CN116790031A - Method for efficiently and directionally embedding zeaxanthin by granular cold water-soluble porous starch - Google Patents
Method for efficiently and directionally embedding zeaxanthin by granular cold water-soluble porous starch Download PDFInfo
- Publication number
- CN116790031A CN116790031A CN202310711728.4A CN202310711728A CN116790031A CN 116790031 A CN116790031 A CN 116790031A CN 202310711728 A CN202310711728 A CN 202310711728A CN 116790031 A CN116790031 A CN 116790031A
- Authority
- CN
- China
- Prior art keywords
- starch
- electric field
- zeaxanthin
- cold water
- porous starch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 265
- 235000019698 starch Nutrition 0.000 title claims abstract description 265
- 239000008107 starch Substances 0.000 title claims abstract description 263
- 239000001775 zeaxanthin Substances 0.000 title claims abstract description 110
- 229940043269 zeaxanthin Drugs 0.000 title claims abstract description 110
- JKQXZKUSFCKOGQ-JLGXGRJMSA-N (3R,3'R)-beta,beta-carotene-3,3'-diol Chemical compound C([C@H](O)CC=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C[C@@H](O)CC1(C)C JKQXZKUSFCKOGQ-JLGXGRJMSA-N 0.000 title claims abstract description 85
- JKQXZKUSFCKOGQ-LQFQNGICSA-N Z-zeaxanthin Natural products C([C@H](O)CC=1C)C(C)(C)C=1C=CC(C)=CC=CC(C)=CC=CC=C(C)C=CC=C(C)C=CC1=C(C)C[C@@H](O)CC1(C)C JKQXZKUSFCKOGQ-LQFQNGICSA-N 0.000 title claims abstract description 85
- QOPRSMDTRDMBNK-RNUUUQFGSA-N Zeaxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCC(O)C1(C)C)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C QOPRSMDTRDMBNK-RNUUUQFGSA-N 0.000 title claims abstract description 85
- JKQXZKUSFCKOGQ-LOFNIBRQSA-N all-trans-Zeaxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C JKQXZKUSFCKOGQ-LOFNIBRQSA-N 0.000 title claims abstract description 85
- KBPHJBAIARWVSC-XQIHNALSSA-N trans-lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C KBPHJBAIARWVSC-XQIHNALSSA-N 0.000 title claims abstract description 85
- 235000010930 zeaxanthin Nutrition 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000005684 electric field Effects 0.000 claims abstract description 146
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000003513 alkali Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 97
- 238000002360 preparation method Methods 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 22
- 238000007873 sieving Methods 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 235000013336 milk Nutrition 0.000 claims description 14
- 239000008267 milk Substances 0.000 claims description 14
- 210000004080 milk Anatomy 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- 102000004139 alpha-Amylases Human genes 0.000 claims description 12
- 108090000637 alpha-Amylases Proteins 0.000 claims description 12
- 229940024171 alpha-amylase Drugs 0.000 claims description 12
- 229920002261 Corn starch Polymers 0.000 claims description 11
- 239000008120 corn starch Substances 0.000 claims description 11
- 102000004190 Enzymes Human genes 0.000 claims description 10
- 108090000790 Enzymes Proteins 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 229940088598 enzyme Drugs 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 239000007974 sodium acetate buffer Substances 0.000 claims description 6
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims 2
- 239000012064 sodium phosphate buffer Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 20
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 89
- 239000002245 particle Substances 0.000 description 39
- 239000003921 oil Substances 0.000 description 19
- 235000019198 oils Nutrition 0.000 description 19
- 238000001000 micrograph Methods 0.000 description 18
- 238000007664 blowing Methods 0.000 description 12
- 239000002585 base Substances 0.000 description 9
- 229940099112 cornstarch Drugs 0.000 description 9
- 239000008187 granular material Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000000338 in vitro Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000004382 Amylase Substances 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- 235000019418 amylase Nutrition 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 230000000968 intestinal effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000005063 solubilization Methods 0.000 description 3
- 230000007928 solubilization Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229920000856 Amylose Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 2
- 230000002496 gastric effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 210000002784 stomach Anatomy 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 125000001695 zeaxanthin group Chemical group 0.000 description 2
- 229920000945 Amylopectin Polymers 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004438 eyesight Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 210000000813 small intestine Anatomy 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical class CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a method for efficiently and directionally embedding zeaxanthin by granular cold water-soluble porous starch, which is characterized in that raw starch is pretreated by a low-intensity pulsed electric field and then subjected to enzymolysis, and finally subjected to low-temperature alcohol-alkali modification and synergistic effect to obtain granular cold water-soluble porous starch with higher oil absorption rate, higher cold water solubility and higher transparency, and holes are uniformly distributed, so that zeaxanthin is efficiently and directionally embedded, and the problems of high energy consumption, harsh reaction conditions, low cold water solubility, low transparency and low embedding rate of the embedded zeaxanthin in the prior art are solved.
Description
Technical field:
the invention relates to the technical field of starch modification, in particular to a method for efficiently and directionally embedding zeaxanthin by granular cold water-soluble porous starch.
The background technology is as follows:
zeaxanthin, fat-soluble yellow powder or oil, is dihydroxyl derivative of beta-carotene, and has chemical formula C 40 H 56 O 2 . Zeaxanthin has effects of protecting eyesight, scavenging free radicals, resisting oxidation, resisting cancer, and preventing cardiovascular diseases in medicine. But the zeaxanthin has poor water solubility, poor stability and low bioavailability, and can be degraded in contact with light, enzyme and metal to cause a great deal of loss, thereby limiting the application of the zeaxanthin in industries such as food, medicine and the like to a certain extent. Therefore, there is a need to find an embedding matrix with low cost and good effect to protect zeaxanthin, and to further explore how to improve the water solubility, stability and bioavailability of zeaxanthin so as to improve the application value of zeaxanthin.
The porous starch is modified starch with a large number of pore structures distributed on the surface or penetrating through the whole starch particles, and the unique hollow structure characteristic becomes a research hot spot in the aspect of porous materials, has the advantages of high porosity, high specific surface area, strong adsorptivity, large load capacity and the like, and simultaneously retains the original properties of safety, non-toxicity, degradability and the like of the starch. Thus, the porous starch can be used as a wall material for embedding the active ingredient, protecting the active ingredient, and playing a role in releasing the active ingredient slowly or specifically. However, porous starch has low solubility in water, poor dispersibility, and because of its high specific gravity, it is easily precipitated in liquid state, and these defects limit the application of porous starch in embedding active ingredients. Most of the starch is required to be gelatinized by heating in industry, so that the water solubility of the starch is enhanced, and therefore, the starch soluble in cold water is used, the industrial production links can be reduced, and the production efficiency is improved. The porous starch preparation method with the best application prospect at present is a complex enzyme hydrolysis method, has the characteristics of specificity, high efficiency, mild reaction conditions, easiness in adjusting and controlling the porosity, industrialization and the like, but has the problems of high energy cost, long time consumption and the like.
The processes disclosed for the preparation of granular cold water soluble starch and the embedding of zeaxanthin mainly comprise: 1) Chinese patent 202011632449.1 discloses a preparation method of V-shaped granular porous starch, which adopts high Wen Chun method to treat starch to prepare V-shaped starch, and then carries out enzymolysis to prepare V-shaped porous starch, however, the method involves high Wen Chunfa energy consumption, harsh reaction conditions, needs to use a high-temperature high-pressure reaction kettle, and has high equipment investment.
