CN111759804A - Preparation method of pickering emulsion with synergistically stabilized clay particles and prolamine particles - Google Patents
Preparation method of pickering emulsion with synergistically stabilized clay particles and prolamine particles Download PDFInfo
- Publication number
- CN111759804A CN111759804A CN202010717649.0A CN202010717649A CN111759804A CN 111759804 A CN111759804 A CN 111759804A CN 202010717649 A CN202010717649 A CN 202010717649A CN 111759804 A CN111759804 A CN 111759804A
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- CN
- China
- Prior art keywords
- prolamine
- particles
- dispersion liquid
- oil
- pickering emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 239000000839 emulsion Substances 0.000 title claims abstract description 110
- 239000004927 clay Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 238000002156 mixing Methods 0.000 claims abstract description 5
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- 229910052901 montmorillonite Inorganic materials 0.000 claims description 50
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- 238000000034 method Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 22
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- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 17
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- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 4
- 235000018936 Vitellaria paradoxa Nutrition 0.000 claims description 4
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- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 claims description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 4
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- 229940057910 shea butter Drugs 0.000 claims description 4
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- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 claims description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 4
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 3
- LADGBHLMCUINGV-UHFFFAOYSA-N tricaprin Chemical compound CCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCC)COC(=O)CCCCCCCCC LADGBHLMCUINGV-UHFFFAOYSA-N 0.000 claims description 3
- NRTKYSGFUISGRQ-UHFFFAOYSA-N (3-heptanoyloxy-2,2-dimethylpropyl) heptanoate Chemical compound CCCCCCC(=O)OCC(C)(C)COC(=O)CCCCCC NRTKYSGFUISGRQ-UHFFFAOYSA-N 0.000 claims description 2
- OVYMWJFNQQOJBU-UHFFFAOYSA-N 1-octanoyloxypropan-2-yl octanoate Chemical compound CCCCCCCC(=O)OCC(C)OC(=O)CCCCCCC OVYMWJFNQQOJBU-UHFFFAOYSA-N 0.000 claims description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical class CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- NFIHXTUNNGIYRF-UHFFFAOYSA-N 2-decanoyloxypropyl decanoate Chemical compound CCCCCCCCCC(=O)OCC(C)OC(=O)CCCCCCCCC NFIHXTUNNGIYRF-UHFFFAOYSA-N 0.000 claims description 2
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 claims description 2
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 claims description 2
- UIVPNOBLHXUKDX-UHFFFAOYSA-N 3,5,5-trimethylhexyl 3,5,5-trimethylhexanoate Chemical compound CC(C)(C)CC(C)CCOC(=O)CC(C)CC(C)(C)C UIVPNOBLHXUKDX-UHFFFAOYSA-N 0.000 claims description 2
- FVKRIDSRWFEQME-UHFFFAOYSA-N 3-methylbutyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCC(C)C FVKRIDSRWFEQME-UHFFFAOYSA-N 0.000 claims description 2
- HBTAOSGHCXUEKI-UHFFFAOYSA-N 4-chloro-n,n-dimethyl-3-nitrobenzenesulfonamide Chemical compound CN(C)S(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 HBTAOSGHCXUEKI-UHFFFAOYSA-N 0.000 claims description 2
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 claims description 2
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- 235000005976 Citrus sinensis Nutrition 0.000 claims description 2
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- CMBYOWLFQAFZCP-UHFFFAOYSA-N Hexyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCCCC CMBYOWLFQAFZCP-UHFFFAOYSA-N 0.000 claims description 2
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 claims description 2
- OQILCOQZDHPEAZ-UHFFFAOYSA-N Palmitinsaeure-octylester Natural products CCCCCCCCCCCCCCCC(=O)OCCCCCCCC OQILCOQZDHPEAZ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004264 Petrolatum Substances 0.000 claims description 2
- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- 235000019485 Safflower oil Nutrition 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 claims description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N benzoic acid ethyl ester Natural products CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 2
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- 229910001919 chlorite Inorganic materials 0.000 claims description 2
- 229910052619 chlorite group Inorganic materials 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 2
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- 235000005687 corn oil Nutrition 0.000 claims description 2
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- SASYSVUEVMOWPL-NXVVXOECSA-N decyl oleate Chemical compound CCCCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC SASYSVUEVMOWPL-NXVVXOECSA-N 0.000 claims description 2
- 229940031578 diisopropyl adipate Drugs 0.000 claims description 2
- PKPOVTYZGGYDIJ-UHFFFAOYSA-N dioctyl carbonate Chemical compound CCCCCCCCOC(=O)OCCCCCCCC PKPOVTYZGGYDIJ-UHFFFAOYSA-N 0.000 claims description 2
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- SRVSYCCHRDXMMS-UHFFFAOYSA-N dodecan-5-yl 2-hydroxybenzoate Chemical compound CCCCCCCC(CCCC)OC(=O)C1=CC=CC=C1O SRVSYCCHRDXMMS-UHFFFAOYSA-N 0.000 claims description 2
- GJQLBGWSDGMZKM-UHFFFAOYSA-N ethylhexyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(CC)CCCCC GJQLBGWSDGMZKM-UHFFFAOYSA-N 0.000 claims description 2
