CN116918861A - Sodium alginate-based gas carrier and preparation method and application thereof - Google Patents
Sodium alginate-based gas carrier and preparation method and application thereof Download PDFInfo
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- CN116918861A CN116918861A CN202310709466.8A CN202310709466A CN116918861A CN 116918861 A CN116918861 A CN 116918861A CN 202310709466 A CN202310709466 A CN 202310709466A CN 116918861 A CN116918861 A CN 116918861A
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- Prior art keywords
- sodium alginate
- gas
- ethylene
- bubble
- carrier
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 53
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 53
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000005977 Ethylene Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000010008 shearing Methods 0.000 claims abstract description 12
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 67
- 229920000858 Cyclodextrin Polymers 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 235000012055 fruits and vegetables Nutrition 0.000 claims description 9
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000004907 flux Effects 0.000 claims description 8
- 230000005070 ripening Effects 0.000 claims description 8
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 7
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 7
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 7
- -1 sucrose fatty acid ester Chemical class 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 230000003100 immobilizing effect Effects 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 6
- 229920000053 polysorbate 80 Polymers 0.000 claims description 6
- 239000001116 FEMA 4028 Substances 0.000 claims description 5
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 5
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 5
- 229960004853 betadex Drugs 0.000 claims description 5
- 108010046377 Whey Proteins Proteins 0.000 claims description 4
- 102000007544 Whey Proteins Human genes 0.000 claims description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 235000021119 whey protein Nutrition 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 2
- JLPULHDHAOZNQI-ZTIMHPMXSA-N 1-hexadecanoyl-2-(9Z,12Z-octadecadienoyl)-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC JLPULHDHAOZNQI-ZTIMHPMXSA-N 0.000 claims description 2
- GUOCOOQWZHQBJI-UHFFFAOYSA-N 4-oct-7-enoxy-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OCCCCCCC=C GUOCOOQWZHQBJI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004277 Ferrous carbonate Substances 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 229940118662 aluminum carbonate Drugs 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 2
- 235000019268 ferrous carbonate Nutrition 0.000 claims description 2
- 229960004652 ferrous carbonate Drugs 0.000 claims description 2
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 2
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 2
- 238000009775 high-speed stirring Methods 0.000 claims description 2
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 235000010987 pectin Nutrition 0.000 claims description 2
- 239000001814 pectin Substances 0.000 claims description 2
- 229920001277 pectin Polymers 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 229940080313 sodium starch Drugs 0.000 claims description 2
- 229940083466 soybean lecithin Drugs 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 12
- 239000011257 shell material Substances 0.000 abstract description 5
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 15
- 238000013270 controlled release Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229940032147 starch Drugs 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 description 2
- 239000005976 Ethephon Substances 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002101 nanobubble Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940051236 barium carbonate Drugs 0.000 description 1
- 229960003563 calcium carbonate Drugs 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 235000012209 glucono delta-lactone Nutrition 0.000 description 1
- 229960003681 gluconolactone Drugs 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 229930195732 phytohormone Natural products 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229940043825 zinc carbonate Drugs 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/144—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
- A23B7/152—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O ; Elimination of such other gases
-
- 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
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Jellies, Jams, And Syrups (AREA)
Abstract
The invention discloses a sodium alginate-based gas carrier and a preparation method and application thereof; the invention prepares a mixed system of sodium alginate aqueous solution and emulsifier; continuously introducing target gas into the mixed system or placing the mixed system in a closed gas environment, and continuously stirring and emulsifying by using a high-speed shearing machine to prepare a bubble system carrying the target gas; adding nano carbonate powder and glucolactone into the bubble system, and inducing the bubble system to be immobilized to prepare the sodium alginate-based gas carrier containing the bubble cavity. The sodium alginate-based gas carrier prepared by the invention can stably store target gas in the carrier, and has the advantages of low cost and simple process. Taking ethylene as an example, sodium alginate is selected as a shell material and can be loaded with 0.31cm 3 The target gas per gram is stored for 28 days conventionally, and the ethylene only releases 32%, so that the stable storage of the ethylene gas is realized.