The invention comprises the following steps:
the invention aims to provide a method for efficiently and directionally embedding zeaxanthin by granular cold water-soluble porous starch, which is characterized in that raw starch is pretreated by a low-intensity pulsed electric field and then subjected to enzymolysis, and finally subjected to low-temperature alcohol-alkali modification and synergistic effect to obtain granular cold water-soluble porous starch with higher oil absorption rate, higher cold water solubility and higher transparency, and holes are uniformly distributed, so that zeaxanthin is efficiently and directionally embedded, and the problems of high energy consumption, harsh reaction conditions, low cold water solubility, low transparency and low embedding rate of zeaxanthin in the prior art are solved.
The invention is realized by the following technical scheme:
a method for efficient directional embedding of zeaxanthin in granular cold water-soluble porous starch, the method comprising the steps of:
(1) Pretreatment of a pulsed electric field: mixing starch and deionized water to form uniform starch suspension, adding an electrolyte solution, adjusting the conductivity of the suspension to 50-300 mu s/cm, pumping into pulse electric field treatment equipment for treatment, wherein the flow rate is 50-250 mL/min, the pulse frequency of a pulse electric field is 800-2000 Hz, the pulse width is 10-100 us, the electric field intensity is 2-15 kV/cm, preferably 4-12kV/cm, the treatment time is 10-120 min, and carrying out vacuum suction filtration, washing, drying, crushing and sieving on the treated starch to obtain pulse electric field pretreated starch;
(2) And (3) enzymolysis treatment: mixing the pulsed electric field pretreated starch obtained in the step (1) with a buffer solution to form a uniform starch suspension, adding alpha-amylase and starch transglucosidase into the mixture for enzymolysis at the temperature of between 40 and 50 ℃ in a water bath, wherein the enzymolysis time is between 0.5 and 5.5 hours, the mass ratio of the alpha-amylase to the starch transglucosidase is between 2:1 and 1:2, the total addition amount of the alpha-amylase and the starch transglucosidase is between 0.5 and 4.0 weight percent, and carrying out vacuum suction filtration, water washing, alcohol washing, drying, crushing and sieving on the starch after enzymolysis to obtain the pulsed electric field assisted preparation of porous starch;
(3) Alcohol alkali treatment: mixing the porous starch prepared in the step (2) with ethanol to form uniform starch milk, adding sodium hydroxide to react in a water bath at 15-35 ℃ and preferably at 20-30 ℃, neutralizing the reacted starch, vacuum filtering, washing with alcohol, drying, crushing and sieving to obtain the granular cold water soluble porous starch prepared in an auxiliary manner by the pulse electric field;
(4) Embedding zeaxanthin: mixing the granular cold water soluble porous starch prepared in the step (3) with ethanol to form uniform starch milk, adding a zeaxanthin absolute ethanol solution to adsorb in a water bath at 15-35 ℃, preferably 25-35 ℃ and the zeaxanthin concentration of 1-5 mg/mL, vacuum filtering the adsorbed inclusion compound, washing with alcohol, drying and crushing to obtain the granular cold water soluble porous starch-zeaxanthin inclusion compound prepared in an auxiliary manner by the pulse electric field.
The starch in the step (1) is one or more of common starches such as corn starch, waxy corn starch and the like; the electrolyte solution is one or two of potassium sulfate and potassium chloride, and the concentration of the electrolyte solution is 0.2-2 mol/L.
The buffer solution in the step (2) is acetic acid-sodium acetate buffer solution or phosphate buffer solution, and the pH value of the buffer solution is 4-7; the enzyme activity of the alpha-amylase is 3000-5000U/mL, and the enzyme activity of the starch transglucosidase is 5000-200000U/mL.
The concentration of the ethanol in the step (3) is 70-100 wt%, and the mass ratio of the ethanol to the pulsed electric field for auxiliary preparation of the porous starch is 4:1-40:1; the mass ratio of the sodium hydroxide to the pulsed electric field for auxiliary preparation of the porous starch is 1:10-1:1; the reaction time is 5-30 min.
The mass ratio of the zeaxanthin to the pulse electric field in the step (4) for assisting in preparing granular cold water-soluble porous starch is 3:1-30:1; the adsorption time is 0.5-4.5 h.
The invention pretreats starch by using a low field strength pulse electric field with the electric field strength of 2-15 kV/cm, continuously, uniformly and stably damages the apparent morphology and the internal crystal structure of starch particles, improves the subsequent enzymolysis and alcohol alkali treatment efficiency, and realizes efficient directional embedding; according to the invention, basic particle morphology of starch can be reserved through alcohol-alkali treatment at the room temperature of 15-35 ℃, a V-shaped metastable cavity structure is constructed, the surface area and the adsorption performance are increased, the cold water solubility is improved, and the solubilization of active substances is realized; by the matched use of the starch and the active substances in a certain proportion, the bioavailability and stability of the target substances are improved, a series of problems that the prior majority of physical and chemical methods are complex in equipment or condition, easy to form pollution and the like for realizing starch embedding can be avoided, and the method has the characteristics of being green, safe, low in energy consumption and the like.
In addition, the inventor unexpectedly discovers that the low field strength pulse electric field pretreatment of 2-15 kV/cm combined with enzymolysis can improve the transparency and cold water solubility of starch, the alcohol alkali treatment at the room temperature of 15-35 ℃ can also improve the transparency and cold water solubility of starch, and the two have obvious positive synergistic effect.
The technical principle of the invention is as follows: under the action of a pulse electric field, charged particles in the starch solution directionally migrate and gather on the surfaces of the starch particles to form macroscopic space charges. When the electric field strength of 2-15 kV/cm is reached, the starch particles are destroyed under the action of instant high-voltage discharge without structural collapse, the pore canal is opened under the action of continuous, uniform and stable electric field, the sensibility of the starch particles to amylase is improved, and the efficient directional embedding is realized. Secondly, the hydroxyl groups on starch molecules are negatively charged in an alkaline environment, so that the starch particles are gradually expanded and further dispersed by intermolecular repulsive force, after a certain degree is reached, the hydrogen bonds are broken, the double-helix structure of the starch is unfolded, and the particle morphology of the starch is maintained under the effects of ethanol inhibition and an amylose crosslinked network structure. The neutralization reaction can lead ethanol and single-helix starch molecules to be combined to form a V-shaped compound, volatile ethanol is evaporated in the high-temperature drying process, a V-shaped metastable cavity structure inside the starch is left, the obtained starch has better cold water solubility and can keep a particle structure more complete, meanwhile, the surface area of the starch is increased, and the starch has certain material adsorption capacity.
The beneficial effects of the invention are as follows:
(1) The invention uses the pulse electric field pretreatment strengthening modification with low field intensity of 2-15 kV/cm to continuously, uniformly and stably destroy the original starch without structural collapse, improves the sensitivity of starch particles to amylase, realizes high-efficiency directional embedding, solves the problem that the enzymolysis time is tens of hours in the traditional porous amylase hydrolysis method, and shortens the enzymolysis time to a few hours.