- 235000008524 evening primrose extract Nutrition 0.000 claims description 2
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 claims description 2
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- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 claims description 2
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- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 claims description 2
- 229940119170 jojoba wax Drugs 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
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- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 2
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- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 claims description 2
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- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
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- A—HUMAN NECESSITIES
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- Colloid Chemistry (AREA)
Abstract
The invention discloses a preparation method of pickering emulsion with synergistic stabilization of clay particles and prolamine particles, which comprises the steps of preparing clay particle dispersion liquid; preparing pickering emulsion: and mixing the clay particle dispersion liquid, the prolamine particle dispersion liquid and the oil phase, and homogenizing at a high speed to obtain the stable pickering emulsion. The pickering emulsion prepared by the invention has the characteristics of pure natural emulsifier raw materials, biological friendliness, environmental friendliness, simple and controllable preparation method and the like, and can be used for effectively preparing stable pickering emulsion.
Description
Technical Field
The invention belongs to the technical field of food, cosmetics and medicines, and particularly relates to a preparation method of pickering emulsion with synergistic and stable clay particles and prolamine particles.
Background
Pickering emulsions are a new type of emulsion stabilized with colloidal particles. The colloid particles are adsorbed on the oil-water interface, and the liquid drops are tightly wrapped to prevent aggregation, so that the emulsion is effectively stabilized. Compared with the traditional emulsion, the pickering emulsion has the advantages of less foaming in the emulsification process, high stability, controllable rheological property and the like. In addition, the colloidal particles replace molecular emulsifiers, so that the cost can be saved and the environmental pollution can be reduced.
So far, many studies have been made to prepare pickering emulsions using synthetic polymer-based colloidal particles. However, these particles generally have the disadvantages of poor biocompatibility and non-biodegradability, which greatly limits the application of the prepared pickering emulsion in the fields of cosmetics, foods, medicines and the like. For this reason, many studies have been focused on inorganic or biomacromolecule colloidal particles of natural origin to develop pickering emulsions that can be applied to the above-mentioned fields.
Wherein, the clay mineral has the advantages of natural source, good biocompatibility, biodegradability, environmental friendliness and the like. However, natural clay particles have strong hydrophilicity and cannot stabilize pickering emulsion alone, so that the surface of the clay particles needs to be modified to have proper wettability so as to stabilize the pickering emulsion. However, most surface modification processes have the disadvantages of complicated process, poor controllability, use of harmful solvents, and the like. Therefore, it remains a problem to be solved to find a simple and green controllable means of applying clay particles to the preparation of pickering emulsions.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The invention provides a method for preparing pickering emulsion with synergistic stabilization of clay particles and prolamine particles, which comprises the following steps,
preparing a clay particle dispersion;
preparing a prolamine particle dispersion;
preparing pickering emulsion: and mixing the clay particle dispersion liquid, the prolamine particle dispersion liquid and the oil phase, and homogenizing at a high speed to obtain the stable pickering emulsion.
As a preferred embodiment of the method for preparing a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to the present invention: the clay is one or more of montmorillonite, kaolin, illite and chlorite clay particles; the prolamine is one or more of zein, wheat prolamine or kafirin.
As a preferred embodiment of the method for preparing a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to the present invention: the clay particle dispersion liquid is prepared by weighing clay particles, adding the clay particles into deionized water, and performing ultrasonic or high-speed shearing dispersion to obtain the clay particle dispersion liquid.
As a preferred embodiment of the method for preparing a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to the present invention: the concentration of the clay particle dispersion liquid is 0.1-10 w/v% in g/mL, the pH value is 3-9, and the size of the clay particles is 100-5000 nm.
As a preferred embodiment of the method for preparing a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to the present invention: the concentration of the clay particle dispersion liquid is 2 w/v% in g/mL, and the pH value of the clay particle dispersion liquid is 4-5.
As a preferred embodiment of the method for preparing a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to the present invention: the preparation of the prolamine particle dispersion liquid comprises the steps of weighing prolamine, adding 55-95% ethanol water solution, stirring for dissolving, adding the solution into water, stirring, and evaporating at 35-75 ℃ to remove ethanol to obtain the prolamine nanoparticle dispersion liquid.
As a preferred embodiment of the method for preparing a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to the present invention: the prolamine nanoparticle dispersion liquid has a concentration of 0.1-10 w/v% in g/mL, a pH of 3-9, and prolamine nanoparticles of 40-2000 nm in size.
As a preferred embodiment of the method for preparing a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to the present invention: the concentration of the prolamine nanoparticle dispersion liquid is 2 w/v% in g/mL, and the pH value of the prolamine nanoparticle dispersion liquid is 4-5.
As a preferred embodiment of the method for preparing a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to the present invention: the preparation of pickering emulsion, wherein the oil phase comprises soybean oil, castor oil, olive oil, peanut oil, corn oil, sunflower oil, safflower oil, avocado butter, grape seed oil, sesame oil, silicone oil, tea tree oil, evening primrose oil, peppermint oil, rose oil, sweet orange oil, cinnamon oil, liquid paraffin, petrolatum, n-hexane, n-hexadecane, isopropyl myristate, ethylhexyl palmitate, isopropyl palmitate, caprylic/capric triglyceride (GTCC), shea butter, isononyl isononanoate, squalane, glyceryl polymethacrylate, jojoba oil, cetyl alcohol, cetearyl alcohol, behenyl alcohol, stearyl alcohol, myristyl alcohol, dioctyl carbonate, pentaerythritol tetrastearate, ethylhexyl cocoate/isooctyl cocoate, decyl oleate, isoamyl laurate, propylene glycol dicaprylate/dicaprate, One or more of C12-15 alcohol benzoate, PEG-7 glycerol cocoate, shea butter, white oil, glycerol tricaprylate, glycerol stearate, butyl octanol salicylate, neopentyl glycol diheptanoate, dipentaerythritol tri-polyhydroxystearate, isododecane, propylene carbonate, hexyl laurate, polymethyl methacrylate, hydrogenated lecithin, polyisobutylene, diisopropyl adipate, octyldodecanol pivalate and distarch phosphate; the oil phase content is 10-85 v/v%, the prolamine nanoparticles and clay particles content is 0.1-10 w/v%, and the mass ratio of the prolamine nanoparticles to the clay particles is 0.1: 1-1: 0.1.
As a preferred embodiment of the method for preparing a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to the present invention: the high-speed homogenization is carried out for 1-30 min at the speed of 5000-25000 rpm.
The invention has the beneficial effects that: the Pickering emulsion prepared by the method has uniform droplet size, the clay particles are also adsorbed on the interface to form stable Pickering emulsion, and the particle stabilizer is adsorbed on the interface to form a physical barrier to provide stability for the prepared Pickering emulsion. The pickering emulsion prepared by the invention has the characteristics of good biocompatibility, biodegradability, small using amount, low price, simple preparation method and the like of the particle stabilizer, and particularly, the prepared pickering emulsion can obviously improve the stability of pickering emulsions prepared from clay particles and alcohol soluble glutelin particles.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a diagram showing the appearance of a Pickering emulsion in example 1 of the present invention.
FIG. 2 is a diagram showing the structure of the interface of Pickering emulsion and the distribution of the particle size of emulsion droplets in example 2 of the present invention, wherein the green fluorescence label is montmorillonite particles and the red fluorescence label is zein particles.
FIG. 3 is a diagram of a Pickering emulsion stabilized with caprylic/capric triglyceride (GTCC) as the oil phase in example 3 of the present invention.
FIG. 4 is a graph of the appearance of the Pickering emulsion of example 4 of the present invention and a comparison of its centrifugal stability at 4000 rpm.
Fig. 5 is a pickering emulsion prepared from zein particles alone (left panel) and clay particles alone (right panel) of comparative example 1 using liquid paraffin as the oil phase at pH 5.
FIG. 6 is a graph of the appearance of pickering emulsions prepared with corn clay particles and prolamine particles of the present invention at concentrations of 0.1 w/v%, respectively.
FIG. 7 is a graph of the appearance of a Pickering emulsion prepared in comparative example 8 at a pH of 10 for the aqueous phase.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Montmorillonite particles, montmorillonite CAS in the present invention: 1318-93-0, is prepared from natural mineral bentonite, has the size of 400-2000 nm and has a molecular formula of Al2O9Si3Molecular weight is 282.2; zein CAS in the invention: 9010-66-6, is derived from corn and has a size of 40-1500 nm. Other raw materials, unless otherwise specified, are commonly commercially available.
