CN114702687B - Preparation method and application of cyclodextrin MOF particle antibiotic substitute - Google Patents
Preparation method and application of cyclodextrin MOF particle antibiotic substitute Download PDFInfo
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- CN114702687B CN114702687B CN202210420678.XA CN202210420678A CN114702687B CN 114702687 B CN114702687 B CN 114702687B CN 202210420678 A CN202210420678 A CN 202210420678A CN 114702687 B CN114702687 B CN 114702687B
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- 239000002245 particle Substances 0.000 title claims abstract description 69
- 239000013119 CD-MOF Substances 0.000 title claims abstract description 47
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 55
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000013110 organic ligand Substances 0.000 claims abstract description 17
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 11
- 239000001116 FEMA 4028 Substances 0.000 claims description 50
- 229960004853 betadex Drugs 0.000 claims description 50
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 37
- -1 glucosyl beta-cyclodextrin Chemical compound 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006467 substitution reaction Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- ODLHGICHYURWBS-LKONHMLTSA-N trappsol cyclo Chemical compound CC(O)COC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)COCC(O)C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1COCC(C)O ODLHGICHYURWBS-LKONHMLTSA-N 0.000 claims description 15
- PCWPQSDFNIFUPO-VDQKLNDWSA-N (1S,3R,5R,6S,8R,10R,11S,13R,15R,16S,18R,20R,21S,23R,25R,26S,28R,30R,31S,33R,35R,36R,37S,38R,39S,40R,41S,42R,43S,44R,45S,46R,47S,48R,49S)-37,39,41,43,45,47,49-heptakis(2-hydroxyethoxy)-5,10,15,20,25,30,35-heptakis(hydroxymethyl)-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontane-36,38,40,42,44,46,48-heptol Chemical compound OCCO[C@H]1[C@H](O)[C@@H]2O[C@H]3O[C@H](CO)[C@@H](O[C@H]4O[C@H](CO)[C@@H](O[C@H]5O[C@H](CO)[C@@H](O[C@H]6O[C@H](CO)[C@@H](O[C@H]7O[C@H](CO)[C@@H](O[C@H]8O[C@H](CO)[C@@H](O[C@H]1O[C@@H]2CO)[C@@H](O)[C@@H]8OCCO)[C@@H](O)[C@@H]7OCCO)[C@@H](O)[C@@H]6OCCO)[C@@H](O)[C@@H]5OCCO)[C@@H](O)[C@@H]4OCCO)[C@@H](O)[C@@H]3OCCO PCWPQSDFNIFUPO-VDQKLNDWSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims 7
- 239000003607 modifier Substances 0.000 claims 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 abstract description 7
- 208000031295 Animal disease Diseases 0.000 abstract description 3
- 244000000074 intestinal pathogen Species 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000002296 dynamic light scattering Methods 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 8
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 7
- 229940088710 antibiotic agent Drugs 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 241000287828 Gallus gallus Species 0.000 description 3
- 241000283973 Oryctolagus cuniculus Species 0.000 description 3
- 235000013330 chicken meat Nutrition 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000002496 gastric effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 241000606860 Pasteurella Species 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000000968 intestinal effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 244000052769 pathogen Species 0.000 description 2
- 244000144977 poultry Species 0.000 description 2
- 235000013594 poultry meat Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 241000194017 Streptococcus Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004534 cecum Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000028709 inflammatory response Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 210000000664 rectum Anatomy 0.000 description 1
- 210000000813 small intestine Anatomy 0.000 description 1
- 238000013097 stability assessment Methods 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/163—Sugars; Polysaccharides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/30—Oligoelements
-
- 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
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/70—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in livestock or poultry
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Food Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Animal Husbandry (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Preparation (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application discloses a preparation method of cyclodextrin MOF particle antibiotic substitute, which comprises the following steps: the metal salt and the organic ligand with the mass ratio of 1 (0.25-2) are weighed and dissolved in deionized water, a regulator is added into the deionized water, the mixture is stirred for 50-100min, the mixed solution is poured into a hydrothermal reaction kettle to react for 12-36h at 50-150 ℃, and the cyclodextrin MOF particles are obtained after drying. The cyclodextrin MOF particles prepared by the preparation method are used as an antibiotic substitute in feed, and the cyclodextrin MOF particles are prepared by combining metal ions and cyclodextrin, so that the cyclodextrin MOF particles have the advantages of excellent antibacterial property, high pH stability, good biocompatibility, high biological safety and the like, can efficiently remove intestinal pathogens, prevent animal diseases and can be used as an antibiotic substitute in feed.