(2) The invention takes the porous starch prepared by the assistance of the pulse electric field as the raw material for further alcohol-alkali modification, reserves the basic particle morphology of the starch, constructs a V-shaped metastable state cavity structure, increases the surface area and the adsorption performance, improves the cold water solubility and realizes the solubilization of active substances.
(3) The low-field-intensity pulsed electric field pretreatment of 2-15 kV/cm is combined with enzymolysis to improve the cold water solubility and transparency of starch, and the alcohol alkali treatment at the room temperature of 15-35 ℃ also improves the cold water solubility and transparency of starch, and the two have obvious forward synergistic effect, so that the cold water solubility and transparency of starch are greatly improved.
(4) The invention realizes the efficient directional embedding and solubilization of the zeaxanthin active substances, can lead the zeaxanthin to be released to the small intestine in a targeted way, improves the bioavailability and stability, and has the characteristics of greenness, safety, low processing cost and the like.
Description of the drawings:
FIG. 1 (a) is a scanning electron microscope image of the corn starch of the present invention.
FIG. 1 (b) is a scanning electron microscope image of the porous starch prepared in comparative example 2 of the present invention.
FIG. 1 (c) is a scanning electron microscope image of the pulsed electric field assisted preparation of porous starch of comparative example 3 having an electric field strength of 20kV/cm according to the present invention.
FIG. 1 (d) is a scanning electron microscope image of the pulsed electric field assisted preparation of porous starch of comparative example 4 having an electric field strength of 12kV/cm according to the present invention.
FIG. 1 (e) is a scanning electron microscope image of granular cold water-soluble starch in comparative example 5 of the present invention.
FIG. 1 (f) is a scanning electron microscope image of granular cold water-soluble porous starch in comparative example 6 of the present invention.
FIG. 1 (g) is a scanning electron microscope image of the preparation of granular cold water-soluble porous starch assisted by a pulsed electric field of 20kV/cm electric field strength in comparative example 7 of the present invention.
FIG. 1 (h) is a scanning electron microscope image of the pulsed electric field assisted preparation of granular cold water soluble porous starch of comparative example 8 having an alcohol base temperature of 50℃according to the present invention.
FIG. 1 (i) is a scanning electron microscope image of the pulsed electric field assisted preparation of granular cold water soluble porous starch in example 1 of the present invention.
FIG. 2 is a graph showing data of transparency of the pulsed electric field-assisted preparation of granular cold water-soluble porous starch in example 1 and starches in comparative examples 1 to 8 according to the present invention.
FIG. 3 is a graph showing the saturation solubility of zeaxanthin and zeaxanthin for the pulsed electric field-assisted preparation of granular cold water-soluble porous starch-zeaxanthin inclusion compounds in example 1 and the raw starch-zeaxanthin inclusion compounds in comparative example 1 of the present invention.
FIG. 4 (a) is a scanning electron microscope image of zeaxanthin in accordance with the invention.
FIG. 4 (b) is a scanning electron microscope image of the primary starch-zeaxanthin inclusion compound in comparative example 1.
FIG. 4 (c) is a scanning electron microscope image of the pulsed electric field assisted preparation of granular cold water soluble porous starch-zeaxanthin inclusion compound in example 1.
FIG. 5 (a) is a graph of the in vitro gastric release of zeaxanthin and zeaxanthin for the pulsed electric field assisted preparation of granular cold water soluble porous starch-zeaxanthin inclusion compounds in example 1 and the raw starch-zeaxanthin inclusion compounds in comparative example 1 of the present invention.
FIG. 5 (b) is a graph showing the in vitro intestinal release of zeaxanthin and zeaxanthin in the pulsed electric field assisted preparation of granular cold water soluble porous starch-zeaxanthin inclusion compound in example 1 and the raw starch-zeaxanthin inclusion compound in comparative example 1 of the present invention.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1:
(1) Pretreatment of a pulsed electric field: 18g of corn starch (see FIG. 1 (a)) and 102g of deionized water were mixed to form a uniform starch suspension, 0.3mL of 0.5mol/L potassium chloride electrolyte solution was added, the conductivity of the suspension was adjusted to 150. Mu.s/cm, and the suspension was pumped into a pulsed electric field treatment apparatus at a flow rate of 120mL/min, at a pulse frequency of 1000Hz, a pulse width of 40. Mu.s, an electric field strength of 12kV/cm, and a treatment time of 45min. Vacuum filtering, washing with deionized water for 3 times, electrothermal blowing and drying for 24 hours, crushing, and sieving with a 100-mesh sieve to obtain pulsed electric field pretreated starch;
(2) And (3) enzymolysis treatment: 9g of pulsed electric field pretreated starch and 27g of acetic acid-sodium acetate buffer solution with pH of 5.0 are mixed to form a uniform starch suspension, and 2wt% of enzyme (alpha-amylase and amylotransglucosidase with mass ratio of 1:1) is added for enzymolysis in a water bath at 50 ℃ for 4.5h. Vacuum filtering, washing with water for 3 times, washing with alcohol for 2 times, electrothermal blowing and drying for 24 hours, crushing, and sieving with 100 mesh sieve to obtain the porous starch with the assistance of the pulse electric field;
(3) Alcohol alkali treatment: 5g of porous starch prepared by the aid of a pulsed electric field and 45g of 80wt% ethanol are mixed to form uniform starch milk, and 2.4g of sodium hydroxide is added to react for 15min in a water bath at 25 ℃. Neutralizing starch, vacuum filtering, washing with alcohol for 3 times, electrothermal blowing and drying for 24 hours, pulverizing, and sieving with 100 mesh sieve to obtain granular cold water soluble porous starch with assistance of pulse electric field. A scanning electron microscope view thereof is shown in fig. 1 (i);
4) Mixing 0.5g of the granular cold water soluble porous starch prepared in the step (3) with 5g of ethanol to form uniform starch milk, adding 7g of zeaxanthin absolute ethanol solution, carrying out water bath adsorption at 25 ℃, wherein the zeaxanthin concentration is 2mg/mL, carrying out vacuum filtration on the adsorbed inclusion compound, carrying out alcohol washing for 3 times, drying and crushing to obtain the granular cold water soluble porous starch-zeaxanthin inclusion compound prepared in an auxiliary way by the pulse electric field. See fig. 4 (c) for a scanning electron microscope image thereof.
