CN102228470A - Preparation method and purpose of copper-loaded chitosan antiseptic - Google Patents
Preparation method and purpose of copper-loaded chitosan antiseptic Download PDFInfo
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- CN102228470A CN102228470A CN2011101670399A CN201110167039A CN102228470A CN 102228470 A CN102228470 A CN 102228470A CN 2011101670399 A CN2011101670399 A CN 2011101670399A CN 201110167039 A CN201110167039 A CN 201110167039A CN 102228470 A CN102228470 A CN 102228470A
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 95
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- 239000010949 copper Substances 0.000 title claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000002421 anti-septic effect Effects 0.000 title abstract 5
- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000012265 solid product Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- 239000003674 animal food additive Substances 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 239000004599 antimicrobial Substances 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 241001465754 Metazoa Species 0.000 claims description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 229910001431 copper ion 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 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 244000144977 poultry Species 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- VMKYLARTXWTBPI-UHFFFAOYSA-N copper;dinitrate;hydrate Chemical compound O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O VMKYLARTXWTBPI-UHFFFAOYSA-N 0.000 claims description 2
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 claims description 2
- VWYGTDAUKWEPCZ-UHFFFAOYSA-L dichlorocopper;hydrate Chemical compound O.Cl[Cu]Cl VWYGTDAUKWEPCZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 3
- 244000144972 livestock Species 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 210000001198 duodenum Anatomy 0.000 description 17
- 241000252983 Caecum Species 0.000 description 16
- 210000004534 cecum Anatomy 0.000 description 16
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- 230000000844 anti-bacterial effect Effects 0.000 description 12
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- 210000003405 ileum Anatomy 0.000 description 8
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- 239000000463 material Substances 0.000 description 8
- 241000186016 Bifidobacterium bifidum Species 0.000 description 7
- 241000588724 Escherichia coli Species 0.000 description 7
- 230000037396 body weight Effects 0.000 description 7
- 230000037406 food intake Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 210000002966 serum Anatomy 0.000 description 6
- 102000016918 Complement C3 Human genes 0.000 description 5
- 108010028780 Complement C3 Proteins 0.000 description 5
- 241000287828 Gallus gallus Species 0.000 description 5
- 241000186660 Lactobacillus Species 0.000 description 5
- 102000016943 Muramidase Human genes 0.000 description 5
- 108010014251 Muramidase Proteins 0.000 description 5
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 5
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
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Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a preparation method of a copper-loaded chitosan antiseptic, comprising the following steps: 1) adding chitosan into an acid solution with a mass concentration of 0.1 to 5% so as to obtain a chitosan acid solution; 2) adjusting the pH value of the chitosan acid solution to be 3 to 5, thereby forming corpuscule emulsion; 3) centrifuging the corpuscule emulsion to obtain corpuscules, adding corpuscules into a copper salt solution, adjusting the pH value of the solution to be 4.5 to 5.5, and standing the mixture for reaction at room temperature for 5 to 10 hours so as to obtain emulsion; 4) adjusting the pH value of the emulsion to be 7 to 9, carrying out rinsing 3 to 7 times, carrying out refiltering or centrifuge dewatering, and collecting solid products; 5) crushing the solid products after drying so as to obtain the copper-loaded chitosan antiseptic. The purpose of the copper-loaded chitosan antiseptic is to use the antiseptic as a feed additive for aquatic livestock.
Description
Technical field
The present invention relates to a kind of preparation method and purposes of copper-loaded chitosan antimicrobial agent.
Background technology
Exist various pathogen in the animal alimentary canal, these pathogen can produce toxin, directly or indirectly destroy the form and the function of intestinal mucosa, thereby reduce livestock and poultry feed efficient and growth performance.If enteric pathogenic bacteria quantity surpasses certain value, the lighter's dyspepsia, diarrhoea, intestinal source property systemic infection may take place in weight person, even threat to life, and this makes antibiotic use in a large number in breeding production.And antibiotic a large amount of use, though played the effect that promotes growth of animal, disease resistance to a certain extent.But life-time service and abuse of antibiotics cause such as Drug resistance, drug resistant gene transfer, residual " three cause " adverse consequencess such as (mutagenesis, teratogenesis, carcinogenic) that reaches of animal products Chinese medicine, will directly or indirectly threaten human health.Because the generation of Resistant strain, the additive capacity of antibiotic in feedstuff increases day by day, and residual in animal product constantly increases, and directly influences human health by food chain.Therefore, it is significant to the sustainable development and the human health of aquaculture to research and develop non-harmful novel antibacterial preparation.
With natural inorganic mineral matter is carrier, load antibacterial metal ions (Ag, Cu, Zn etc.) or metal-oxide (ZnO) and the inorganic antibacterial material made has high temperature resistant, chemical stability is good, and wide spectrum, antibacterial be difficult for producing drug resistance, can be made into powder body, and be safe in utilization, convenient.At present, research in pottery, organic fiber, plastics, coating, food, medicine and other fields both at home and abroad all has report with application, but there is no wide popularization and application, and main cause is these inorganic antibacterial materials, its antibacterial activity is relatively low, can't be widely used in prevention and clinical treatment.Therefore, how fully to select effective Organic substance carrier, the inorganic microelement of load tool sterilizing function is made composite antibacterial material, is the developing direction of development and development of new safety antibacterial.
The metal ion anti-microbial property is with Ag
+The best, it all has intensive killing effect to various malignant bacterias, and desired concn is extremely low, but valuable product.In addition, Ag
+Very easily be reduced into metallic copper under light, the heating condition seeing, can also with the Cl in the aqueous medium
-, HS
-, S
2-And SO
4 2-Etc. multiple anionic reactive, form water-fast AgCl and Ag
2S, thus antibacterial activity lost.Copper is the essential trace element of animal, has bactericidal property preferably, adds high doses of copper diarrhea and growth promotion effect significantly in the diet.
The chitosan chemical name is (1,4)-2-acetamido-2-deoxidation-β-D-glucose, be the marine resources of a class enormous amount, for being that occurring in nature is only second to cellulosic second largest natural biological high polymer, owing to its excellent biological compatibility, degradability, nontoxic and unique physical and chemical properties and physiologically active are subjected to extensive concern.Chitosan all has in various degree facilitation to animal body nonspecific immunity and specific immunity, is a kind of good immunopotentiating agent.And chitosan shows the antibiotic feature of class because of containing highly active functional group in its complicated spatial structure, and the growth that can suppress various bacteria is with active.Chitosan has been applied to agricultural, industry and medicine and other fields as multiple functional materials such as feed additive, heavy metal chelant, adsorbent and medicinal slow release agents.
" the Changes in composition a metabolism of caecal microbiota in rats fed diets supplemented with copper-loaded chitosan nanoparticles " that delivered in 2010 the Han Xin swallow informed copper sulfate by mass volume ratio 0.3% (W/V) adding chitosan nano suspension, room temperature magnetic agitation 12 hours, the product of gained can exert an influence to rat growth and digestive tract.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method and purposes of copper-loaded chitosan antimicrobial agent.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of copper-loaded chitosan antimicrobial agent, may further comprise the steps successively:
1), in 20～60 ℃, be that 0.1～5% acid solution adds chitosan in mass concentration, the chitosan acid solution; The mass concentration of chitosan in the chitosan acid solution is 0.1～5%;
2), to utilize mass concentration be that 0.1～5% acid solution is regulated the chitosan acid solution, making its pH value is 3～5; Thereby form the micropartical emulsion;
3), centrifugalize micropartical emulsion, micropartical;
(slowly) adds micropartical in the copper salt solution that copper ion concentration is 100-1000mg/L under stirring condition, mixed liquor, mantoquita be in the step 1) chitosan weight 5～30%; Utilizing concentration then is that the pH value that the alkaline solution of 0.5～10mol/L is regulated mixed liquor is 4.5～5.5, room temperature reaction 5～10 hours, emulsion;
4), in the emulsion of step 3) gained, add concentration be the alkaline solution of 0.5～10mol/L to regulate pH value be 7～9, wash then 3～7 times, refilter or centrifuge dehydration; Collect solid product;
5), step 4) gained solid product oven dry back is pulverized, copper-loaded chitosan antimicrobial agent.
Improvement as the preparation method of copper-loaded chitosan antimicrobial agent of the present invention: the chitosan in the step 1) is that molecular weight is the chitosan of 2～80kDa.
Further improvement as the preparation method of copper-loaded chitosan antimicrobial agent of the present invention: the mantoquita in the step 3) is copper chloride, copper nitrate, copper sulfate, copper chloride hydrate, copper nitrate hydrate or copper sulfate hydrate.
Further improvement as the preparation method of copper-loaded chitosan antimicrobial agent of the present invention: step 1) and step 2) acid in is acetic acid or hydrochloric acid.
Further improvement as the preparation method of copper-loaded chitosan antimicrobial agent of the present invention: alkali is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate in step 3) and the step 4); The optium concentration of alkaline solution is 0.5～10mol/L.
Further improvement as the preparation method of copper-loaded chitosan antimicrobial agent of the present invention: the bake out temperature of step 5) is 50～70 ℃, is crushed to and can crosses 300 purposes sieve at least.
The present invention also provides the purposes of the copper-loaded chitosan antimicrobial agent that utilizes above-mentioned any one method preparation and get simultaneously: as the feed additive of poultry or aquatic animal.
In the present invention, chitosan is that molecular weight is 2-80kDa., and deacetylation is 80-95%.
Centrifugal or the filtering means dehydration of step 4) is serosity dewatering process commonly used.The filter cake (being solid product) of dehydration back gained can use conventional drying plant drying.A kind of copper-carried silicate antimicrobial agent after the oven dry is block, can select for use conventional equipment to be crushed to granularity less than 300 orders.
Copper-loaded chitosan antimicrobial agent of the present invention has characteristics such as antibiotic property is strong, antibacterial is difficult for producing drug resistance, safe in utilization; can effectively suppress animal intestinal pathogen propagation; the protection intestinal mucosa; enhancing immunity; significantly improve breeding performonce fo animals; reduce diarrhea rate, alternative antibiotic and antibacterials, the animal product of production antibiotic-free.
The specific embodiment
The preparation method of embodiment 1, a kind of copper-loaded chitosan antimicrobial agent, carry out following steps successively:
1), in 25 ℃, adding molecular weight at the hydrochloric acid solution of mass concentration 0.1% is the chitosan of 2kDa, the chitosan acid solution; The mass concentration of chitosan in the chitosan acid solution is 1%;
2), utilize the hydrochloric acid solution of mass concentration 0.1% to regulate the chitosan acid solution, making its pH value is 3.5; Thereby form the micropartical emulsion;
3), centrifugal (4000rpm/ minute rotating speed, the time is 15 minutes) separate fine particle emulsion, micropartical;
Slowly micropartical is added under stirring condition in the copper chloride solution that copper ion concentration is 500mg/L, get mixed liquor, the weight ratio of chitosan is 15% in described copper chloride and the step 1); The pH value that utilizes concentration to regulate mixed liquor for the sodium hydroxide solution of 0.5mol/L then is 5.5, and room temperature reaction 5 hours gets emulsion;
4), in the emulsion of step 3) gained, add concentration be the sodium hydroxide solution of 0.5mol/L to regulate pH value be 7.0, wash then 5 times (each water consumption equals the volume of step 3) gained emulsion), refilter; Get filter cake;
5), with 60 ℃ of step 4) gained filter cakes oven dry 24 hours, pulverize then and can cross 300 purposes sieve at least, copper-loaded chitosan antimicrobial agent.
In this copper-loaded chitosan antimicrobial agent, the mass concentration of mantoquita and chitosan is respectively: the content of copper ion was about for 4.7% (content that is copper chloride is about 10%, and chitosan content is about 90%).
Experiment 1, select the 21 age in days DLY three way cross ablactational baby pig of 54 about 7.2kg of body weight for use, principle close by body weight, male and female half and half is divided into 3 groups at random, every group of 3 repetitions, and each repeats 6 pigs.
Experimental group: the feeding daily ration is: the copper-loaded chitosan antimicrobial agent that adds 100mg embodiment 1 gained in every kg conventional feed;
Blank group: the feeding daily ration is: conventional feed;
Contrast groups 1: the feeding daily ration is: add 10mg copper chloride and 90mg chitosan (that is same experimental group of addition of assurance copper chloride and chitosan, in every kg conventional feed.)
Above-mentioned experimental group, blank group and contrast groups be subfield group feeding under identical raising condition, free choice feeding and drinking-water all, tested 28 days by a definite date.
After feeding experiment finished, vena cava anterior blood sampling system serum was measured immune indexes, and respectively chose 6 approaching pigs of body weight (each repeats 2, male and female half and half) and butcher from experimental group, blank group and contrast groups.Aseptic duodenum, jejunum, ileum and the cecal content taked, the intestinal microbial population analysis; Get one section of the middle part duodenum of 0.5cm * 0.5cm, it is rinsed well, be tiled on the filter paper liquid is blotted, immerse formaldehyde fixed liquid, spectroscopic analysis with 0.9%NaCl.
The result shows:
Experimental group is organized with respect to blank:
Ablactational baby pig daily gain and daily ingestion amount have improved 82.24% (P＜0.05), 29.76% (P＜0.05) respectively, material anharmonic ratio 28.82% (P＜0.05) that descended, diarrhea rate 29.84% (P＜0.05) that descended; Serum complement C3 level and lysozyme content have improved 57.14% (P＜0.05), 28.70% (P＜0.05) respectively; Duodenum, jejunum, ileum and caecum escherichia coli quantity have significantly reduced by 25.85%, 15.89%, 13.28% and 12.04% respectively, jejunum and caecum lactic acid bacterium number have increased by 13.27% (P＜0.05) and 10.75% (P＜0.05) respectively, and duodenum and caecum bacillus bifidus quantity have increased by 10.40% (P＜0.05) and 10.93% (P＜0.05) respectively; Duodenum intestinal villus height has increased by 7.28% (P＜0.05), and the crypts degree of depth has reduced by 24.73% (P＜0.05).
Contrast groups is organized with respect to blank: the ablactational baby pig daily gain has improved 22.24% (P＜0.05), material anharmonic ratio 10.82% (P＜0.05) that descended, and daily ingestion amount and diarrhea rate do not have significant change; Serum complement C3 level and lysozyme content have improved 17.25% (P＜0.05), 15.28% (P＜0.05) respectively; Duodenum, jejunum, ileum and caecum escherichia coli, lactobacillus and bacillus bifidus quantity do not have significant change; The duodenum intestinal villus height and the crypts degree of depth do not have significant change yet.
The preparation method of embodiment 2, a kind of copper-loaded chitosan antimicrobial agent, carry out following steps successively:
1), in 40 ℃, adding molecular weight at the hydrochloric acid solution of mass concentration 1% is the chitosan of 10kDa, the chitosan acid solution; The mass concentration of chitosan in the chitosan acid solution is 3%;
2), utilize the hydrochloric acid solution of mass concentration 1% to regulate the chitosan acid solution, making its pH value is 4.5; Thereby form the micropartical emulsion;
3), centrifugalize micropartical emulsion, micropartical;
Slowly micropartical is added under stirring condition in the copper nitrate solution that copper ion concentration is 800mg/L, get mixed liquor, the weight ratio of chitosan is 25% in copper nitrate and the step 1); The pH value that utilizes concentration to regulate mixed liquor for the potassium hydroxide solution of 1mol/L then is 5.5, and room temperature reaction 8 hours gets emulsion;
4), in the emulsion of step 3) gained, add concentration be the potassium hydroxide solution of 1mol/L to regulate pH value be 8.5, wash centrifugal again (4000rpm/ minute rotating speed, the time is 15 minutes) then 6 times; Get solid product;
5), with 50 ℃ of step 4) gained solid products oven dry 24 hours, be crushed to then and can cross 400 purposes sieve at least, copper-loaded chitosan antimicrobial agent.
