instant whole lotus root powder containing highly-resistant starch and preparation method of instant whole lotus root powder containing highly-resistant starch | |
CN108967895A (en) | A kind of nutrition recombination rice and preparation method | |
CN106879940A (en) | A kind of preparation method of pure oatmeal | |
CN106616348A (en) | Banana and brown rice blended powder capable of relaxing bowels and preparation method thereof | |
CN113396995A (en) | Preparation method of matcha superfine powder | |
CN106879945A (en) | A kind of High Efficiency Solid-State digests the preparation method of coarse rice powder | |
CN108142826B (en) | Preparation method of ginkgo compound grain and ginkgo compound grain | |
CN107495327B (en) | Instant tremella wall-broken powder and preparation method thereof | |
CN116158509B (en) | Preparation method of instant brown rice flour | |
CN106578891A (en) | Sweet scented osmanthus stomach-invigorating corn brewing powder and preparation method thereof | |
CN110613084A (en) | Processing method of wall-broken bran powder through steam heat treatment | |
CN114027445A (en) | Preparation method for producing germinated glutinous brown rice powder with low glycemic index by microwave combined wet and heat treatment | |
CN109363124A (en) | A kind of method and application preparing potato dregs dietary fiber using cylinder drying | |
AU2021105255A4 (en) | Method for Preparing Dietary Fiber from Sweet Potato Residue by Using Drum Drying and Its Application | |
CN112262959A (en) | Processing method of high-gelatinization instant coarse cereal mixing powder with broken rice as main material | |
AU2021105529A4 (en) | Preparation method of purple sweet potato reconstituted powder with multi-grain and its application | |
CN112617106B (en) | Selenium-enriched Jin Maimian | |
CN108719784A (en) | A kind of production method of the nutrition fine dried noodles with weight losing function | |
CN114403344B (en) | Oat extract beneficial to maintaining oat flavor and preparation process thereof | |
CN116076663B (en) | Whole-grain highland barley semi-dry noodles and processing method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |