CN113842375B - Microcapsule with gradient capsule wall structure and preparation method thereof - Google Patents
Microcapsule with gradient capsule wall structure and preparation method thereof Download PDFInfo
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- CN113842375B CN113842375B CN202111190826.5A CN202111190826A CN113842375B CN 113842375 B CN113842375 B CN 113842375B CN 202111190826 A CN202111190826 A CN 202111190826A CN 113842375 B CN113842375 B CN 113842375B
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 52
- 239000002775 capsule Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011162 core material Substances 0.000 claims abstract description 24
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 86
- 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 claims description 73
- 235000010413 sodium alginate Nutrition 0.000 claims description 73
- 239000000661 sodium alginate Substances 0.000 claims description 72
- 229940005550 sodium alginate Drugs 0.000 claims description 72
- 229920001661 Chitosan Polymers 0.000 claims description 62
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000001110 calcium chloride Substances 0.000 claims description 21
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- -1 sucrose fatty acid ester Chemical class 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000002285 corn oil Substances 0.000 claims description 2
- 235000005687 corn oil Nutrition 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 235000021323 fish oil Nutrition 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000006041 probiotic Substances 0.000 claims description 2
- 235000018291 probiotics Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000004886 process control Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- 239000000648 calcium alginate Substances 0.000 description 5
- 235000010410 calcium alginate Nutrition 0.000 description 5
- 229960002681 calcium alginate Drugs 0.000 description 5
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000005354 coacervation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000017 hydrogel Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 235000010443 alginic acid Nutrition 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000283973 Oryctolagus cuniculus Species 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229940072056 alginate Drugs 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 210000000845 cartilage Anatomy 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- 206010061762 Chondropathy Diseases 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
- A61K9/5021—Organic macromolecular compounds
- A61K9/5036—Polysaccharides, e.g. gums, alginate; Cyclodextrin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K35/00—Medicinal preparations containing materials or reaction products thereof with undetermined constitution
- A61K35/56—Materials from animals other than mammals
- A61K35/60—Fish, e.g. seahorses; Fish eggs
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K35/00—Medicinal preparations containing materials or reaction products thereof with undetermined constitution
- A61K35/66—Microorganisms or materials therefrom
- A61K35/74—Bacteria
- A61K35/741—Probiotics
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5089—Processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Molecular Biology (AREA)
- Marine Sciences & Fisheries (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention provides a microcapsule with a gradient capsule wall structure and a preparation method thereof, wherein the microcapsule with the gradient capsule wall structure is prepared and obtained by using an excessive amount of cross-linking agent and process control, and the gradient capsule wall structure is characterized in that the hardness is increased from inside to outside due to different cross-linking degrees from outside to inside. The outermost layer firstly reacts with glutaraldehyde, the crosslinking degree is highest, a harder crosslinking shell structure is formed, the crosslinking degree is reduced and the capsule shell strength is reduced as the crosslinking degree is closer to the inside of the core material, so that a microcapsule shell structure with gradient hardness is formed; the microcapsule shell has high strength, high toughness and high elasticity, and is favorable to maintaining excellent shape and stability in the application process of the microcapsule, avoiding the leakage of capsule core matters, effectively protecting the capsule core, enabling the capsule core to release slowly and prolonging the activity and effectiveness of the capsule core.
Description
Technical Field
The invention relates to the technical field of microcapsule preparation, in particular to an oil-in-water microcapsule and a preparation method thereof.
Background
Sodium alginate is a byproduct of brown algae kelp or gulfweed after extracting iodine and mannitol, is a natural linear anionic polymer polysaccharide, mainly consists of sodium salt of alginic acid, and is a main commercial product of alginic acid. In the prior art, the sodium alginate hydrogel and SIS composite are used as a scaffold material, and soft bone cells are inoculated to construct the effect of repairing the full-thickness articular cartilage defect of the rabbit by tissue engineering cartilage. Randomly dividing an age-appropriate rabbit into an experimental group and a control group, wherein the experimental group is used for placing a composite material at a defect part, and a SIS film is sewn and covered on the surface to completely fill the defect; the control group is filled with pure sodium alginate hydrogel and is sewed by covering SIS film. The experimental result shows that the sodium alginate and SIS composite material has the function of promoting cartilage tissue regeneration.