Example 2
(1) Pretreatment of a pulsed electric field: 18g of corn starch and 102g of deionized water are mixed to form a uniform starch suspension, 0.3mL of 0.5mol/L potassium chloride electrolyte solution is added, the conductivity of the suspension is regulated to 150 mu s/cm, a pulse electric field treatment device is pumped at a flow rate of 120mL/min, the pulse frequency is 1000Hz, the pulse width is 40 mu s, the electric field strength is 12kV/cm, and the treatment time is 45min. Vacuum filtering, washing with deionized water for 3 times, electrothermal blowing and drying for 24 hours, crushing, and sieving with a 100-mesh sieve to obtain pulsed electric field pretreated starch;
(2) And (3) enzymolysis treatment: 9g of pulsed electric field pretreated starch and 27g of acetic acid-sodium acetate buffer solution with pH of 5.0 are mixed to form a uniform starch suspension, and 2wt% of enzyme (alpha-amylase and amylotransglucosidase with mass ratio of 1:1) is added for enzymolysis in a water bath at 45 ℃ for 2.5h. Vacuum filtering, washing with water for 3 times, washing with alcohol for 2 times, electrothermal blowing and drying for 24 hours, crushing, and sieving with 100 mesh sieve to obtain the porous starch with the assistance of the pulse electric field;
(3) Alcohol alkali treatment: 5g of porous starch prepared by the aid of a pulsed electric field and 40g of 80wt% ethanol are mixed to form uniform starch milk, and 2.0g of sodium hydroxide is added for water bath reaction for 15min at 30 ℃. Neutralizing starch, vacuum filtering, washing with alcohol for 3 times, electrothermal blowing and drying for 24 hours, pulverizing, and sieving with 100 mesh sieve to obtain granular cold water soluble porous starch with the assistance of pulse electric field;
4) Mixing 0.5g of the granular cold water soluble porous starch prepared in the step (3) with 5g of ethanol to form uniform starch milk, adding 3g of zeaxanthin absolute ethanol solution, carrying out water bath adsorption at 25 ℃, wherein the zeaxanthin concentration is 5mg/mL, carrying out vacuum filtration on the adsorbed inclusion compound, carrying out alcohol washing for 3 times, drying and crushing to obtain the granular cold water soluble porous starch-zeaxanthin inclusion compound prepared in an auxiliary way by the pulse electric field.
Example 3
(1) Pretreatment of a pulsed electric field: 18g of waxy corn starch and 102g of deionized water are mixed to form a uniform starch suspension, 0.3mL of 0.5mol/L potassium chloride electrolyte solution is added, the conductivity of the suspension is regulated to 150 mu s/cm, a pulse electric field treatment device is pumped at a flow rate of 120mL/min, the pulse frequency is 1000Hz, the pulse width is 40 mu s, the electric field strength is 4kV/cm, and the treatment time is 45min. Vacuum filtering, washing with deionized water for 3 times, electrothermal blowing and drying for 24 hours, crushing, and sieving with a 100-mesh sieve to obtain pulsed electric field pretreated starch;
(2) And (3) enzymolysis treatment: 9g of pulsed electric field pretreated starch and 27g of acetic acid-sodium acetate buffer solution with pH of 5.0 are mixed to form a uniform starch suspension, and 2wt% of enzyme (alpha-amylase and amylotransglucosidase with mass ratio of 1:1) is added for enzymolysis in a water bath at 50 ℃ for 4.5h. Vacuum filtering, washing with water for 3 times, washing with alcohol for 2 times, electrothermal blowing and drying for 24 hours, crushing, and sieving with 100 mesh sieve to obtain the porous starch with the assistance of the pulse electric field;
(3) Alcohol alkali treatment: 5g of porous starch prepared by the aid of a pulsed electric field and 45g of 80wt% ethanol are mixed to form uniform starch milk, and 2.4g of sodium hydroxide is added for water bath reaction for 15min at 20 ℃. Neutralizing starch, vacuum filtering, washing with alcohol for 3 times, electrothermal blowing and drying for 24 hours, pulverizing, and sieving with 100 mesh sieve to obtain granular cold water soluble porous starch with the assistance of pulse electric field;
4) Mixing 0.5g of the granular cold water soluble porous starch prepared in the step (3) with 5g of ethanol to form uniform starch milk, adding 12g of zeaxanthin absolute ethanol solution, carrying out water bath adsorption at 30 ℃, wherein the zeaxanthin concentration is 1mg/mL, carrying out vacuum filtration on the adsorbed inclusion compound, carrying out alcohol washing for 3 times, drying and crushing to obtain the granular cold water soluble porous starch-zeaxanthin inclusion compound prepared in an auxiliary way by the pulse electric field.
Example 4
(1) Pretreatment of a pulsed electric field: 18g of corn starch and 102g of deionized water are mixed to form a uniform starch suspension, 0.3mL of 0.5mol/L potassium chloride electrolyte solution is added, the conductivity of the suspension is regulated to 150 mu s/cm, a pulse electric field treatment device is pumped at a flow rate of 120mL/min, the pulse frequency is 1000Hz, the pulse width is 40 mu s, the electric field strength is 12kV/cm, and the treatment time is 45min. Vacuum filtering, washing with deionized water for 3 times, electrothermal blowing and drying for 24 hours, crushing, and sieving with a 100-mesh sieve to obtain pulsed electric field pretreated starch;
(2) And (3) enzymolysis treatment: 9g of pulsed electric field pretreated starch and 27g of acetic acid-sodium acetate buffer solution with pH of 5.0 are mixed to form a uniform starch suspension, and 2wt% of enzyme (alpha-amylase and amylotransglucosidase with mass ratio of 1:1) is added for enzymolysis in a water bath at 40 ℃ for 3.5h. Vacuum filtering, washing with water for 3 times, washing with alcohol for 2 times, electrothermal blowing and drying for 24 hours, crushing, and sieving with 100 mesh sieve to obtain the porous starch with the assistance of the pulse electric field;
(3) Alcohol alkali treatment: 5g of porous starch prepared by the aid of a pulsed electric field and 45g of 80wt% ethanol are mixed to form uniform starch milk, and 2.6g of sodium hydroxide is added to react for 15min in a water bath at 25 ℃. Neutralizing starch, vacuum filtering, washing with alcohol for 3 times, electrothermal blowing and drying for 24 hours, pulverizing, and sieving with 100 mesh sieve to obtain granular cold water soluble porous starch with the assistance of pulse electric field;
4) Mixing 0.5g of the granular cold water soluble porous starch prepared in the step (3) with 5g of ethanol to form uniform starch milk, adding 8g of zeaxanthin absolute ethanol solution, carrying out water bath adsorption at 35 ℃ to obtain a zeaxanthin concentration of 2mg/mL, carrying out vacuum filtration on the adsorbed inclusion compound, carrying out alcohol washing for 3 times, drying and crushing to obtain the granular cold water soluble porous starch-zeaxanthin inclusion compound prepared in an auxiliary way by the pulse electric field.
Comparative example 1
Reference example 1 is different in that the common corn starch (see fig. 1 (a) for scanning electron microscopy) is directly used without going through steps (1) - (3), i.e. the raw starch is embedded with zeaxanthin. The scanning electron microscope of the raw starch-zeaxanthin inclusion compound obtained is shown in fig. 4 (b).
Comparative example 2
Referring to example 1, the pulsed electric field pretreatment and alcohol base treatment and step (4) were omitted, and the other conditions were the same as in example 1. The scanning electron microscope image of the porous starch prepared is shown in FIG. 1 (b).
Comparative example 3
Referring to example 1, except that the electric field strength was 20kV/cm, the alcohol alkali treatment and step (4) were omitted, and the other conditions were the same as in example 1. The scanning electron for the preparation of porous starch assisted by a pulsed electric field with an electric field strength of 20kV/cm is shown in FIG. 1 (c).
Comparative example 4
The procedure of example 1 was followed except that the alcohol base treatment and step (4) were omitted, and the other conditions were the same as in example 1. A scanning electron microscope image of the pulsed electric field assisted preparation of porous starch with an electric field strength of 12kV/cm is shown in FIG. 1 (d).