Description
Technical Field
The invention belongs to the technical field of food and chemical industry, and particularly relates to a sodium alginate-based gas carrier, and a preparation method and application thereof.
Background
The gas is usually stored in high pressure steel bottles, with some risk of leakage and explosion. At present, a plurality of technologies encapsulate gas in a solid medium, and the treatment method can provide safety guarantee for preservation and transportation, but is difficult to popularize and apply in a large range due to the limitation of encapsulation efficiency. Therefore, the invention provides a more efficient and convenient gas encapsulation method, which is beneficial to large-scale popularization and application in the field of gas application. The practical significance and application of the invention will be described in detail by taking ethylene as an example.
Ethylene is a phytohormone that increases the maturity, texture, color and flavor of fruits and vegetables (Critical Reviews in Food Science and Nutrition,2007, 47:543-560). In order to facilitate long-distance transportation and preservation, fruits and vegetables need to be picked in advance, and ripening treatment is carried out before the fruits and vegetables are sold or eaten by consumers. The method commonly used in China is to use ethylene gas or ethephon for ripening, however, the problem that the gas leakage risk and the ethephon corrosiveness reduce the quality of fruits and vegetables exists (Food Chemistry,2013, 141:4208-4214). The problem can be well solved by encapsulating the gas in the solid medium, but the production cost and encapsulation efficiency of the solid medium limit the wide popularization and application of the material. Therefore, in order to solve the problem, the invention discloses a sodium alginate-based gas carrier and a preparation method thereof.
Currently, the solid medium for encapsulating ethylene gas mainly comprises cyclodextrin, metal organic framework, V-shaped starch and the like. Cyclodextrin has certain limitations in encapsulating different gases due to the fixed cavity diameter and effective encapsulation efficiency; the cyclodextrin metal organic frame material can remarkably improve the encapsulation efficiency of gas (ACS Applied Materials & Interfaces,2020, 12:34095-34104), but is difficult to popularize and apply on a large scale due to higher cost; the V-type crystalline starch has better ethylene loading performance (Journal of Agricultural and Food Chemistry,2017, 65:2189-2197), but the release speed of the gas is too high, which is not beneficial to practical application; the outer surface of the V-shaped starch is covered with an oil film, so that the release rate of ethylene (Carbohydrate Polymers,2022,291: 119556) can be obviously reduced, but the production process and the cost of the phase change are increased, and the actual application requirements are not met.
The concept of bubbles generally refers to spherical bubbles formed by wrapping a gas with a liquid or a solid, and can be classified into nanobubbles, microbubbles, and macroscopic bubbles according to the size of the bubbles (Advances in Colloid and Interface Science,2017, 246:40-51). After 2001, various bulk nano-bubbles have emerged as a preparation technology for various applications in various fields, such as water treatment, drug transport, surface cleaning, mineral flotation, and the like, and in particular, drug transport includes transport of therapeutic gases (Journal of Controlled Release,2015, 209:139-49), such as oxygen, xenon, nitric oxide, and the like. Research on bubble carriers at home and abroad is rapidly developing, and provides possibility for carrying ethylene. However, the type of bubble shell structure material, the pH of the solution, the ionic strength, the system temperature, etc., significantly affect the stability of the bubbles (Journal of Controlled Release,2021, 339:164-94). The shell structure formed by different materials has different flexibility and plasticity, such as oxygen-carrying bubbles formed by phospholipid with certain flexibility, and the stability of carrier gas can reach 21 days while ensuring excellent oxygen-carrying performance; the pH value of the solution system influences the zeta potential of the bubbles, and meanwhile, the existence of hydroxyl ions can form hydrogen bonds with shell materials of the bubbles, so that the long-term stability of the bubbles is facilitated, for example, the size of the bubbles constructed under the condition of higher pH value is not changed obviously after the bubbles are placed for 18 days; cations in the system can influence the interaction between hydroxide ions and the surfaces of bubbles, so that the system potential is reduced, the repulsive force between the bubbles is reduced, and the stability of the bubbles is reduced; in addition, studies have shown that an increase in system temperature enhances the mobility of hydroxide ions, so that the mutual repulsive force between bubbles is weakened, bubble collisions are easy to break, and the stability of the bubble system is reduced. Therefore, if the bubble carrier can be used for loading ethylene ripening agent, the development of the ripening industry of agricultural products, fruits and vegetables is promoted. Currently, existing ethylene carriers, including starches, have certain limitations. Aiming at the limitations, the invention researches and develops the ethylene bubble gel carrier which is low in price, stable in storage performance and capable of being practically applied by taking sodium alginate as a raw material.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the preparation method of the sodium alginate-based gas carrier, which is simple and convenient to operate, short in time consumption and low in cost, and can remarkably improve the ethylene loading performance. The sodium alginate-based gas carrier can effectively store gas and is applied to ripening of fruits and vegetables.