Chitosan hydrogels are often used in wound dressings due to their antimicrobial properties. Many Kangzhikang et al use silver nitrate, polyethylene glycol and chitosan as raw materials to prepare the chitosan/polyglycolic acid sponge containing nano silver/polyethylene glycol by acetalation reaction, and the performance and structure of the material are detected. The result and conclusion are that the prepared sponge can release nano silver particles with good antibacterial property, so that the sponge has good antibacterial property. The dressing has good physical properties, biocompatibility and sterilization effect.
The property of the wall material used for preparing the microcapsule in the prior art determines the specific application mode of the microcapsule, and how to prepare the wall material with excellent mechanical properties becomes a technical problem to be solved by the person skilled in the art.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a microcapsule with a gradient capsule wall structure and a preparation method thereof.
In order to achieve the above purpose, the invention provides a microcapsule with a gradient capsule wall structure, which comprises a wall material and an oily capsule core material, and is characterized in that the wall material is a polymer formed by glutaraldehyde crosslinking of chitosan/sodium alginate, and the chemical structural formula of the polymer is shown as formula (I):
the invention also provides a preparation method of the microcapsule with the gradient capsule wall structure, which comprises the following steps:
a. dissolving sodium alginate in acetic acid solution to obtain sodium alginate solution;
b. dissolving chitosan in acetic acid solution to obtain chitosan solution;
c. dissolving sucrose fatty acid ester in oily capsule core material to obtain oily mixed solution;
d. adding the oily mixed solution in the step c into the chitosan mixed solution in the step b, and fully emulsifying to obtain mixed emulsion;
e. adding acetic acid solution into the mixed emulsion in the step d for dilution;
f. dropwise adding the sodium alginate solution in the step a into the emulsion in the step e, and dropwise adding the sodium alginate solution under the condition of 25-30 ℃ while stirring;
g. adding a calcium chloride solution into the reaction system in the step f, stopping dripping when insoluble matters appear in the solution, and completely reacting;
h. and (3) adding excessive glutaraldehyde water solution into the reaction system in the step (g) to react completely, thereby obtaining the microcapsule with the gradient capsule wall structure.
Preferably, the oily capsule core material is one or more of corn oil, olive oil, soybean oil, fish oil, oily essence and oily probiotics.
Preferably, the step c specifically includes: the sucrose fatty acid ester and oily cystic material are stirred at 800rpm for 5-10min at 25-30deg.C.
Preferably, the step d specifically includes: the emulsifying temperature is 25-30deg.C, the emulsifying time is 30min, and the stirring speed is 600-800rpm.
Preferably, the step f specifically includes: dropwise adding the sodium alginate aqueous solution in the step a into the mixed emulsion in the step e, stirring at 25-30 ℃ while dropwise adding, controlling the dropwise adding speed to be 1mL/min, stirring at 800rpm, adjusting the pH value to be 5.5, and reacting for 60min.
Preferably, the concentration of the calcium chloride solution in the step g is 0.3-0.4mol/L, the dropping speed of the calcium chloride solution is controlled to be 1mL/min, and when insoluble matters exist in the solution, the dropping is stopped, and the curing reaction is carried out for 30min at 50 ℃.
Preferably, the glutaraldehyde solution in the step h is 25% in mass fraction.
Preferably, the step h further comprises adding deionized water into the reaction system for suction filtration and washing to remove unreacted glutaraldehyde, thus obtaining the microcapsule with the gradient capsule wall structure.
Preferably, the weight fraction of each component is as follows: 60-70 parts of sodium alginate, 60-70 parts of chitosan, 8-15 parts of oily capsule core material, 0.3-0.6 part of sucrose fatty acid ester, 15-30 parts of calcium chloride and 7-10 parts of glutaraldehyde.
Compared with the prior art, the method has the beneficial effects that the microcapsule with the gradient capsule wall structure is prepared and obtained by using excessive crosslinking agent and process control, and the gradient capsule wall structure is characterized by increasing the hardness from inside to outside due to different crosslinking degrees from outside to inside. The outermost layer firstly reacts with glutaraldehyde, the crosslinking degree is highest, a harder crosslinked shell structure is formed, the crosslinking degree is reduced and the capsule shell strength is reduced as the crosslinking degree is closer to the inside of the core material, so that a microcapsule shell structure with gradient hardness is formed; the microcapsule shell has high strength, high toughness and high elasticity, and is favorable to maintaining excellent shape and stability in the application process of the microcapsule, avoiding the leakage of capsule core matters, effectively protecting the capsule core, enabling the capsule core to release slowly and prolonging the activity and effectiveness of the capsule core.