Comparative example 5
The method of example 1 was referred to, except that the pulsed electric field pretreatment and the enzymatic hydrolysis treatment and step (4) were omitted, and the other conditions were the same as in example 1. The scanning electron microscope image of the granular cold water-soluble starch prepared by the alcohol base treatment is shown in FIG. 1 (e).
Comparative example 6
Referring to the method of example 1, the pulsed electric field pretreatment and step (4) were omitted, and the other conditions were the same as in example 1. Scanning electron microscopy images of granular cold water-soluble porous starch after enzymatic hydrolysis and alcohol base treatment are shown in FIG. 1 (f).
Comparative example 7
The procedure of example 1 was followed except that the electric field strength was 20kV/cm and that the procedure was as in (4), except that the procedure was as in example 1. The scanning electron microscope image of the obtained pulsed electric field assisted preparation of porous starch is shown in fig. 1 (g).
Comparative example 8
The procedure of example 1 was followed except that the alcohol base treatment temperature was 50℃and step (4), and the other conditions were the same as in example 1. The scanning electron microscope image of the obtained pulsed electric field assisted preparation of porous starch is shown in fig. 1 (h).
Fig. 1 (a) shows the granular state of cornstarch: a small number of grooves and tiny holes are formed on the surface of part of the particles; FIG. 1 (b) is the granular state of the porous starch prepared in comparative example 2: the surface presents grooves and holes; FIG. 1 (c) is a state of particles of comparative example 3 in which a pulsed electric field having an electric field strength of 20kV/cm was used to assist in the preparation of porous starch: the surface presents grooves and holes, starch particles are excessively destroyed due to high field strength of 20kV/cm, and part of the particles form larger openings and even crack, because the electric field strength of a pulse electric field is too high, the energy for collapsing the starch particles is too high, the starch particles are crushed, the capillary action of the holes is weakened, and the adsorption performance is reduced; FIG. 1 (d) is a state of particles of comparative example 4 in which a pulsed electric field having an electric field strength of 12kV/cm was used to assist in the preparation of porous starch: compared with comparative example 2, the surface presents significantly larger grooves and more deeper holes, because the pulsed electric field increases the enzymolysis efficiency, has the effect of assisting in pore formation, and compared with comparative example 3, the hole distribution is relatively uniform, and the integrity of the particles is still maintained, because the starch particles can be directionally formed into pores to a certain extent under the action of the low field strength electric field and the starch particles are not damaged; FIG. 1 (e) shows the granular state of granular cold water-soluble starch of comparative example 5: still keeping the granule shape, compared with comparative example 1, the starch granule has different degrees of granule expansion under the action of alcohol alkali treatment, increases the surface area, and changes the smooth surface into distortion recess; FIG. 1 (f) is the granular state of the granular cold water-soluble porous starch of comparative example 6: the porous structure on the surface is also changed into a twisting concave structure, but the holes are still obviously visible; FIG. 1 (g) is a particle state of comparative example 7 pulsed electric field assisted in preparing granular cold water soluble porous starch with an electric field strength of 20 kV/cm: the porous structure on the surface is changed into a twisting dent, starch particles are excessively destroyed due to high field strength of 20kV/cm, larger open pores are formed, and the capability of adsorbing substances is weakened; FIG. 1 (h) is a particle state of the comparative example 8 pulsed electric field assisted preparation of granular cold water soluble porous starch at an alcohol base treatment temperature of 50 ℃): the porous structure on the surface is changed into a twisting dent, so that the twisting dent is excessively swelled at the high temperature of 50 ℃, the cracking degree of particles is high, and the adsorption capacity is reduced; FIG. 1 (i) is a particle state of example 1 pulsed electric field assisted preparation of granular cold water soluble porous starch: the porous structure of the surface is also changed into a twisted dent, and the twisted dent is larger in dent and more holes compared with comparative example 6, the holes are distributed relatively uniformly compared with comparative example 7, and the integrity of the particles is maintained compared with comparative example 8, because the pulsed electric field is assisted to prepare granular cold water soluble porous starch with more deep holes, the reaction rate of alcohol alkali is accelerated, and the excessive swelling and cracking of the starch are caused by the high temperature of the alcohol alkali reaction. These results show that the starch granules can form holes with relatively uniform distribution under the continuous, uniform and stable low field intensity effect of 2-15 kV/cm and the alcohol alkali treatment effect at the room temperature of 15-35 ℃ in the pulsed electric field pretreatment, and the active substances can be efficiently and directionally embedded.
The method for measuring the oil absorption of the starch in the examples and comparative examples of the present invention is as follows:
the mass of 50mL centrifuge tube was weighed, denoted M0, about 1.0g of starch (dry basis) was added, the combined mass of centrifuge tube and starch (dry basis) was weighed, denoted M1, 10mL soybean oil was added, shaking and mixing were performed, absorption was performed at a constant temperature of 25℃for 30min, centrifugation was performed at 8000rpm/min for 20min to remove floating soybean oil, and the combined mass of centrifuge tube and residual residue was weighed, denoted M2. The oil absorption OA of the starch to be measured can be calculated by the following formula:
OA＝(M2-M1)/(M1-M0)×100％
wherein OA represents the oil absorption rate of the starch to be measured.
The method for measuring the cold water solubility of starch in the examples and comparative examples of the present invention is as follows:
the mass of starch (dry basis) is weighed and marked as M3, deionized water is added to prepare starch suspension with the mass fraction of 1%, the starch suspension is stirred for 20min in a water bath kettle with the temperature of 25 ℃, the starch suspension is transferred into a centrifuge tube, the centrifuge tube is centrifuged for 20min at 3000rpm, the supernatant is transferred into a flat weighing bottle which is accurately weighed in advance, the starch is dried at the temperature of 105 ℃ for 6h to constant weight, and the mass of cold water soluble starch in the flat weighing bottle is weighed and marked as M4. The cold water solubility S of the starch to be measured can be calculated by the following formula:
S＝M4/M3×100％
wherein S represents the cold water solubility of the starch to be tested.
Table 1 shows the measurement results of oil absorption and cold water solubility of examples and comparative examples.
Compared with the original starch of comparative example 1, the preparation of granular cold water-soluble porous starch with the assistance of the pulse electric field of example 1 has the advantages that the oil absorption rate is improved by 74.0%, the cold water solubility is improved by 78.0%, and the improvement is 12.00 times; compared with the original starch of comparative example 1, the oil absorption rate of the porous starch prepared by the pulsed electric field assistance with the electric field intensity of 12kV/cm is improved by 54.0%, and the cold water solubility is improved by 5.5%; compared with the original starch of comparative example 1, the granular cold water soluble starch obtained by alcohol alkali treatment of comparative example 5 has the oil absorption rate increased by 25.0 percent and the cold water solubility increased by 66.1 percent; as can be seen from the comparison between comparative example 1 and comparative examples 4 and 5, the pulse electric field assisted preparation of granular cold water-soluble porous starch in example 1 has a cold water solubility enhancement value of 78.0% compared with the original starch in comparative example 1, which is greater than the transparency of the granular cold water-soluble porous starch prepared in comparative example 4 compared with the cold water solubility enhancement value of 5.5% in comparative example 1, and is greater than 66.1% compared with the original starch in comparative example 5, and which is greater than the sum of 71.6% in comparative example 1, the cold water solubility of starch is improved by the combination of the low field pulse electric field pretreatment and enzymolysis of 12kV/cm, and the cold water solubility of starch is improved by the alcohol alkali treatment at room temperature, and the two have obvious forward synergistic effects.