Description
Technical Field
The invention belongs to the field of biological functional materials, and particularly relates to a preparation method and application of a cyclodextrin MOF particle antibiotic substitute.
Background
The use of antibiotics in the aquaculture industry has severely compromised environmental safety and human health, and may also lead to the development of "superbacteria". The bacteria have drug resistance, drug-resistant strains appear, antibiotics can remain in livestock and poultry bodies, and the drug-resistant bacteria are transferred, so that potential hazards exist. Because of the specificity of antibiotic products, the application range in feed is wide and the dosage is large, and no single product can completely replace antibiotics at present.
The metal-organic framework (MOF) material is a three-dimensional structure material with metal as a connecting point and organic ligand as a framework, is a coordination polymer which is rapidly developed in the last ten years, and has great prospect in the biomedical field due to the advantages of high porosity, high specific surface area, low density and the like. The cyclodextrin and the derivatives thereof have the advantages of no toxicity, no harm and no side effect, can reduce the irritation, the side effect, the bad smell and the like of medicaments, and are widely applied to the fields of foods and medicaments. The cyclodextrin and the derivative thereof are used as organic ligands to prepare the MOF material, so that various performances of the MOF material can be greatly improved. At present, no research on cyclodextrin MOF particles for replacing antibiotics is available, and therefore, a preparation method and application of cyclodextrin MOF particle antibiotic replacement agent are provided for solving the problems.
Disclosure of Invention
The application provides a preparation method and application of a cyclodextrin MOF particle antibiotic substitute, and solves the problem that the cyclodextrin MOF particle is not used for antibiotic substitution research at present.
The application provides a preparation method of cyclodextrin MOF particle antibiotic substituting agent, which comprises the following steps:
the ratio of the metal salt to the organic ligand is 1 (0.25-2), and the metal salt is any one of chloroauric acid, chloroplatinic acid, silver chloride, copper chloride and zinc chloride; the organic ligand is any one of beta-cyclodextrin, glycine-beta-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, glucosyl beta-cyclodextrin and galactosyl beta-cyclodextrin, wherein the substitution degree of the glycine-beta-cyclodextrin, the hydroxypropyl beta-cyclodextrin, the hydroxyethyl beta-cyclodextrin, the glucosyl beta-cyclodextrin and the galactosyl beta-cyclodextrin is 1-3;
adding a regulator into the deionized water, stirring for 50-100min, pouring the mixed solution into a hydrothermal reaction kettle, reacting for 12-36h at 50-150 ℃, and drying to obtain cyclodextrin MOF particles, wherein the regulator is any one of N, N-dimethylformamide, absolute ethyl alcohol and potassium hydroxide.
Preferably, the ratio of the amount of metal salt to the amount of organic ligand material is 1:0.5 or 1:1 or 1:2.
preferably, the degree of substitution of the glycine- β -cyclodextrin, the hydroxypropyl β -cyclodextrin, the hydroxyethyl β -cyclodextrin, the glucosyl β -cyclodextrin, the galactosyl β -cyclodextrin is 2 or 2.5 or 3.
Preferably, the ratio of the amount of the regulator to the amount of the metal salt substance is 1 (2-4).
Preferably, the ratio of the amount of the regulator to the amount of the metal salt substance is 1:2 or 1:3 or 1:4.
preferably, the hydrothermal reaction temperature is 60 ℃ or 80 ℃ or 100 ℃ or 130 ℃.
Preferably, the hydrothermal reaction time is 15h or 20h or 24h or 30h.
Preferably, the cyclodextrin MOF particles have a size of 50-800nm.
Preferably, the cyclodextrin MOF particles have a size of 50nm or 100nm or 200nm or 400nm or 600nm or 800nm.
The invention also provides an application of the cyclodextrin MOF particles obtained by the preparation method of the cyclodextrin MOF particle antibiotic substitute as an antibiotic substitute in feed.
According to the technical scheme, the invention provides a preparation method of cyclodextrin MOF particles.
The preparation method comprises the following steps: weighing metal salt and organic ligand, dissolving in deionized water, adding regulator, stirring, then pouring the mixed solution into a hydrothermal reaction kettle for reaction, and drying to obtain MOF material;
wherein the metal salt is any one of chloroauric acid, chloroplatinic acid, silver chloride, copper chloride and zinc chloride. Different metal salts can be selected to obtain different metal-based MOF materials;
the organic ligand is any one of beta-cyclodextrin, glycine-beta-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, glucosyl beta-cyclodextrin and galactosyl beta-cyclodextrin;
and the substitution degree of glycine-beta-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, glucosyl beta-cyclodextrin and galactosyl beta-cyclodextrin is 1-3.
The cyclodextrin MOF particles have a size of 50-800nm.
The beneficial effects of the invention are as follows: the cyclodextrin MOF particles are prepared by combining metal ions and cyclodextrin, have the advantages of excellent antibacterial property, high pH stability, good biocompatibility, high biosafety and the like, can efficiently remove intestinal pathogens, prevent animal diseases and can be used as an antibiotic substitute in feed.
Drawings
For a clearer description of the technical solutions of the present application, the drawings that are necessary for the implementation will be briefly described, it being obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a flow chart of a process for preparing a cyclodextrin MOF particle antibiotic agent according to the present invention;
Detailed Description
In order to better understand the technical solutions in the present application, the following description will clearly and completely describe the technical solutions in the embodiments of the present application with reference to the accompanying drawings.
Referring to fig. 1, a method for preparing a cyclodextrin MOF particulate antibiotic replacement agent comprises:
s1, weighing metal salt and organic ligand with the mass ratio of 1 (0.25-2), and dissolving the metal salt and the organic ligand in deionized water, wherein the metal salt is any one of chloroauric acid, chloroplatinic acid, silver chloride, copper chloride and zinc chloride; the organic ligand is any one of beta-cyclodextrin, glycine-beta-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, glucosyl beta-cyclodextrin and galactosyl beta-cyclodextrin, wherein the substitution degree of the glycine-beta-cyclodextrin, the hydroxypropyl beta-cyclodextrin, the hydroxyethyl beta-cyclodextrin, the glucosyl beta-cyclodextrin and the galactosyl beta-cyclodextrin is 1-3;
s2, adding a regulator into deionized water, wherein the mass ratio of the regulator to the metal salt is 1 (2-4), stirring for 50-100min, pouring the mixed solution into a hydrothermal reaction kettle for reacting for 12-36h at the temperature of 50-150 ℃, and drying to obtain cyclodextrin MOF particles with the size of 50-800nm, wherein the regulator is any one of N, N-dimethylformamide, absolute ethyl alcohol and potassium hydroxide.
In the present invention, the ratio of the amounts of the metal salt to the organic ligand substance is 1:0.5 or 1:1 or 1:2;
glycine-beta-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, glucosyl beta-cyclodextrin, galactosyl beta-cyclodextrin has a degree of substitution of 2 or 2.5 or 3;
the ratio of the amounts of the substances of the regulator to the metal salt is 1:2 or 1:3 or 1:4, a step of;
the hydrothermal reaction temperature is 60 ℃ or 80 ℃ or 100 ℃ or 130 ℃;
the hydrothermal reaction time is 15h or 20h or 24h or 30h;
the cyclodextrin MOF particles have a size of 50-800nm;
the cyclodextrin MOF particles have a size of 50nm or 100nm or 200nm or 400nm or 600nm or 800nm.