Drawings
FIG. 1 is a graph of pH and corresponding conductivity of chitosan and sodium alginate solutions of example 2.
FIG. 2 is a graph of the effect of calcium chloride concentration on conductivity peaks for example 2.
FIG. 3 is a graph showing the effect of calcium chloride concentration on conductivity change in example 2.
FIG. 4 is a schematic structural diagram of the microcapsule prepared in example 1.
Fig. 5 is a thermogravimetric plot of chitosan, sodium alginate and the microcapsules prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1 preparation of microcapsules with gradient wall structures
The detailed preparation method of the microcapsule with the gradient capsule wall structure in the embodiment is as follows:
a. weighing sodium alginate with a certain mass, adding 100mL of deionized water and 1mL of acetic acid solution, stirring for dissolution, and swelling for 8 hours to obtain sodium alginate solution;
b. weighing chitosan with a certain mass, adding 100mL of deionized water and 1mL of acetic acid solution, and stirring and dissolving completely to obtain chitosan mixed solution;
c. adding a certain mass of oily substance and emulsifier sucrose fatty acid ester into a three-mouth beaker, and stirring for 5min at a stirring speed of 800rpm at room temperature; obtaining an oily mixed solution;
d. adding the oily mixed solution in the step c into the chitosan mixed solution in the step b, and stirring at 800rpm for 30min at room temperature to obtain mixed emulsion;
e. adding 30mL of water into the three-mouth sesame seed cake, dropwise adding 0.3mL of acetic acid, respectively dropwise adding the sodium alginate solution, the chitosan mixed solution and the mixed emulsion into a three-mouth flask at room temperature at a dropwise adding speed of 1mL for 1min, stirring at a speed of 800rpm, adjusting the pH value to 5.5, and carrying out complex coacervation reaction for 60min; in an acidic medium at pH 5.5, the free amino groups on chitosan are protonated to form-NH 3 + The molecular chain is provided with a large number of positive charges, and the sodium alginate molecule is provided with a large number of carboxyl groups with negative charges, so that the chitosan and the sodium alginate form a polyelectrolyte membrane under a certain pH value due to the electrostatic interaction between positive and negative charges, complex coacervation is generated, and the stability of the microcapsule is improved;
in the step, the electrostatic interaction reaction formula of chitosan and sodium alginate is as follows:
f. adding 0.3604mol/L calcium chloride solution into the reaction system, wherein the dropping speed is 1mL/min, stopping dropping when insoluble substances exist in the solution, and controlling the temperature to be 50-60 ℃ for curing reaction for 30min; na on sodium alginate G segment + With Ca 2+ Ion exchange is carried out to form hydrogel with an egg box structure, and calcium chloride is coordinated with hydroxyl, amino and glycosidic bond on sodium alginate to form the egg box structure "Egg box structure;
in this step, the reaction formula of the reaction process of sodium alginate and calcium chloride is as follows:
g. and f, adding excessive 25% glutaraldehyde solution into the reaction system of the step f, reacting glutaraldehyde with free amino groups and hydroxyl groups on chitosan, and curing for 20min at room temperature to obtain the chitosan/sodium alginate microcapsule, wherein the shell structure of the microcapsule is characterized in that the hardness is increased from inside to outside, and the crosslinking degree is different from outside to inside. The outermost layer firstly reacts with glutaraldehyde, the crosslinking degree is highest, a harder crosslinking shell structure is formed, the crosslinking degree is reduced and the shell strength is reduced as the core material is closer to the inside of the core material, so that a microcapsule shell structure with gradient hardness is formed;
in the step, the structural formula obtained by the crosslinking reaction of glutaraldehyde and chitosan is shown as follows:
h. and (c) adding deionized water into the reaction system for suction filtration and washing to remove unreacted glutaraldehyde, thereby obtaining the microcapsule with the gradient capsule wall structure.