Example 1 pulsed electric field assisted preparation of granular cold water soluble porous starch improved oil absorption by 31.5% and cold water solubility by 9.56 times compared to comparative example 2 porous starch; compared with the preparation of porous starch with the assistance of a pulse electric field with the electric field strength of 20kV/cm in comparative example 3, the oil absorption rate of example 1 is improved by 26.5%, and the cold water solubility is improved by 7.89 times, because the electric field strength is too high and the too strong energy causes the starch particles to collapse to rupture, so that the oil absorption rate of comparative example 3 is reduced; compared with the preparation of porous starch with the assistance of a pulse electric field with the electric field strength of 12kV/cm in comparative example 4, the oil absorption rate of the porous starch is improved by 20.0%, and the cold water solubility is improved by 6.04 times, because the starch forms a loose V-shaped single-spiral cavity structure by alcohol alkali treatment, the specific surface area is increased, certain material adsorption capacity is achieved, and the oil absorption rate of the porous starch in example 1 is greatly improved; example 1 has an oil absorption increased by 49.0% and a cold water solubility increased by 11.9% compared to the granular cold water soluble starch of comparative example 5; compared with the granular cold water soluble porous starch of the comparative example 6, the oil absorption rate of the granular cold water soluble porous starch of the example 1 is improved by 18.0%, and the cold water solubility of the example 1 is improved by 9.0%, because the pulse electric field has the effect of destroying the apparent morphology and the internal crystal structure of the starch granules to form more and larger holes, so that the short chain amylopectin and the amylose are easier to dissolve in the starch granules, and the cold water solubility of the example 1 is improved; example 1 has an oil absorption rate improved by 12.5% and a cold water solubility improved by 11.3% compared to comparative example 7 in which the pulsed electric field with an electric field strength of 20kV/cm was used to assist in preparing granular cold water-soluble porous starch, because broken starch particles are difficult to react with alkali in sufficient contact during alcohol alkali treatment to swell, resulting in a decrease in cold water solubility of comparative example 7. Compared with the preparation of granular cold water soluble porous starch by the assistance of a pulse electric field with the alcohol alkali treatment temperature of 50 ℃ in the embodiment 1, the oil absorption rate is improved by 16.0%, and the cold water solubility is improved by 11.7%, because the porous starch prepared by the assistance of the pulse electric field has deeper holes than the traditional porous starch, the contact area with alcohol alkali is larger, the reaction rate is accelerated, the excellent granular cold water soluble porous starch can be obtained by the alcohol alkali treatment at room temperature, and when the temperature is too high, the starch particles are excessively swelled, the integrity of the starch particles is damaged, and the cold water solubility of the comparative example 8 is reduced.
The transparency of the starch in the examples and comparative examples of the present invention was measured as follows:
1.000g of starch (dry basis) is accurately weighed into a 250mL conical flask, 99mL of deionized water is added to prepare starch milk with the mass fraction of 1%, the starch milk is stirred for 20min in a water bath kettle with the temperature of 100 ℃, the volume of starch paste is kept unchanged in the process, the transmittance is measured at 620nm by taking deionized water (with the transmittance of 100%) as a blank, the same sample is measured for 3 times, and the average value is obtained.
FIG. 2 is a data graph of the transparency of starch, example 1 pulsed electric field assisted preparation of granular cold water soluble porous starch having a transparency of 78.28%; example 1 has a 10.69% improvement in transparency over the raw starch of comparative example 1, a 67.59% improvement, and a 6.32-fold improvement; the transparency of the granular cold water-soluble porous starch prepared in comparative example 4 was 23.13%, which is improved by 12.44% compared to the transparency of the raw starch in comparative example 1 of 10.69%. The granular cold water soluble starch prepared in comparative example 5 had a transparency of 62.82% which was 52.13% higher than the original starch of comparative example 1, transparency of 10.69%. As can be seen from the comparison between the example 1 and the comparative examples 4 and 5, the transparency of the granular cold water-soluble porous starch prepared in the example 1 is improved by 67.59% compared with the original starch in the comparative example 1, the transparency of the granular cold water-soluble porous starch prepared in the comparative example 4 is improved by 12.44% compared with the original starch in the comparative example 1, the transparency of the granular cold water-soluble starch obtained in the alcohol alkali treatment in the comparative example 5 is also improved by 52.13% compared with the original starch in the comparative example 1, the transparency of the starch is improved by the combination of the low-field pulse electric field pretreatment and enzymolysis of 12kV/cm, the transparency of the starch is improved by the alcohol alkali treatment at room temperature, and the transparency of the starch is obviously improved by the combination of the low-field pulse electric field pretreatment and the alcohol alkali treatment.
Example 1 increased 2.76 times compared to comparative example 2 porous starch with 20.83% transparency; example 1 compared with comparative example 3 with 20.33% transparency, the pulsed electric field assisted preparation of porous starch with 20kV/cm electric field strength increased by 2.85 times; in example 1, compared with the preparation of porous starch with the assistance of a pulse electric field with the electric field strength of 12kV/cm in comparative example 4 and the transparency of 23.13%, the preparation is improved by 2.38 times, because the alcohol alkali treatment can dissolve starch molecules in water and interact with water molecules, the reflection strength and the refraction strength of light are weakened, and the transparency of example 1 is greatly improved; example 1 increased 15.46% compared to the granular cold water soluble starch of comparative example 5 having a transparency of 62.82%; example 1 improved 7.55% compared to the granular cold water soluble porous starch of comparative example 6 having a transparency of 70.73% because the pulsed electric field low field strength pretreatment destroyed the starch granule structure, favoring light transmission and refraction, and the transparency of example 1 improved; example 1 the preparation of granular cold water-soluble porous starch with the aid of a pulsed electric field having an electric field strength of 20kV/cm compared to comparative example 7 with a transparency of 68.69% is improved by 9.59% because of the poor dispersibility of the broken starch particles and increased obstruction of suspended matter with a high field strength of 20kV/cm, resulting in a reduced transparency of comparative example 7. Example 1 improved 13.12% compared to the pulsed electric field assisted preparation of granular cold water soluble porous starch at an alcohol base treatment temperature of 50 ℃ for comparative example 8 with a transparency of 65.16% because the pulsed electric field assisted preparation of porous starch had more deeper pores than the conventional porous starch, accelerating the alcohol base treatment reaction rate, and when the temperature was too high, the starch molecules moved too fast, the particles excessively swelled to crack, blocking light transmission and refraction, resulting in reduced transparency for comparative example 8.
These results show that the granular cold water soluble porous starch prepared by the starch granules under the continuous, uniform and stable low field intensity effect of the pulsed electric field pretreatment and the effect of the room temperature alcohol alkali treatment can obviously reduce the enzymolysis time and improve the oil absorption rate, cold water solubility and transparency of the porous starch.