Example 1
2mmol chloroauric acid and 1mmol glycine-beta-cyclodextrin with substitution degree of 2 are weighed and dissolved in 100mL deionized water, 8mmol of N, N-dimethylformamide is added, stirring is carried out for 60min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 15h at 60 ℃, the obtained sample is rinsed 3 times with absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle size was 193nm as measured by dynamic light scattering.
Example 2
1mmol of chloroplatinic acid and 1mmol of hydroxypropyl beta-cyclodextrin with the substitution degree of 2.5 are weighed and dissolved in 100mL of deionized water, 3 mmole of N, N-dimethylformamide is added, stirring is carried out for 80min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 20h at 60 ℃, the obtained sample is rinsed 3 times with absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle size was 182nm as measured by dynamic light scattering.
Example 3
1mmol of silver chloride and 2mmol of glucosyl beta-cyclodextrin with the substitution degree of 3 are weighed and dissolved in 100mL of deionized water, 4 mmole of N, N-dimethylformamide is added, stirring is carried out for 90min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 24h at 60 ℃, the obtained sample is rinsed 3 times with absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle size was 170nm as measured by dynamic light scattering.
Example 4
2mmol of zinc chloride and 1mmol of hydroxyethyl beta-cyclodextrin with the substitution degree of 2 are weighed and dissolved in 100mL of deionized water, 6 mmole of N, N-dimethylformamide is added, stirring is carried out for 60min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 30h at 60 ℃, the obtained sample is rinsed 3 times with absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle size was 153nm as measured by dynamic light scattering.
Example 5
1mmol of copper chloride and 1mmol of glycine-beta-cyclodextrin with the substitution degree of 2.5 are weighed and dissolved in 100mL of deionized water, 4mmol of absolute ethyl alcohol is added, stirring is carried out for 80min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 15h at the temperature of 100 ℃, the obtained sample is rinsed 3 times by absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle size was 156nm as measured by dynamic light scattering.
Example 6
1mmol chloroauric acid and 2mmol hydroxypropyl beta-cyclodextrin with the substitution degree of 3 are weighed and dissolved in 100mL deionized water, 3mmol absolute ethyl alcohol is added, stirring is carried out for 90min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 20h at the temperature of 100 ℃, the obtained sample is rinsed 3 times by absolute ethyl alcohol, and the MOF particles are obtained after suction filtration and drying. The average particle size was 135nm as measured by dynamic light scattering.
Example 7
2mmol of chloroplatinic acid and 1mmol of glucosyl beta-cyclodextrin with the substitution degree of 2 are weighed and dissolved in 100mL of deionized water, 8mmol of absolute ethyl alcohol is added, stirring is carried out for 80min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 24h at the temperature of 100 ℃, the obtained sample is rinsed 3 times by absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle diameter was 113nm as measured by dynamic light scattering.
Example 8
1mmol of silver chloride and 1mmol of hydroxyethyl beta-cyclodextrin with the substitution degree of 2.5 are weighed and dissolved in 100mL of deionized water, 2mmol of absolute ethyl alcohol is added, stirring is carried out for 90min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 30h at the temperature of 100 ℃, the obtained sample is rinsed 3 times by absolute ethyl alcohol, and the MOF particles are obtained after suction filtration and drying. The average particle size was 96nm as measured by dynamic light scattering.
Example 9
1mmol of zinc chloride and 2mmol of glycine-beta-cyclodextrin with the substitution degree of 3 are weighed and dissolved in 100mL of deionized water, 3mmol of potassium hydroxide is added, stirring is carried out for 60min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 15h at 130 ℃, the obtained sample is rinsed for 3 times by absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle size was 102nm as measured by dynamic light scattering.
Example 10
2mmol of copper chloride and 1mmol of hydroxypropyl beta-cyclodextrin with the substitution degree of 2 are weighed and dissolved in 100mL of deionized water, 6mmol of potassium hydroxide is added, stirring is carried out for 90min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 20h at 130 ℃, the obtained sample is rinsed 3 times with absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle size was 99nm as measured by dynamic light scattering.