Example 1:
(1) dispersing 0.1g of montmorillonite particles into 5mL of deionized water to obtain montmorillonite particle dispersion liquid;
(2) dropwise adding 1M HCl to the montmorillonite particle dispersion liquid of step (1) and adjusting pH to 5 to obtain a montmorillonite particle dispersion liquid of 2 w/v% (g/mL) and pH to 5;
(3) dissolving 1g zein in 25mL80 v/v% ethanol water solution, and magnetically stirring at 500rpm/min for 30 min;
(4) adding the zein ethanol aqueous solution obtained in the step (3) into 75mL of deionized water at the speed of 500rpm/min, and stirring for 2h to obtain zein particle ethanol water dispersion;
(5) rotary evaporating the dispersion obtained in the step (4) at 42 ℃ to remove ethanol and part of water to obtain zein particle dispersion liquid of about 2 w/v% (g/mL);
(6) dropwise adding 1M HCl or 1M NaOH into the zein particle dispersion liquid obtained in the step (5) to adjust the pH to be 5, so as to obtain a zein particle dispersion liquid with the pH to be 5 and the concentration of 2 w/v%;
(7) 5mL of the dispersion of step (2) and 10mL of the dispersion of step (6) and 15mL of silicone oil were mixed and homogenized at 15000rpm for 2min at high speed to obtain a Pickering emulsion.
FIG. 1 is an appearance of the emulsion of example 1, which is more stable.
Example 2:
(1) dispersing 0.2g of montmorillonite particles into about 10mL of deionized water to obtain montmorillonite particle dispersion liquid;
(2) dropwise adding 1M HCl to the montmorillonite particle dispersion liquid of step (1) and adjusting pH to 5 to obtain a montmorillonite particle dispersion liquid of 2 w/v% (g/mL) and pH to 5;
(3) dissolving 0.5g zein in 12.5mL 80 v/v% ethanol water solution, and magnetically stirring at 500rpm/min for 30 min;
(4) dropwise adding the zein ethanol aqueous solution obtained in the step (3) into 37.5mL of deionized water under the condition of 500rpm/min, and stirring for 3h to obtain zein particle ethanol aqueous dispersion;
(5) and (3) performing rotary evaporation on the dispersion liquid obtained in the step (4) at the temperature of 45 ℃ to remove ethanol and part of water, so as to obtain a zein particle dispersion liquid of 2 w/v% (g/mL).
(6) Dropwise adding 1M HCl or 1M NaOH into the zein particle dispersion liquid obtained in the step (5) to adjust the pH to 5, so as to obtain a zein particle dispersion liquid with the pH to 5;
(7) 5mL of the dispersion of step (2) and 10mL of the dispersion of step (5) and 15mL of liquid paraffin were homogenized at 15000rpm for 2min at high speed to obtain a Pickering emulsion.
Example 3:
(1) dispersing 2g of montmorillonite particles into about 100mL of deionized water to obtain montmorillonite particle dispersion liquid;
(2) dropwise adding 1M HCl to the montmorillonite particle dispersion liquid of step (1) and adjusting pH to 5 to obtain a montmorillonite particle dispersion liquid of 2 w/v% (g/mL) and pH to 5;
(3) dissolving 2g of zein in 50mL of 80 v/v% ethanol water solution, and magnetically stirring at 500rpm/min for 30 min;
(4) dropwise adding the zein ethanol aqueous solution obtained in the step (3) into 150mL of deionized water under the condition of 500rpm/min, and stirring for 3h to obtain zein particle ethanol water dispersion liquid;
(5) and (3) performing rotary evaporation on the dispersion liquid obtained in the step (4) at the temperature of 45 ℃ to remove ethanol and part of water, so as to obtain a zein particle dispersion liquid of 2 w/v% (g/mL).
(6) Dropwise adding 1M HCl or 1M NaOH into the zein particle dispersion liquid obtained in the step (5) to adjust the pH to 5, so as to obtain a zein particle dispersion liquid with the pH to 5;
(7) 10mL of the dispersion of step (2) and 5mL of the dispersion of step (5) and 15mL of GTCC were homogenized at 15000rpm for 2min at high speed to obtain a Pickering emulsion.
FIG. 3 is an appearance of the emulsion of example 3, which is more stable.