The aim of the invention is realized by the following technical scheme:
the preparation method of the sodium alginate-based gas carrier comprises the following steps:
(1) Preparing a sodium alginate aqueous solution system with the mass concentration of 0.2-5%, adding cyclodextrin with the mass concentration of 0-15%, and fully stirring for dissolution;
(2) Adding 0.1-5wt% of emulsifier into the sodium alginate solution obtained in the step (1), and fully stirring and mixing;
(3) Continuously introducing gas into the mixed system obtained in the step (2) at a flux of 0.1-100mL/min or placing the mixed system in a closed gas environment, and simultaneously shearing at a high speed of 1000-30000rpm for 2-10min to prepare a bubble system;
(4) Adding 0.1-10wt% of nano carbonate powder into the bubble system obtained in the step (3), uniformly mixing, adding 0.1-3wt% of glucolactone, and standing and immobilizing bubbles for 10-60min to obtain a bubble gel system containing gas.
Preferably, in the step (1), the cyclodextrin is one of α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin;
further preferably, the cyclodextrin is α -cyclodextrin.
Preferably, in the step (1), the mass concentration of the sodium alginate aqueous solution system is 1-3%.
Preferably, in the step (1), the mass concentration of the added cyclodextrin is 10-15%.
Preferably, in the step (2), the emulsifier is one of tween 80, tween 20, span80, whey protein isolate, whey protein concentrate, soybean lecithin, sucrose fatty acid ester, monoglyceride, pectin, and sodium starch octenyl succinate.
Preferably, in the step (2), the mass concentration of the added emulsifier is 0.5-2%.
Preferably, in step (3), the gas is ethylene, carbon dioxide, nitrogen; the pressure of the operation of the load gas is normal pressure, and the temperature is normal temperature;
preferably, in step (3), the closed gas environment refers to one of a glove box and a container chamber filled with the target gas.
Preferably, in step (3), the gas flux is 10-50mL/min.
Preferably, in the step (3), the gas flux is 0.1-100mL/min/50mL of the mixed system.
Preferably, in the step (3), the high-speed shearing means one of a high-speed shearing machine or a device with a high-speed stirring paddle;
preferably, in step (3), the high shear rate is 5000-20000rpm.
Preferably, in the step (3), the time of the high-speed shearing is 2-5min.
Preferably, in the step (4), the carbonate is one of calcium carbonate, magnesium carbonate, zinc carbonate, ferrous carbonate, barium carbonate and aluminum carbonate.
Preferably, in the step (4), the carbonate is added in an amount of 0.1-2% by mass.
Preferably, in the step (4), the mass percentage of the gluconolactone is 0.1-1%.
Preferably, in the step (4), the air bubbles are kept stand and immobilized for 20-30min.
Preferably, the operating temperature of steps (1), (2), (3), (4) is 15 to 35 ℃.
The sodium alginate-based gas carrier prepared by the preparation method is provided.
The sodium alginate-based gas carrier is applied to ripening of fruits and vegetables.
Preferably, the gas is ethylene.