Example 2 isoelectric point and conductivity measurement
The pH value of the solution to be measured is adjusted by adopting a 1.0% NaOH solution and an HCl solution in an experiment, the pH value of the solution is measured by using an acidity tester, and meanwhile, the conductivity change of the solution is measured by using a conductivity tester, so that the relation between the pH value and the conductivity of the solution to be measured is obtained.
1.00g of sodium alginate is weighed and added into a beaker, 100mL of deionized water is added and placed into a heat-collecting constant-temperature heating magnetic stirrer, the water bath temperature is 60 ℃, the magnetic stirring is carried out at 150rpm until the sodium alginate is fully dissolved, the sodium alginate is naturally cooled until bubbles disappear, the sodium alginate is recorded as 1% sodium alginate solution, 5 parts of sodium alginate solution are prepared for standby under the same conditions, and the sodium alginate solution is swelled for 8 hours under the natural conditions for standby. Taking 200mL beaker, adding 100.0mL of 1% acetic acid solution, heating in water bath at constant temperature of 50 ℃, stirring at the speed of 200rpm, weighing 1.00g of chitosan, adding into the beaker, dripping 1.00mL, stirring until the chitosan is dissolved, obtaining 1.0% chitosan solution, and preparing 5 parts for standby under the same conditions.
50.0mL of 1.0% chitosan solution was taken into a 100mL beaker, the pH was gradually adjusted to 3.0 using 1.0% HCl solution, and the pH versus conductivity was recorded every 5 drops. Another 50.0mL of 1.0% chitosan solution was taken into a 100mL beaker, the pH was gradually adjusted to 11.0 using 1.0% NaOH solution, and the relationship between pH and conductivity was recorded every 5 drops. The relationship between pH and conductivity of 1.0% sodium alginate was measured under the same conditions.
45.0mL of 1.0% chitosan solution and 5.0mL of 3.0% CaCl were taken 2 The solution was brought to a 100mL beaker and the pH was gradually adjusted to 3.0 using 1.0% hcl solution and the relationship between pH and conductivity was recorded every 5 drops. Another 50.0mL of 1.0% chitosan solution was taken into a 100mL beaker, the pH was gradually adjusted to 11.0 using 1% NaOH solution, and the pH versus conductivity was recorded every 5 drops. Measurement of 40.0mL of 1.0% chitosan solution and 10.0mL of 1.0% CaCl under the same conditions 2 Mixed solution, 25.0mL,1.0% chitosan solution and 25.0mL,1.0% CaCl 2 Mixed solution, 20.0mL,1.0% chitosan solution and 30.0mL,1.0% CaCl 2 Relationship between pH and conductivity of the mixed solution.
The pH values and the corresponding conductivities of the chitosan and sodium alginate solutions measured through experiments are plotted as shown in fig. 1. As can be seen from FIG. 1, when the conductivity of the sodium alginate solution is higher than 4.7, the conductivity of the sodium alginate solution increases with the increase of the pH value, and the conductivity of the solution changes greatly, which means that-COOH groups in the sodium alginate in the solution are continuously dissociated and-COO - The number increases; at pH value of 3-4.1, the conductivity of sodium alginate solution is reduced by less than pH value of 4.7-7, which is due to H in the process of regulating pH value + And Cl - Increasing the number leads to an increase in the conductivity of the solution, -COO - The ability to convert to-COOH is reduced, so that it can be determined that the isoelectric point of sodium alginate is in the pH range of 4.1-4.7, and-COO in the sodium alginate solution - Near the minimum, there is little further decrease in pHquantity-COO - Converting into-COOH, maintaining the sodium alginate molecule neutral, and continuously dissociating a large number of-COOH groups into-COO when the pH value is larger than the interval - The sodium alginate molecules are thus negatively charged.
The chitosan molecule contains-NH 2 The groups being protonated in an acidic environment to form-NH 3 + As can be seen from fig. 1, when the pH is less than 6, the conductivity of the chitosan solution increases with decreasing pH, and the conductivity of the solution changes greatly, indicating that the amount of chitosan in the solution increases and the protonated-NH is formed 3 + The ions increase. When the pH is between 6 and 6.7, the conductivity of the solution changes less, which indicates that the chitosan amount in the chitosan solution is not obviously changed at the moment and reaches a saturated state. When the pH is more than 6.7, the conductivity increases more slowly with increasing pH, which is-OH in the process of adjusting pH - And Na (Na) + The increase in number results in an increase in the conductivity of the solution, but the increase in magnitude is negligible compared to the decrease in conductivity below pH 6, so that it can be determined that the isoelectric point of chitosan is in the pH range 6-6.7, below which the chitosan molecule is due to the presence of a significant amount of-NH 3 + With a positive charge, above this interval, the chitosan molecules precipitate out due to reduced solubility, keeping neutral.