Example 4:
(1) dispersing 0.1g of montmorillonite particles into about 5mL of deionized water to obtain montmorillonite particle dispersion liquid;
(2) dropwise adding 1M HCl to the montmorillonite particle dispersion liquid of step (2), and adjusting pH to 8 to obtain a montmorillonite particle dispersion liquid of 2 w/v% (g/mL) and pH to 8;
(3) dissolving 1g of zein in 80% ethanol water solution, and magnetically stirring at 500rpm/min for 30 min;
(4) dropwise adding the zein ethanol aqueous solution obtained in the step (3) into 75mL of deionized water under the condition of 500rpm/min, and stirring for 2h to obtain zein particle ethanol water dispersion liquid;
(5) rotary evaporating the dispersion obtained in the step (4) at 42 ℃ to remove ethanol and part of water to obtain zein particle dispersion liquid of about 2 w/v% (g/mL);
(6) dropwise adding 1M HCl or 1M NaOH into the zein particle dispersion liquid obtained in the step (5) to adjust the pH to 8, so as to obtain a zein particle dispersion liquid with the pH to 8 and the concentration of 2 w/v%;
(7) and (3) mixing the dispersion liquids obtained in the step (2) and the step (6) according to different proportions to form a mixed liquid, mixing 15mL of the mixed liquid with 15mL of liquid paraffin, and homogenizing at a high speed of 15000rpm for 2min to obtain the emulsion.
The test conditions and results are shown in Table 1.
TABLE 1
Comparative results of the centrifugation of the emulsion at 4000rpm are shown in FIG. 4. It can be seen that when the ratio of zein to smectite particle dispersion reaches 1: and 2, the stability of the pickering emulsion can be obviously improved. The montmorillonite has high hydrophilicity and cannot independently stabilize the pickering emulsion, and after a proper amount of zein nano particles are added, the zein nano particles and the montmorillonite have opposite charges and form an aggregate with proper wettability through electrostatic attraction, so that the stable pickering emulsion can be formed.
Example 5:
(1) dispersing 0.1g of montmorillonite particles into about 5mL of deionized water to obtain montmorillonite particle dispersion liquid;
(2) dropwise adding 1M HCl to the montmorillonite particle dispersion liquid of step (2), and adjusting pH to 5 to obtain a montmorillonite particle dispersion liquid of 2 w/v% (g/mL) and pH to 5;
(3) dissolving 1g of zein in 80% ethanol water solution, and magnetically stirring at 500rpm/min for 30 min;
(4) dropwise adding the zein ethanol aqueous solution obtained in the step (3) into 75mL of deionized water under the condition of 500rpm/min, and stirring for 2h to obtain zein particle ethanol water dispersion liquid;
(5) rotary evaporating the dispersion obtained in the step (4) at 42 ℃ to remove ethanol and part of water to obtain zein particle dispersion liquid of about 2 w/v% (g/mL);
(6) dropwise adding 1M HCl or 1M NaOH into the zein particle dispersion liquid obtained in the step (5) to adjust the pH to be 5, so as to obtain a zein particle dispersion liquid with the pH to be 5 and the concentration of 2 w/v%;
(7) 10mL of the dispersion of step (2) and 5mL of the dispersion of step (6) were mixed with different volumes of liquid paraffin, and homogenized at 15000rpm for 2min at high speed to obtain an emulsion. The test conditions and results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the emulsion oil phase volume fraction is preferably 50-70 v/v%, the prepared emulsion is better in stability, when the oil phase content is low, the amount of the formed emulsion is low, a large amount of water phase can be separated out, and when the oil phase content is excessive, the stabilizer particles are not enough to completely wrap oil drops, and the emulsion cannot be formed.
Example 6:
(1) dispersing 0.1g of montmorillonite particles into about 5mL of deionized water to obtain montmorillonite particle dispersion liquid;
(2) dropwise adding 1M HCl to the montmorillonite particle dispersion liquid of step (2), and adjusting pH to 3 to obtain a montmorillonite particle dispersion liquid of 2 w/v% (g/mL) and pH to 3;
(3) dissolving 1g of zein in 25mL of 80 v/v% ethanol water solution, and magnetically stirring at 500rpm/min for 30 min;
(4) dropwise adding the zein ethanol aqueous solution obtained in the step (3) into 75mL of deionized water under the condition of 500rpm/min, and stirring for 2h to obtain zein particle ethanol water dispersion liquid;
(5) rotary evaporating the dispersion obtained in the step (4) at 42 ℃ to remove ethanol and part of water to obtain zein particle dispersion liquid of about 2 w/v% (g/mL);
(6) dropwise adding 1M HCl or 1M NaOH into the zein particle dispersion liquid obtained in the step (5) to adjust the pH to be 3, so as to obtain a zein particle dispersion liquid with the pH to be 3 and the concentration of 2 w/v%;
(7) 10mL of the dispersion of step (2) and 5mL of the dispersion of step (6) and 15mL of liquid paraffin were mixed and homogenized at 15000rpm for 2min at high speed to obtain a Pickering emulsion.