According to the invention, the air is loaded by utilizing the cavity structure of the air bubble, and the breakage of the air bubble is prevented or slowed down by utilizing the immobilization of the air bubble, so that the loading capacity and the loading stability of the air are obviously improved. In the construction of a bubble system, surfactant molecules can be adsorbed on a water-air interface, so that the interfacial tension is reduced, and the stability of a bubble structure is effectively maintained; after the coagulant is added, the released salt ions can interact with sodium alginate molecules in the system, so that the bubble structure is fixed, a solid gel ethylene carrier with a cavity structure is formed, and the high-efficiency and stable loading and storage of gas are realized. In the invention, not only the shell structure of the bubbles prevents gas from escaping, but also water molecules in the system can form a compact water film around the bubble structure, thereby further preventing the release of the gas. As the water molecules decrease, the gel structure collapses, thereby achieving an efficient release of ethylene from the carrier material. Meanwhile, the preparation process is simple, the cost is low, and the operation is easy.
Compared with the prior art, the invention has the advantages that:
(1) The sodium alginate-based gas carrier prepared by the method has a large number of bubble structures, can obviously improve the gas loading performance under the normal pressure condition, and forms gel after the bubble carrier is solidified to form a closed bubble structure, so that the effective load stores ethylene.
(2) Compared with the traditional solid phase loading method, the preparation method of the sodium alginate-based solid carrier has the advantages of remarkably reducing the technical requirements of product preparation, along with short time consumption, easy operation, low cost, simple process and more contribution to industrial production and large-scale popularization and application.
(3) The encapsulating material adopted by the invention has wide sources, is cheap and easy to obtain, and has simple equipment and preparation flow, and is environment-friendly.
Drawings
FIG. 1 shows release curves of ethylene in sodium alginate-based bubble systems and bubble gel systems obtained in comparative example 1, comparative example 2 and examples 1 and 2.
FIG. 2 is a diagram showing the appearance of the sodium alginate-based bubble gel system obtained in example 1 (A, B) and example 2 (C, D).
FIG. 3 shows the ethylene content of the sodium alginate-based bubble gel system obtained in example 1 and example 2.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to the scope expressed by the examples.
The following examples illustrate the technical aspects of the invention with ethylene gas. The technical scheme of the invention is not limited to ethylene gas, and other gases such as carbon dioxide, nitrogen and the like are also applicable.
The apparent morphology of the sodium alginate-based gas controlled release carrier is observed by adopting the following method: and freeze-drying the obtained carrier, slicing, adhering the carrier to an objective table adhered with a conductive double faced adhesive tape, and then observing the apparent morphology of the carrier by a scanning electron microscope.
In the examples, determination of ethylene content in sodium alginate based gas carrier: a certain amount of bubbles or bubble gel carrier is taken in a headspace bottle, 1mL of 0.1M sodium hydroxide solution is added, and the bottle cap is quickly screwed. Stirring overnight at 400r/min, completely destroying bubbles or bubble gel structure to release ethylene completely, and measuring ethylene content by headspace-gas chromatography. The gas chromatograph was equipped with a hydrogen Flame Ion Detector (FID) and a DB-5 column (30 m 0.32mm 0.25 μm), and the carrier gas was high purity nitrogen with a flow rate of 40mL/min. The test conditions of the headspace sampler are as follows: oven temperature 60 ℃, sample injection temperature 250 ℃, headspace bottle pressurization time 0.2min. The peak area of ethylene was converted to ethylene concentration based on ethylene standard.
Example 1
(1) Preparing 50mL of sodium alginate aqueous solution system with mass concentration of 1%, and fully stirring and dissolving;
(2) Adding 0.5wt% of Tween 80 as an emulsifier into the solution obtained in the step (1), and fully stirring and mixing;
(3) Continuously introducing ethylene into the mixed system obtained in the step (2) at a flux of 20 mL/min; simultaneously shearing at 20000rpm for 2min to prepare a bubble system;
(4) Adding 0.5wt% of nano calcium carbonate powder into the bubble system obtained in the step (3), uniformly mixing, adding 0.1wt% of glucolactone, standing and immobilizing bubbles for 30min to obtain a bubble gel system containing ethylene.
As shown in FIG. 3, the ethylene loading in the resulting bubble gel system was 0.31mL/g. As shown in fig. 1, the ethylene in the obtained sodium alginate-based gas carrier can be stably stored, and only 32% of ethylene is released within a measurement time of 28 days, so that the stable storage of ethylene is realized.