By adding CaCl with different concentrations into chitosan solution 2 Testing the conductivity to obtain CaCl 2 The effect of concentration on conductivity peak is shown in figure 2, caCl 2 As can be seen from FIGS. 2 and 3, no CaCl addition was found as shown in FIG. 3, which shows the effect of concentration on the change in conductivity 2 Isoelectric point ph=5.5 of chitosan solution, increasing CaCl without changing volume 2 The isoelectric point of the solution is not changed, but the conductivity peak value of the solution is increased, and the conductivity peak value of the solution is increased along with CaCl 2 The trend of the ratio increase in the solution is shown in FIG. 2, which can prove that the Cl in the mixed solution is under the condition of unchanged solution volume - And Ca 2+ An increase in ionic solubility may increase the conductivity peak.
As can be seen from FIG. 3, cl in the mixed solution - And Ca 2+ The difference between the conductivity peak and the conductivity minimum is also the difference with increasing ion concentration, and Cl in the mixed solution - And Ca 2+ The ion concentration is increased, the conductivity change value is firstly increased and then decreased, the highest value is reached when the mass ratio of chitosan to calcium chloride is 1:0.5, and CaCl is obtained under the condition of the ratio 2 The ionization of chitosan is promoted to a certain extent, and the reaction can be promoted in the gel preparation process by the complex coacervation method. When the ratio of chitosan to calcium chloride is greater than 1, the conductivity change of the solution is more gentle compared with that of a single-component chitosan solution in a pH=4-10 region, the conductivity difference is smaller, and the reason is that the chitosan ratio in the mixed solution is reduced, and Cl is contained in the mixed solution - And Ca 2+ The ionic conductivity is strong and therefore the conductivity change is relatively small, and high concentrations of calcium chloride may be detrimental to the complex coacervation process.
It is determined by the experiment of isoelectric point and conductivity in this example 2 that the reaction condition control in step e of example 1 was achieved, and the pH of the reaction system in which the aqueous sodium alginate solution of step a and the mixed emulsion of step d were respectively added dropwise to a heating vessel was controlled to 5.5.
Example 3 selection experiment of calcium chloride
In step f of example 1 of the present invention, caCl is added to the reaction system 2 The solution was designed to increase the mechanical properties of the final microcapsules, and the experimental procedure was chosen as follows.
1、CaCl 2 Influence on sodium alginate gel
At pH 7.0 and 50 ℃,4% sodium alginate solution reacts with deionized water, 0.3604mol/L calcium chloride, zinc chloride and magnesium chloride solution for 30min to prepare gel respectively, and the experimental results of maximum stretching length, dehydration rate and elastic recovery time are shown in Table 1.
TABLE 1 influence of coagulant type on gel
| Coagulant type (%) | Deionized water | Calcium chloride | Zinc chloride | Magnesium chloride |
| Maximum tensile length (cm) | 0.2 | 1.5 | 0.5 | 0.3 |
| Dehydration percentage (%) | 97.8 | 95.8 | 89.2 | 95.2 |
| Elastic recovery time(s) | 5.0s | 4.5s | 4.8s | 5.2s |
As can be seen from Table 1, the gel prepared by reacting the calcium chloride solution with the same concentration for 30min has better performance advantage than the gel prepared by reacting the zinc chloride solution and the magnesium chloride solution with the 4% sodium alginate solution. The tensile strength and the dehydration property of the calcium alginate gel are higher than those of zinc alginate and magnesium alginate gels, and the elasticity of the four gels is close to that of the four gels, because the gel elasticity is mainly related to the concentration of sodium alginate.
2. Influence of calcium chloride usage on sodium alginate gel
The maximum tensile length, dehydration rate and elastic recovery time experimental results of the gel prepared by respectively reacting sodium alginate solution with deionized water, 0.1802mol/L, 0.3604mol/L and 0.5405mol/L calcium chloride solution for 30min at pH 7.0 and temperature of 50 ℃ are shown in Table 2.