Example 7:
(1) dispersing 0.1g of montmorillonite particles into about 5mL of deionized water to obtain montmorillonite particle dispersion liquid;
(2) dropwise adding 1M HCl to the montmorillonite particle dispersion liquid of step (2) and adjusting pH to 7 to obtain a montmorillonite particle dispersion liquid of 2 w/v% (g/mL) and pH to 7;
(3) dissolving 1g of zein in 25mL of 80 v/v% ethanol water solution, and magnetically stirring at 500rpm/min for 30 min;
(4) dropwise adding the zein ethanol aqueous solution obtained in the step (3) into 75mL of deionized water under the condition of 500rpm/min, and stirring for 2h to obtain zein particle ethanol water dispersion liquid;
(5) rotary evaporating the dispersion obtained in the step (4) at 42 ℃ to remove ethanol and part of water to obtain zein particle dispersion liquid of about 2 w/v% (g/mL);
(6) dropwise adding 1M HCl or 1M NaOH into the zein particle dispersion liquid obtained in the step (5) to adjust the pH to be 7, so as to obtain a zein particle dispersion liquid with the pH to be 7 and the concentration of 2 w/v%;
(7) 10mL of the dispersion of step (2) and 5mL of the dispersion of step (6) and 15mL of liquid paraffin were mixed and homogenized at 15000rpm for 2min at high speed to obtain a Pickering emulsion.
Example 8:
(1) dispersing 0.1g of montmorillonite particles into about 5mL of deionized water to obtain montmorillonite particle dispersion liquid;
(2) dropwise adding 1M HCl to the montmorillonite particle dispersion liquid of step (2), and adjusting pH to 9 to obtain a montmorillonite particle dispersion liquid of 2 w/v% (g/mL) and pH to 9;
(3) dissolving 1g of zein in 25mL of 80 v/v% ethanol water solution, and magnetically stirring at 500rpm/min for 30 min;
(4) dropwise adding the zein ethanol aqueous solution obtained in the step (3) into 75mL of deionized water under the condition of 500rpm/min, and stirring for 2h to obtain zein particle ethanol water dispersion liquid;
(5) rotary evaporating the dispersion obtained in the step (4) at 42 ℃ to remove ethanol and part of water to obtain zein particle dispersion liquid of about 2 w/v% (g/mL);
(6) dropwise adding 1M HCl or 1M NaOH into the zein particle dispersion liquid obtained in the step (5) to adjust the pH to 9, so as to obtain a zein particle dispersion liquid with the pH to 9 and the concentration of 2 w/v%;
(7) 10mL of the dispersion of step (2) and 5mL of the dispersion of step (6) and 15mL of liquid paraffin were mixed and homogenized at 15000rpm for 2min at high speed to obtain a Pickering emulsion.
TABLE 3
| Example 6 | Example 1 | Example 7 | Example 8 | |
| pH | 3 | 5 | 7 | 9 |
| Stabilization effect | Instability of the emulsion | Emulsion stabilization | Emulsion stabilization | Instability of the emulsion |
As can be seen from Table 3, the Pickering emulsion is stable when the pH reaches 5, a large number of free particles are not adsorbed on the interface when the pH is too high, and the emulsion elutriation phenomenon is severe when the pH is too low. When the pH value is too high, zein particles and montmorillonite particles are negatively charged, the repulsion action between the particles is enhanced, and in the emulsification process, part of the particles are difficult to be adsorbed on an interface due to the repulsion force, so that more free particles exist in a water phase.
Example 9:
(1) dispersing 0.1g of montmorillonite particles into about 5mL of deionized water to obtain montmorillonite particle dispersion liquid;
(2) dropwise adding 1M HCl to the montmorillonite particle dispersion liquid of step (2), and adjusting pH to 5 to obtain a montmorillonite particle dispersion liquid of 2 w/v% (g/mL) and pH to 5;
(3) dissolving 1g of wheat gliadin in 25mL of 70 v/v% ethanol water solution, and magnetically stirring at 500rpm/min for 30 min;
(4) adding the wheat alcohol soluble protein ethanol aqueous solution obtained in the step (3) into 75mL of deionized water at the speed of 500rpm/min, and stirring for 2h to obtain an ethanol aqueous dispersion of wheat alcohol soluble protein particles;
(5) performing rotary evaporation on the dispersion liquid obtained in the step (4) at 45 ℃ to remove ethanol and part of water to obtain a wheat gliadin particle dispersion liquid with the concentration of about 2 w/v% (g/mL);
(6) dropwise adding 1M HCl or 1M NaOH into the wheat gliadin particle dispersion liquid obtained in the step (5) to adjust the pH to be 5, so as to obtain a wheat gliadin particle dispersion liquid with the pH to be 5 and the concentration of 2 w/v%;
(7) 5mL of the dispersion of step (2) and 10mL of the dispersion of step (6) and 15mL of silicone oil were mixed and homogenized at 15000rpm for 2min at high speed to obtain a Pickering emulsion.