Example 11
1mmol of chloroauric acid and 1mmol of galactosyl beta-cyclodextrin with the substitution degree of 2.5 are weighed and dissolved in 100mL of deionized water, 4mmol of potassium hydroxide is added, stirring is carried out for 60min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 24h at 130 ℃, the obtained sample is rinsed 3 times with absolute ethyl alcohol, and the MOF particles are obtained after suction filtration and drying. The average particle size was 95nm as measured by dynamic light scattering.
Example 12
1mmol of chloroplatinic acid and 2mmol of galactosyl beta-cyclodextrin with the substitution degree of 3 are weighed and dissolved in 100mL of deionized water, 2mmol of potassium hydroxide is added, stirring is carried out for 80min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 30h at 130 ℃, the obtained sample is rinsed 3 times by absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle size was 82nm as measured by dynamic light scattering.
Example 13
1mmol of chloroauric acid and 2mmol of beta-cyclodextrin are weighed and dissolved in 100mL of deionized water, 4mmol of potassium hydroxide is added, stirring is performed for 80min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 20h at 80 ℃, the obtained sample is rinsed for 3 times with absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle size was 760nm as measured by dynamic light scattering.
Example 14
1mmol of silver chloride and 1mmol of beta-cyclodextrin are weighed and dissolved in 100mL of deionized water, 2mmol of absolute ethyl alcohol is added, stirring is carried out for 90min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 24h at 100 ℃, the obtained sample is rinsed for 3 times by the absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle size was 700nm as measured by dynamic light scattering.
Example 15
2mmol of zinc chloride and 1mmol of beta-cyclodextrin are weighed and dissolved in 100mL of deionized water, 6 mmole of N, N-dimethylformamide is added, stirring is carried out for 60min, then the mixed solution is poured into a hydrothermal reaction kettle for reaction for 30h at 130 ℃, the obtained sample is rinsed 3 times with absolute ethyl alcohol, and MOF particles are obtained after suction filtration and drying. The average particle size was 610nm as measured by dynamic light scattering.
Example 16
The synthesized cyclodextrin MOF particles were subjected to pH stability assessment in simulated gastric fluid. Five groups of samples (examples 1, 3, 7, 8 and 12) were selected, poured into the prepared simulated gastric fluid, reacted for a certain period of time, 3mL of the mixed solution was taken, and the supernatant was removed by centrifugation. The content of the metal element in the supernatant was measured by inductively coupled plasma mass spectrometry (ICP-MS). Within 3 hours, all samples had a dissolution rate of less than 5% in simulated gastric fluid.
Example 17
The synthesized cyclodextrin MOF particles were evaluated for in vitro antimicrobial activity. Typical pathogens (e.g., escherichia coli, salmonella, pasteurella, streptococcus and staphylococcus) of poultry such as cattle, sheep, chickens and rabbits were selected as target bacteria, five groups of samples (examples 2, 6, 8, 10, 12, 13, 14 and 15) were selected for antibacterial performance, and the antibacterial rate of the samples was calculated by colony counting. The cyclodextrin MOF particles taking the cyclodextrin derivative as the organic ligand have the antibacterial efficiency of more than 95% on typical pathogenic bacteria.
Example 18
The synthesized cyclodextrin MOF particles were subjected to in vivo antibacterial property evaluation. Five samples (examples 3, 4, 6, 9, 12, 13, 14 and 15) were randomly selected and feed containing the selected samples was continuously administered to chickens and rabbits for 1 week (50 mg/kg added) and then exposed to the classical pathogen Pasteurella, and for evaluation, the experiments included a blank. The animal was taken from the five viscera, small intestine, cecum and rectum, the inflammatory response was evaluated by histopathological methods, and the intestinal flora was sequenced to evaluate the infection. As shown in the following table, the cyclodextrin MOF particles with cyclodextrin derivatives as organic ligands did not produce infection and intestinal inflammation after feeding chickens and rabbits. This shows that the prepared cyclodextrin MOF particles have very good antibacterial effect in animals and high safety.
The embodiment of the invention provides a preparation method of a cyclodextrin MOF particle antibiotic substitute, and the preparation method of the cyclodextrin MOF particle antibiotic substitute provided by the embodiment of the invention is used for preparing the cyclodextrin MOF particle antibiotic substitute.