Example 2
(1) Preparing 50mL of sodium alginate aqueous solution system with the mass concentration of 1wt%, and simultaneously adding alpha-cyclodextrin with the mass concentration of 10% relative to water, and fully stirring for dissolution;
(2) Adding 0.5wt% of Tween 80 as an emulsifier into the solution obtained in the step (1), and fully stirring and mixing;
(3) Continuously introducing ethylene into the mixed system obtained in the step (2) at a flux of 20 mL/min; simultaneously shearing at 20000rpm for 2min to prepare a bubble system;
(4) Adding 0.5wt% of nano calcium carbonate powder into the bubble system obtained in the step (3), uniformly mixing, adding 0.1wt% of glucolactone, standing and immobilizing bubbles for 30min to obtain a bubble gel system containing ethylene.
As shown in FIG. 3, the ethylene loading in the resulting bubble gel system was 0.23mL/g. As shown in fig. 1, the ethylene controlled release performance of the obtained sodium alginate-based gas controlled release carrier is better, and the ethylene release rate in the release measurement of 28 days is 25%; realizes the stable storage of ethylene in the carrier.
Example 3
(1) Preparing 50mL of sodium alginate aqueous solution system with the mass concentration of 1wt%, and simultaneously adding beta-cyclodextrin with the mass concentration of 10% relative to water, and fully stirring for dissolution;
(2) Adding 0.5wt% of Tween 80 as an emulsifier into the solution obtained in the step (1), and fully stirring and mixing;
(3) Continuously introducing ethylene into the mixed system obtained in the step (2) at a flux of 20 mL/min; simultaneously shearing at 20000rpm for 2min to prepare a bubble system;
(4) Adding 0.5wt% of nano calcium carbonate powder into the bubble system obtained in the step (3), uniformly mixing, adding 0.1wt% of glucolactone, standing and immobilizing bubbles for 30min to obtain a bubble gel system containing ethylene.
The ethylene loading in the bubble gel system was tested to be 0.18mL/g. The obtained sodium alginate-based gas controlled release carrier has good ethylene controlled release performance, and the ethylene release rate in 28 days is 26%, so that the sodium alginate-based gas controlled release carrier is a stable ethylene storage carrier.
Example 4
(1) Preparing 50mL of sodium alginate aqueous solution system with mass concentration of 2%, and fully stirring and dissolving;
(2) Adding 0.5wt% of Tween 80 as an emulsifier into the solution obtained in the step (1), and fully stirring and mixing;
(3) Continuously introducing ethylene into the mixed system obtained in the step (2) at a flux of 20 mL/min; simultaneously shearing at 20000rpm for 2min to prepare a bubble system;
(4) Adding 0.5wt% of nano calcium carbonate powder into the bubble system obtained in the step (3), uniformly mixing, adding 0.1wt% of glucolactone, standing and immobilizing bubbles for 30min to obtain a bubble gel system containing ethylene.
The ethylene loading in the resulting bubble gel system was tested to be 0.28mL/g. The obtained sodium alginate gas controlled release carrier has good ethylene controlled release performance, and the ethylene release rate in 28 days is 32.8%, so that the sodium alginate gas controlled release carrier is a stable ethylene storage carrier.
Comparative example 1
According to the steps (1), (2) and (3) of example 1, sodium alginate is used as a raw material to prepare a bubble system, and the gas storage and release effects are measured. After taking out, samples were taken at regular intervals, and the ethylene retention in the bubbles was measured.
The ethylene loading in the resulting bubble system was tested to be 0.57mL/g. As shown in fig. 1, the ethylene release rate of sodium alginate bubbles reaches 90% on day 3, mainly bubble collapse, resulting in rapid ethylene release.
Comparative example 2
According to the steps (1), (2) and (3) of example 2, sodium alginate and alpha-cyclodextrin are used as raw materials to prepare a bubble system, and the gas storage and release effects are measured. After taking out, samples were taken at regular intervals, and the ethylene retention in the bubbles was measured.
The ethylene loading in the resulting bubble system was tested to be 0.51mL/g. As shown in fig. 1, the ethylene release rate of sodium alginate bubbles was 80% or more at day 7, and most of the ethylene gas was released, so that ethylene could not be stably stored.