Comparative example 1:
the dispersion of montmorillonite particles having a pH of 5 prepared in step (2) of example 1 and liquid paraffin were mixed in a volume ratio of 1:1, preparing pickering emulsion by high-speed homogenization at 15000rpm for 2 min;
and 2 w/v% (g/mL) zein particles with pH 5 prepared in example 1, step (6) and liquid paraffin 1: pickering emulsion was prepared by high speed homogenization at 15000rpm for 2min under 1 condition.
FIG. 5 is a graph of the emulsion of comparative example 1 and the results of the centrifugal stability at 4000rpm, and after standing for 24 hours, clouding and delamination of the aqueous phase were observed, and the emulsion was broken significantly after centrifugation.
Comparative example 2:
the concentration of nanoparticles in the clay particle dispersion of example 1 was adjusted to 0.1 w/v%, and the concentration of zein particle dispersion was adjusted to 0.1 w/v%, and the rest of the procedure was the same as in example 1. The pickering emulsion obtained is shown in FIG. 6.
Comparative example 3:
the procedure of example 1 was repeated except that the concentration of the clay particle dispersion of example 1 was adjusted to 15 w/v% and the concentration of the zein particle dispersion was adjusted to 15 w/v%.
A particle precipitate was generated at the bottom of the emulsion.
Comparative example 4:
the ratio of the montmorillonite particle dispersion liquid and the zein dispersion liquid of example 1 was adjusted to 1: 10, the rest of the procedure was the same as in example 1.
No emulsion could be formed.
Comparative example 5:
the dispersion of montmorillonite particles and the dispersion of zein in example 1 were mixed with 1mL each of 11mL of liquid paraffin, and the procedure was the same as in example 1.
No emulsion could be formed.
Comparative example 6:
14mL of the dispersion of montmorillonite particles in example 1 was mixed with 7mL of the dispersion of zein and 5mL of liquid paraffin, and the procedure was the same as in example 1.
No emulsion could be formed.
Comparative example 7:
the pH of the dispersion of montmorillonite particles and the dispersion of zein in example 1 was adjusted to 10, and the mixture was mixed with liquid paraffin, and the rest of the procedure was the same as in example 2, and the resulting pickering emulsion was shown in fig. 7. The lower aqueous phase of the emulsion was cloudy, indicating that a large number of free particles were not adsorbed to the interface and the particle utilization was low.
The Pickering emulsion prepared by the method has relatively uniform droplet size, both prolamine and clay particles can be adsorbed to an oil-water interface to form stable Pickering emulsion, and a particle stabilizer is adsorbed to the interface to form a physical barrier to provide stability for the prepared Pickering emulsion. Meanwhile, part of clay particles are dissociated in the water phase, so that a three-dimensional network structure can be formed, and the stability of the emulsion is further improved. The pickering emulsion prepared by the invention has the characteristics of pure natural emulsifier raw materials, biological friendliness, environmental friendliness, simple and controllable preparation method and the like, and can be used for effectively preparing stable pickering emulsion.
The stabilizer particles used in the invention are all natural, the montmorillonite can be applied to the fields of food, medicine, cosmetics and the like, and the zein is derived from plants. The Pickering emulsion prepared by the method has uniform droplet size, the prolamine and clay particles can form an aggregate with proper wettability through electrostatic force, and then the aggregate is adsorbed to an oil-water interface to form stable Pickering emulsion, and the particle stabilizer is adsorbed to the interface to form a physical barrier to provide stability for the prepared Pickering emulsion. Meanwhile, part of clay particles are dissociated in the water phase, so that a three-dimensional network structure can be formed, and the stability of the emulsion is further improved. The pickering emulsion prepared by the invention has the characteristics of good biocompatibility, biodegradability, small using amount, low price, simple preparation method and the like of the particle stabilizer, and particularly, the prepared pickering emulsion can obviously improve the stability of pickering emulsions prepared from clay particles and alcohol soluble glutelin particles. According to the invention, the addition amounts of the clay particle dispersion liquid, the prolamine particle dispersion liquid and the oil phase and the preparation processes of the clay particle dispersion liquid and the prolamine particle dispersion liquid are optimized, the pickering emulsion has good stability, and when the addition amounts are not in the range of the invention, the stability of the prepared emulsion is reduced.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A method for preparing pickering emulsion with synergistically stabilized clay particles and prolamine particles is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
preparing a clay particle dispersion;
preparing a prolamine particle dispersion;
preparing pickering emulsion: and mixing the clay particle dispersion liquid, the prolamine particle dispersion liquid and the oil phase, and homogenizing at a high speed to obtain the pickering emulsion.