TABLE 2 influence of calcium chloride usage on the gel process
| Calcium chloride concentration (%) | 0 | 0.1802mol/L | 0.3604mol/L | 0.5405mol/L |
| Maximum tensile length (cm) | 0.2cm | 0.5cm | 1.5cm | 1.2cm |
| Dehydration percentage (%) | 97.8％ | 94.8％ | 89.2％ | 90.6％ |
| Elastic recovery time(s) | 5.0s | 4.8s | 4.5s | 4.5s |
As shown in Table 2, the gel prepared by reacting 0.3604mol/L calcium chloride solution with 4% sodium alginate solution for 30min has better tensile strength and dehydration property. As the concentration of the reacted calcium chloride increases, the tensile strength and the dehydration property of the calcium alginate gel increase gradually, because Ca is likely to be present when the concentration of the calcium chloride is 0.3604mol/L 2+ Substitution of Na in sodium alginate + Saturated, the concentration of calcium chloride continues to increase, and Na is not contained in the calcium alginate gel + Is substituted. Therefore, the concentration of calcium chloride is controlled to be in the preferred concentration range of 0.3 to 0.4 mol/L.
4. Influence of the reaction temperature on the sodium alginate gel
The maximum tensile length, dehydration rate and elastic recovery time of the gel prepared by reacting 2.0% sodium alginate solution and 0.3604mol/L calcium chloride solution at different temperatures for 30min at pH 7.0 are shown in Table 3.
TABLE 3 influence of temperature on the gel process
As can be seen from Table 4, as the gel reaction temperature increases, the tensile properties of the prepared calcium alginate, the water absorption and the elasticity increase and decrease, and the performance is the best at 50 ℃. The reason is that the degree of entanglement of the sodium alginate molecular chain is reduced with the increase of the reaction temperature, and the sodium alginate molecular chain is in a stretched state, ca 2+ Easy to replace Na + Form a network structure, so that the gel performance is improved in the range of 20-50 ℃. The temperature continues to increase, the G section and the M section of the sodium alginate are more active, the formed chain segment becomes loose and flicksReduced performance, ca 2+ Substituted Na + It is difficult to form a net structure after that, and moisture is not easily preserved, and thus the stretchability and the dehydratability are lowered.
The temperature has the most obvious influence on the synthesis of sodium alginate/chitosan gel, the condensation degree is low when the temperature is lower than 40 ℃, the synthesized gel is less, and the stability is poor. The degree of coagulation is increased when the temperature is higher than 40 ℃, the synthesized gel is increased, the stability is better, the synthesized gel at 50 ℃ is saturated, wrinkles can be clearly seen, and the gel starts to be resolved when the temperature is higher than 50 ℃, because the high temperature damages the coagulation reaction of chitosan and sodium alginate, and in addition, if the temperature is continuously increased, the molecular chains of the sodium alginate and the chitosan are easy to break. Therefore, the water bath temperature is preferably 50 ℃.
Example 3 gradient Structure
Fig. 4 is a schematic structural diagram of a microcapsule prepared according to embodiment 1 of the present invention, where the microcapsule wall has a strength gradient structure, i.e. the shell has a relatively high strength, relatively low internal strength, and relatively high strength, toughness and elasticity, so that the microcapsule is beneficial to maintaining good morphology and stability in the application process of the microcapsule, avoiding leakage of core materials, effectively protecting the core, enabling the core to release slowly, and prolonging the efficacy of the core.
Example 3 thermogravimetric analysis (TG)
The chitosan, sodium alginate and the microcapsule prepared in example 1 were each weighed 6mg of sample, and analyzed by a TG thermal analyzer, the temperature was raised from room temperature to 600 ℃ at a heating rate of 10 ℃/min, and the atmosphere was nitrogen. The thermal decomposition temperature tables of the obtained chitosan, sodium alginate and the microcapsules of example 1 are shown in table 1, and the TG diagram of the chitosan, sodium alginate and the microcapsules prepared in example 1 is shown in fig. 4.
TABLE 1 thermal decomposition temperatures of gelatin, sodium alginate and example 1 microcapsules
As can be seen from table 1, the thermal decomposition stability temperature of the chitosan/sodium alginate microcapsule prepared by using glutaraldehyde and calcium chloride as cross-linking agents is 267 ℃, which is higher than the thermal decomposition temperature of chitosan and sodium alginate, thus indicating that glutaraldehyde and calcium chloride cross-linking improves the thermal stability of chitosan and sodium alginate.