According to the technical scheme, the cyclodextrin MOF particles are prepared by combining metal ions and cyclodextrin, have the advantages of excellent antibacterial property, high pH stability, good biocompatibility, high biosafety and the like, can efficiently remove intestinal pathogens, prevent animal diseases and can be used as an antibiotic substitute in feed.
The present invention will be described in detail by way of the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced by relying on the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, including equivalent substitution of materials such as chloroauric acid, chloroplatinic acid, silver chloride, cupric chloride, zinc chloride, beta-cyclodextrin, glycine-beta-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, glucosyl beta-cyclodextrin, galactosyl beta-cyclodextrin, N-dimethylformamide, absolute ethyl alcohol, potassium hydroxide, etc., addition of auxiliary components, selection of specific modes, etc., fall within the scope of the present invention and the scope of the disclosure
Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. This application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope of the application being indicated by the following claims.
It is to be understood that the present application is not limited to the precise arrangements and instrumentalities shown in the drawings, which have been described above, and that various modifications and changes may be effected without departing from the scope thereof. The above-described embodiments of the present application are not intended to limit the scope of the present application.
Claims (8)
1. Use of a cyclodextrin MOF pellet antibiotic replacement in the manufacture of a feed comprising:
the ratio of the weighed substances is 1 (0.25-2), namely metal salt and organic ligand, are dissolved in deionized water, wherein the metal salt is any one of chloroauric acid, chloroplatinic acid, silver chloride, copper chloride and zinc chloride; the organic ligand is any one of glycine-beta-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, glucosyl beta-cyclodextrin and galactosyl beta-cyclodextrin, wherein the substitution degree of the glycine-beta-cyclodextrin, the hydroxypropyl beta-cyclodextrin, the hydroxyethyl beta-cyclodextrin, the glucosyl beta-cyclodextrin and the galactosyl beta-cyclodextrin is 1-3;
adding a regulator into the deionized water, stirring for 50-100min, pouring the mixed solution into a hydrothermal reaction kettle, reacting for 12-36h at 50-150 ℃, and drying to obtain cyclodextrin MOF particles, wherein the regulator is any one of N, N-dimethylformamide, absolute ethyl alcohol and potassium hydroxide, and the obtained cyclodextrin MOF particles with the size of 50-200nm are used as an antibiotic substitute in feed.
2. Use of a cyclodextrin MOF pellet antibiotic replacement agent according to claim 1, in the production of feed, characterized in that the ratio of the amount of metal salt to organic ligand substance is 1:0.5 or 1:1 or 1:2.
3. the use of a cyclodextrin MOF pellet antibiotic substitute according to claim 1 for the production of feed, wherein the degree of substitution of glycine- β -cyclodextrin, hydroxypropyl β -cyclodextrin, hydroxyethyl β -cyclodextrin, glucosyl β -cyclodextrin, galactosyl β -cyclodextrin is 2 or 2.5 or 3.
4. Use of a cyclodextrin MOF pellet antibiotic replacement according to claim 1 in the manufacture of feed, wherein the ratio of the amount of the modifier to the amount of the metal salt is 1 (2-4).
5. The use of a cyclodextrin MOF pellet antibiotic replacement agent according to claim 4 in the production of feed, wherein the ratio of the amounts of the modifier to the metal salt is 1:2 or 1:3 or 1:4.
6. use of a cyclodextrin MOF pellet antibiotic replacement agent according to claim 1 for the production of feed, wherein the hydrothermal reaction temperature is 60 ℃ or 80 ℃ or 100 ℃ or 130 ℃.
7. Use of a cyclodextrin MOF pellet antibiotic replacement according to claim 1 for the production of feed, wherein the hydrothermal reaction time is 15h or 20h or 24h or 30h.
8. Use of cyclodextrin MOF particle antibiotic replacement according to claim 1 for the production of feed, wherein the cyclodextrin MOF particle has a size of 50nm or 100nm or 200nm.
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