The methods for determining the entrapment rate and the adsorption rate of zeaxanthin of the inclusion compound in the examples and comparative examples of the present invention are as follows:
accurately weighing 10.00mg of inclusion compound, completely dispersing the inclusion compound in 5mL of dimethyl sulfoxide by intense vortex, centrifuging for 10min at 3000r/min, collecting the record volume of supernatant, diluting by 10 times, and measuring absorbance value at 446nm by adopting an ultraviolet spectrophotometer. The Entrapment Rate (ER) and Adsorption (AC) of zeaxanthin of the inclusion compound to be tested can be calculated according to the zeaxanthin standard curve by the following formula:
ER＝M5/M6×100％
wherein ER represents the entrapment rate of zeaxanthin in the clathrate to be tested, M5 represents the mass of zeaxanthin adsorbed by the clathrate to be tested, and M6 represents the mass of total zeaxanthin added to the clathrate to be tested.
AC＝cV×10/0.01/1000mg/g
Wherein AC represents the adsorption amount of zeaxanthin in the clathrate to be tested, c represents the concentration of zeaxanthin adsorbed by the clathrate to be tested, V represents the volume of supernatant, 10 represents dilution factor, and 0.01 represents the mass of clathrate.
The method for measuring the saturated solubility of zeaxanthin in the samples of the examples and comparative examples of the present invention is as follows:
placing excessive sample into deionized water, shaking at 37deg.C for 48h, centrifuging for 20min at 5000r/min, collecting supernatant, diluting, adding dimethyl sulfoxide, and colorizing at 446nm wavelength with ultraviolet spectrophotometer. The Saturation Solubility (SS) of zeaxanthin in the sample to be tested can be calculated according to the zeaxanthin standard curve by the following formula:
SS＝M7/Vμg/mL
wherein SS represents the saturated solubility of zeaxanthin in the sample to be tested, M7 represents the mass of water-soluble zeaxanthin in the sample to be tested, and V represents the volume of deionized water.
The method for measuring the cumulative release rate of zeaxanthin from the samples of example 1 and comparative example 1 according to the present invention is as follows:
5.00mg of sample was dispersed in 5mL SGF and SIF, respectively, and 1mL of digest was collected every 0.5h with shaking at 37℃and 1mL of liquid was added to each solution after each aliquot collection was completed to compensate for the volume loss. Dimethyl sulfoxide is added into the collected digestion liquid, the mixture is centrifuged for 10min at 3000r/min after being vigorously vortexed, and the supernatant is collected and diluted and is subjected to color comparison at 446nm by an ultraviolet spectrophotometer. The cumulative release rate (ZR) of zeaxanthin from the sample to be tested can be calculated according to the zeaxanthin standard curve as follows:
ZR＝Mt/M 0 ×100％
wherein ZR represents the cumulative release rate of zeaxanthin from the sample to be tested, mt represents the mass of zeaxanthin released from the sample to be tested at time t, M 0 Indicating the quality of the initial zeaxanthin in the sample to be tested.
Table 2 shows the measurement results of the embedding rate and the adsorption rate of examples 1 to 4 and comparative example 1.
By comparative analysis of the embedding rate, the embedding rate of the example 1 is improved by 32.3 percent compared with that of the original starch-zeaxanthin inclusion compound of the comparative example 1, and the adsorption quantity is improved by 9.1mg/g, which shows that the pulse electric field assisted preparation of granular cold water soluble porous starch can realize efficient embedding of zeaxanthin.
FIG. 3 is a graph of data for the saturated solubility of zeaxanthin, 9.22. Mu.g/mL for zeaxanthin and for the inclusion compound of example 1, comparative example 1, 10.33. Mu.g/mL for primary starch-zeaxanthin inclusion compound, and 14.45. Mu.g/mL for zeaxanthin for the pulsed electric field-assisted preparation of granular cold water-soluble porous starch-zeaxanthin inclusion compound, 4.12. Mu.g/mL for zeaxanthin versus comparative example 1, and 5.23. Mu.g/mL for primary starch-zeaxanthin inclusion compound versus comparative example 1. These results demonstrate that the pulsed electric field assisted preparation of granular cold water soluble porous starch enhances the water solubility of zeaxanthin, a very good embedding wall material.
Fig. 4 (a) is the granular state of zeaxanthin: irregular bar and plate crystals; FIG. 4 (b) is the particle state of the primary starch-zeaxanthin inclusion compound of comparative example 1: the surface of the particle is a complete and smooth polyhedron, a small number of grooves and tiny holes exist on the surface of part of the particle, and zeaxanthin fragments only adsorbed on the surface exist; FIG. 4 (c) is the particle state of the pulsed electric field assisted preparation of granular cold water soluble porous starch-zeaxanthin inclusion compound of example 1: the surface exhibits a porous structure of distorted pits, but still maintains the integrity of the particles, and most of the pores are filled with zeaxanthin fragments, as compared to comparative example 1, allowing for efficient directional entrapment of zeaxanthin.
FIG. 5 (a) is a graph of the in vitro release data of zeaxanthin from the stomach for zeaxanthin and inclusion complexes, the cumulative release rates of zeaxanthin from zeaxanthin, the comparative example 1 primary starch-zeaxanthin inclusion complex and the pulse electric field-assisted preparation of granular cold water-soluble porous starch-zeaxanthin inclusion complex of example 1 being 54.31%, 42.26% and 36.04%, respectively, over 2 hours; FIG. 5 (b) is a graph of the in vitro release data of zeaxanthin from the intestinal portion of zeaxanthin and of the inclusion compound, the cumulative release rates of zeaxanthin from zeaxanthin, the primary starch-zeaxanthin inclusion compound of comparative example 1 and the pulse electric field-assisted preparation of the particulate cold water-soluble porous starch-zeaxanthin inclusion compound of example 1 being 58.94%, 52.90% and 48.28%, respectively, over 2 hours. The pure zeaxanthin cannot be slowly released under the condition of the stomach/intestine, and the inclusion compound prepared by embedding the zeaxanthin into granular cold water-soluble porous starch with the assistance of a pulse electric field can play a certain role in controlling the release of the zeaxanthin in the gastric digestion process, and release a large amount of zeaxanthin in the intestinal digestion process, so that the zeaxanthin is absorbed and utilized by a human body.
It should be noted that the embodiments of the present invention are not limited by the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A method for efficient directional embedding of zeaxanthin in granular cold water-soluble porous starch, the method comprising the steps of:
(1) Pretreatment of a pulsed electric field: mixing starch and deionized water to form uniform starch suspension, adding an electrolyte solution, adjusting the conductivity of the suspension to 50-300 mu s/cm, pumping into pulse electric field treatment equipment for treatment, wherein the flow rate is 50-250 mL/min, the pulse frequency of a pulse electric field is 800-2000 Hz, the pulse width is 10-100 us, the electric field intensity is 2-15 kV/cm, the treatment time is 10-120 min, and carrying out vacuum suction filtration, washing, drying, crushing and sieving on the treated starch to obtain pulse electric field pretreated starch;
(2) And (3) enzymolysis treatment: mixing the pulsed electric field pretreated starch obtained in the step (1) with a buffer solution to form a uniform starch suspension, adding alpha-amylase and starch transglucosidase into the mixture for enzymolysis at the temperature of between 40 and 50 ℃ in a water bath, wherein the enzymolysis time is between 0.5 and 5.5 hours, the mass ratio of the alpha-amylase to the starch transglucosidase is between 2:1 and 1:2, the total addition amount of the alpha-amylase and the starch transglucosidase is between 0.5 and 4.0 weight percent, and carrying out vacuum suction filtration, water washing, alcohol washing, drying, crushing and sieving on the starch after enzymolysis to obtain the pulsed electric field assisted preparation of porous starch;
(3) Alcohol alkali treatment: mixing the porous starch prepared in the step (2) with ethanol to form uniform starch milk, adding sodium hydroxide to react in a water bath at 15-35 ℃, neutralizing the reacted starch, vacuum filtering, washing with alcohol, drying, crushing, and sieving to obtain the granular cold water soluble porous starch prepared in an auxiliary manner by the pulse electric field;
(4) Embedding zeaxanthin: mixing the granular cold water soluble porous starch prepared in the step (3) with ethanol to form uniform starch milk, adding a zeaxanthin absolute ethanol solution, carrying out water bath adsorption at 15-35 ℃ to obtain a zeaxanthin inclusion compound, carrying out vacuum filtration on the adsorbed inclusion compound, carrying out alcohol washing, drying and crushing to obtain the granular cold water soluble porous starch-zeaxanthin inclusion compound prepared in an auxiliary manner by the pulse electric field.