From Table 1, it is clear that the thermal stability of the microcapsules of example 1 is lower than that of chitosan, but higher than that of sodium alginate, because calcium chloride reacts with sodium alginate to form calcium alginate, which is decomposed to form CaCO3 at a lower temperature, and CaCO3 is further oxidized to form CaO and Ca (OH) 2, and thus starts to decompose at a lower temperature than that of chitosan.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should be covered by the protection scope of the present invention by equally replacing or changing the technical scheme and the inventive concept thereof.
Claims (9)
1. The preparation method of the microcapsule with the gradient capsule wall structure specifically comprises the following steps:
a. dissolving sodium alginate in acetic acid solution to obtain sodium alginate solution;
b. dissolving chitosan in acetic acid solution to obtain chitosan solution;
c. dissolving sucrose fatty acid ester in oily capsule core material to obtain oily mixed solution;
d. adding the oily mixed solution in the step c into the chitosan mixed solution in the step b, and fully emulsifying to obtain mixed emulsion;
e. adding acetic acid solution into the mixed emulsion in the step d for dilution;
f. dropwise adding the sodium alginate solution in the step a into the emulsion in the step e, and dropwise adding the sodium alginate solution under the condition of 25-30 ℃ while stirring;
g. adding a calcium chloride solution into the reaction system in the step f, stopping dripping when insoluble substances exist in the solution, and completely reacting;
h. adding excessive glutaraldehyde water solution into the reaction system in the step g, and completely reacting to obtain microcapsules with gradient capsule wall structures;
the step d specifically comprises the following steps: the emulsifying temperature is 25-30deg.C, the emulsifying time is 30min, and the stirring speed is 600-800rpm.
2. The method for preparing microcapsules with gradient capsule wall structures according to claim 1, wherein the oily capsule core material is one or more of corn oil, olive oil, soybean oil, fish oil, oily essence and oily probiotics.
3. The method for preparing microcapsules having a gradient capsule wall structure according to claim 1, wherein the step c specifically comprises: the sucrose fatty acid ester and oily cystic material are stirred at 800rpm for 5-10min at 25-30deg.C.
4. The method for preparing microcapsules with gradient capsule wall structure according to claim 1, wherein: the step f specifically comprises the following steps: dropwise adding the sodium alginate aqueous solution in the step a into the mixed emulsion in the step e, stirring at 25-30 ℃ while dropwise adding, controlling the dropwise adding speed to be 1mL/min, stirring at 800rpm, adjusting the pH value to be 5.5, and reacting for 60min.
5. The method for preparing microcapsules with gradient capsule wall structure according to claim 1, wherein: and (3) controlling the concentration of the calcium chloride solution in the step (g) to be 0.3-0.4mol/L, controlling the dropping speed of the calcium chloride solution to be 1mL/min, stopping dropping when insoluble substances exist in the solution, and performing curing reaction at 50 ℃ for 30min.
6. The method for preparing microcapsules having a gradient capsule wall structure according to claim 1, wherein the glutaraldehyde solution in step h has a mass fraction of 25%.
7. The method for preparing the microcapsule with the gradient capsule wall structure according to claim 1, wherein the step h further comprises the steps of adding deionized water into a reaction system for suction filtration and washing to remove unreacted glutaraldehyde, so as to obtain the microcapsule with the gradient capsule wall structure.
8. The method for preparing the microcapsule with the gradient capsule wall structure according to claim 1, wherein the proportions of the components in mass fraction are as follows: 60-70 parts of sodium alginate, 60-70 parts of chitosan, 8-15 parts of oily capsule core material, 0.3-0.6 part of sucrose fatty acid ester, 15-30 parts of calcium chloride and 7-10 parts of glutaraldehyde.
9. The microcapsule with a gradient capsule wall structure prepared by the preparation method of the microcapsule with a gradient capsule wall structure as claimed in any one of claims 1 to 8 comprises a wall material and an oily capsule core material, and is characterized in that the wall material is a polymer formed by glutaraldehyde crosslinking chitosan/sodium alginate, and the chemical structural formula of the polymer is shown as formula (I):
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