2. A process for preparing a pickering emulsion having synergistically stabilized clay particles and prolamine particles according to claim 1, wherein: the clay is one or more of montmorillonite, kaolin, illite and chlorite clay particles; the prolamine is one or more of zein, wheat prolamine or kafirin.
3. A process for the preparation of a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to claim 1 or 2, wherein: the clay particle dispersion liquid is prepared by weighing clay particles, adding the clay particles into deionized water, and performing ultrasonic or high-speed shearing dispersion to obtain the clay particle dispersion liquid.
4. A process for preparing a pickering emulsion having synergistically stabilized clay particles and prolamine particles according to claim 3, wherein: the concentration of the clay particle dispersion liquid is 0.1-10 w/v% in g/mL, the pH value is 3-9, and the size of the clay particles is 100-5000 nm.
5. The method of making a pickering emulsion having synergistically stabilized clay particles and prolamine particles according to claim 4, wherein: the concentration of the clay particle dispersion liquid is 2 w/v% in g/mL, and the pH value of the clay particle dispersion liquid is 4-5.
6. A process for the preparation of a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to claim 1 or 2, wherein: the preparation of the prolamine particle dispersion liquid comprises the steps of weighing prolamine, adding 55-95% ethanol water solution, stirring for dissolving, adding the solution into water, stirring, and evaporating at 35-75 ℃ to remove ethanol to obtain the prolamine nanoparticle dispersion liquid.
7. A method of making a pickering emulsion having synergistically stabilized clay particles and prolamine particles according to claim 6, wherein: the prolamine nanoparticle dispersion liquid has a concentration of 0.1-10 w/v% in g/mL, a pH of 3-9, and prolamine nanoparticles of 40-2000 nm in size.
8. A method of making a pickering emulsion having synergistically stabilized clay particles and prolamine particles according to claim 7, wherein: the concentration of the prolamine nanoparticle dispersion liquid is 2 w/v% in g/mL, and the pH value of the prolamine nanoparticle dispersion liquid is 4-5.
9. A process for the preparation of a pickering emulsion with synergistically stabilized clay particles and prolamine particles according to claim 1 or 2, wherein: the preparation of pickering emulsion, wherein the oil phase comprises soybean oil, castor oil, olive oil, peanut oil, corn oil, sunflower oil, safflower oil, avocado butter, grape seed oil, sesame oil silicone oil, tea tree oil, evening primrose oil, peppermint oil, rose oil, sweet orange oil, cinnamon oil, liquid paraffin, petrolatum, n-hexane, n-hexadecane, isopropyl myristate, ethylhexyl palmitate, isopropyl palmitate, caprylic/capric triglyceride (GTCC), shea butter, isononyl isononanoate, squalane, glyceryl polymethacrylate, jojoba oil, cetyl alcohol, cetearyl alcohol, behenyl alcohol, stearyl alcohol, myristyl alcohol, dioctyl carbonate, pentaerythritol tetrastearate, ethylhexyl cocoate/isooctyl cocoate, decyl oleate, isoamyl laurate, propylene glycol dicaprylate/dicaprate, or dicaprate, One or more of C12-15 alcohol benzoate, PEG-7 glycerol cocoate, shea butter, white oil, glycerol tricaprylate, glycerol stearate, butyl octanol salicylate, neopentyl glycol diheptanoate, dipentaerythritol tri-polyhydroxystearate, isododecane, propylene carbonate, hexyl laurate, polymethyl methacrylate, hydrogenated lecithin, polyisobutylene, diisopropyl adipate, octyldodecanol pivalate and distarch phosphate; the oil phase content is 10-85 v/v%, the prolamine nanoparticles and clay particles content is 0.1-10 w/v%, and the mass ratio of the prolamine nanoparticles to the clay particles is 0.1: 1-1: 0.1.
10. A method of making a pickering emulsion having synergistically stabilized clay particles and prolamine particles according to claim 7, wherein: the high-speed homogenization is carried out for 1-30 min at the speed of 5000-25000 rpm.
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