Comparative example 3
According to example 3, steps (1), (2) and (3) were carried out without adding sodium alginate, and a bubble system was prepared from beta-cyclodextrin as a raw material, and the gas storage and release effects were measured. After taking out, samples were taken at regular intervals, and the ethylene retention in the bubbles was measured.
The ethylene loading in the resulting bubble system was tested to be 0.64mL/g. Ethylene release rate of the beta-cyclodextrin bubble system reaches 70% on day 7, and ethylene cannot be stably stored.
FIG. 1 shows release curves of ethylene in sodium alginate-based bubble systems and bubble gel systems obtained in comparative example 1, comparative example 2 and examples 1 and 2.
FIG. 2 is a diagram showing the appearance of the sodium alginate-based bubble gel system obtained in example 1 (A, B) and example 2 (C, D).
As shown in FIG. 1, in comparative example 1, the ethylene release rate in sodium alginate bubbles was faster, and the ethylene release rate reached 85% or more on day 3. In comparative example 2, after the alpha-cyclodextrin was added, the release rate of ethylene in the bubbles was slowed down and the release rate of ethylene reached 80% or more on day 7. Nevertheless, the mixed system of sodium alginate and alpha-cyclodextrin bubbles are still not able to stabilize ethylene in the preservation material. The sodium alginate bubble gel carrier prepared in example 1 can significantly improve the storage performance of the gas, and only releases 32% of the gas in a 28-day stability test; the addition of cyclodextrin small molecule polysaccharide to the bubble gel carrier prepared in example 2 further reduced the ethylene release rate by only 25% over 28 days. The results show that the sodium alginate-based bubble carrier is a relatively stable ethylene carrier, can meet the storage and transportation requirements of gas and can also meet the application requirements of actual ripening fruits and vegetables.
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 equivalent to the embodiments described above, and are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the sodium alginate-based gas carrier is characterized by comprising the following steps of:
(1) Preparing a sodium alginate aqueous solution system with the mass concentration of 0.2-5%, adding 0-15% by weight of cyclodextrin, and fully stirring for dissolution;
(2) Adding 0.1-5wt% of emulsifier into the sodium alginate solution obtained in the step (1), and fully stirring and mixing;
(3) Continuously introducing gas into the mixed system obtained in the step (2) at a flux of 0.1-100mL/min or placing the mixed system in a closed gas environment, and simultaneously shearing at a high speed of 1000-30000rpm for 2-10min to prepare a bubble system;
(4) Adding 0.1-10wt% of nano carbonate powder into the bubble system obtained in the step (3), uniformly mixing, adding 0.1-3wt% of glucolactone, and standing and immobilizing bubbles for 10-60min to obtain the sodium alginate-based gas carrier containing gas.
2. The method according to claim 1, wherein in the step (1), the cyclodextrin is one of α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin.
3. The method according to claim 1, wherein in the step (2), the emulsifier is one of tween 80, tween 20, span80, whey protein isolate, whey protein concentrate, soybean lecithin, sucrose fatty acid ester, monoglyceride, pectin, and sodium starch octenyl succinate.
4. The method according to claim 1, wherein in the step (3), the gas is ethylene, carbon dioxide, nitrogen; the pressure of the load gas operation is normal pressure, and the temperature is normal temperature.
5. The method according to claim 1, wherein in the step (3), the closed gas atmosphere means a glove box or container filled with the target gas.
6. The method according to claim 1, wherein in the step (3), the high-speed shearing means using a high-speed shearing machine or an apparatus with a high-speed stirring paddle.
7. The method according to claim 1, wherein in the step (4), the carbonate is one of calcium carbonate, magnesium carbonate, zinc carbonate, ferrous carbonate, barium carbonate, and aluminum carbonate.
8. The process according to claim 1, wherein the operating temperature of steps (1), (2), (3), (4) is 15 to 35 ℃.
9. The sodium alginate-based gas carrier produced by the production method of any one of claims 1 to 8.
10. The use of the sodium alginate-based gas carrier of claim 9 in ripening fruits and vegetables.
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