2. The method of claim 1, wherein the starch in step (1) is one or more of corn starch and waxy corn starch; the electric field strength is 4-12 kV/cm.
3. The method according to claim 1, wherein the electrolyte solution is one or both of potassium sulfate and potassium chloride solution, and the concentration of the electrolyte solution is 0.2 to 2mol/L.
4. The method according to claim 1, wherein the buffer in step (2) is acetic acid-sodium acetate buffer or phosphate buffer, and the pH of the buffer is 4-7.
5. The method according to claim 1, wherein the enzyme activity of the alpha-amylase is 3000 to 5000U/mL and the enzyme activity of the amylotransglucosidase is 5000 to 200000U/mL.
6. The method according to claim 1, wherein the ethanol concentration in step (3) is 70 to 100wt%.
7. The method according to claim 1, wherein the mass ratio of ethanol to pulsed electric field-assisted preparation of porous starch in step (3) is 4:1-40:1; the mass ratio of the sodium hydroxide to the pulsed electric field for auxiliary preparation of the porous starch is 1:10-1:1.
8. The method according to claim 1, wherein the water bath reaction in the step (3) is carried out at 20-30 ℃ for 5-30 min.
9. The method according to claim 1, wherein the mass ratio of zeaxanthin and pulsed electric field-assisted preparation of granular cold water-soluble porous starch in step (4) is 3:1-30:1.
10. The method according to claim 1, wherein the water bath temperature in the step (4) is 25-35 ℃ and the adsorption time is 0.5-4.5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310711728.4A CN116790031A (en) | 2023-06-15 | 2023-06-15 | Method for efficiently and directionally embedding zeaxanthin by granular cold water-soluble porous starch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310711728.4A CN116790031A (en) | 2023-06-15 | 2023-06-15 | Method for efficiently and directionally embedding zeaxanthin by granular cold water-soluble porous starch |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116790031A true CN116790031A (en) | 2023-09-22 |
Family
ID=88035718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310711728.4A Pending CN116790031A (en) | 2023-06-15 | 2023-06-15 | Method for efficiently and directionally embedding zeaxanthin by granular cold water-soluble porous starch |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116790031A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824165A (en) * | 2010-05-04 | 2010-09-08 | 西南大学 | Granular cold water soluble porous starch |
| CN102433367A (en) * | 2011-09-26 | 2012-05-02 | 西北大学 | Preparation method of microporous starch having high specific surface area |
| CN111067096A (en) * | 2019-11-28 | 2020-04-28 | 中新国际联合研究院 | Porous starch microcapsule embedding lutein and preparation method thereof |
| CN112831081A (en) * | 2020-12-31 | 2021-05-25 | 江南大学 | Preparation method of V-shaped granular porous starch |
-
2023
- 2023-06-15 CN CN202310711728.4A patent/CN116790031A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824165A (en) * | 2010-05-04 | 2010-09-08 | 西南大学 | Granular cold water soluble porous starch |
| CN102433367A (en) * | 2011-09-26 | 2012-05-02 | 西北大学 | Preparation method of microporous starch having high specific surface area |
| CN111067096A (en) * | 2019-11-28 | 2020-04-28 | 中新国际联合研究院 | Porous starch microcapsule embedding lutein and preparation method thereof |
| CN112831081A (en) * | 2020-12-31 | 2021-05-25 | 江南大学 | Preparation method of V-shaped granular porous starch |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2023151350A1 (en) | Curcumin-loaded composite gel microsphere based on cross-linked corn porous starch, and preparation method therefor | |
| Cai et al. | Curcumin loading and colon release of pectin gel beads: Effect of different de-esterification method | |
| Vandenberg et al. | Evaluation of protein release from chitosan-aginate microcapsules produced using external or internal gelation | |
| CN111067096B (en) | Porous starch microcapsule embedding lutein and preparation method thereof | |
| CN110918095A (en) | Carbon/titanium dioxide/noble metal composite material, photocatalyst and preparation method thereof | |
| CN108970587B (en) | Composite modified montmorillonite chitosan cross-linked adsorbent and preparation method thereof | |
| CN115109303B (en) | pH response type oxidative crosslinking starch gel embedded with procyanidine and preparation method thereof | |
| CN112690463A (en) | Hericium erinaceus dietary fiber, and preparation method and application thereof | |
| CN116790031A (en) | Method for efficiently and directionally embedding zeaxanthin by granular cold water-soluble porous starch | |
| CN114146679A (en) | Millimeter-grade nitrogen-doped porous carbon sphere and preparation and application thereof | |
| CN109453743A (en) | A kind of graphene oxide/bentonite nano piece aeroge, preparation method and application | |
| Khorasani et al. | Pectin/lignocellulose nanofibers/chitin nanofibers bionanocomposite as an efficient biosorbent of cholesterol and bile salts | |
| Zhao et al. | Synthesis and applications of pectin-based nanomaterials | |
| CN114948908A (en) | Preparation method of high-load oral paclitaxel capsule for colon sustained release | |
| CN112495435B (en) | Chitosan-based graphene/TiO 2 Composite microsphere and preparation method thereof | |
| CN1554330A (en) | Konjaku gluocomannan-calcium alginate microball for carrying medicine and preparing method | |
| CN111359549B (en) | Preparation method of composite hydrogel and aerogel | |
| CN116570620A (en) | Chitin-based multifunctional nano-enzyme and preparation method and application thereof | |
| CN116570552A (en) | Carrier hydrogel for targeted slow release of probiotics and preparation method and application thereof | |
| CN115300480B (en) | Calcium alginate suspension microcapsule for encapsulating probiotics and preparation method and application thereof | |
| WO2023231292A1 (en) | Beet pulp all-component emulsifying thickener, preparation method therefor, and application thereof | |
| CN115919805A (en) | Sea urchin-shaped mesoporous silica-loaded curcumin nanoparticles and preparation method thereof | |
| CN111481503B (en) | Vitamin D3-loaded nano calcium carbonate pickering emulsion and preparation method and application thereof | |
| CN109290064B (en) | Preparation method of graphene/titanium dioxide/polyacrylamide composite self-degradation flocculant | |
| CN106111085A (en) | Material of chitosan-based adsorbent a kind of of quick process waste water from dyestuff and preparation 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 |