In this copper-loaded chitosan antimicrobial agent, the mass concentration of mantoquita and chitosan is respectively: the content of copper ion was about for 6.8% (content of copper nitrate is about 20%, and chitosan content is about 80%).
Test 2, chosen 180 the healthy Ai Wei mattress of 1 age in days broiler chicken that body weight is close, be divided into 3 groups at random, each group has 3 repetitions, and each repeats 20 chickens (male and female half and half),
Experimental group: the feeding daily ration is: the copper-loaded chitosan antimicrobial agent that adds 100mg embodiment 2 gained in every kg conventional feed;
Blank group: the feeding daily ration is: conventional feed;
Contrast groups: the feeding daily ration is: add 20mg copper nitrate and 80mg chitosan chitosan (that is same experimental group of addition of assurance copper nitrate and chitosan, in every kg conventional feed.)
Above-mentioned experimental group, blank group all adopt under identical raising condition with contrast groups and raise in cages, and free choice feeding and drinking-water were tested 42 days by a definite date.
After feeding experiment finishes, choose close test chicken 12 plumages of body weight (male and female half and half) for every group, the totally 36 plumages not feed that feeds water, fasting 12 hours is butchered, and aseptic jejunum and the caecum content taked carried out the intestinal microbial population analysis; Get one section of the middle part duodenum of 0.5cm * 0.5cm, it is rinsed well, be tiled on the filter paper liquid is blotted, immerse formaldehyde fixed liquid, spectroscopic analysis with 0.9%NaCl.
The result shows:
Experimental group is organized with respect to blank: broiler daily gain and daily ingestion amount have improved 12.35% (P＜0.05), 10.26% (P＜0.05) respectively, and the quantity of bacillus bifidus has significantly improved 24.35% (P＜0.05), 23.26% (P＜0.05) respectively in jejunum, the caecum; The quantity of lactobacillus has significantly improved 15.34% (P＜0.05) in the caecum, the escherichia coli quantity of jejunum and caecum descended respectively 33.25% (P＜0.05), 21.23% (P＜0.05); Duodenum, jejunum and ileum height of naps improved 22.23% (P＜0.05), 14.54% (P＜0.05) 21.42% (P＜0.05) respectively, the crypts degree of depth has reduced by 24.54% (P＜0.05), 13.26% (P＜0.05), 11.31% (P＜0.05) respectively.
Contrast groups is organized with respect to blank: broiler daily gain and daily ingestion amount have improved 6.79% and 4.48% respectively, but difference is not remarkable.The quantity of bacillus bifidus has improved 4.91%, 3.85% respectively in jejunum, the caecum, and the quantity of lactobacillus has improved 3.31% in the caecum, and the escherichia coli quantity of jejunum and caecum has descended 3.49%, 5.71% respectively, but does not all reach significant level.The height of naps of duodenum, jejunum and ileum and the crypts degree of depth do not have significant change.
The preparation method of embodiment 3, a kind of copper-loaded chitosan antimicrobial agent, carry out following steps successively:
1), in 50 ℃, adding molecular weight at the acetic acid solution of mass concentration 2% is the chitosan of 80kDa, the chitosan acid solution; The mass concentration of chitosan in the chitosan acid solution is 5%;
2), utilize the acetic acid solution of mass concentration 2% to regulate the chitosan acid solution, making its pH value is 5; Thereby form the micropartical emulsion;
3), centrifugalize micropartical emulsion, micropartical;
Slowly micropartical is added under stirring condition in the copper-bath that copper ion concentration is 1000mg/L, get mixed liquor, the weight ratio of chitosan is 30% in copper sulfate and the step 1); The pH value that utilizes concentration to regulate mixed liquor for the sodium bicarbonate solution of 2mol/L then is 6, and room temperature reaction 10 hours gets emulsion;
4), in the emulsion of step 3) gained, add concentration be the sodium bicarbonate solution of 2mol/L to regulate pH value be 8.5, wash then 6 times, centrifugal again; Get solid product;
5), with 70 ℃ of step 4) gained solid products oven dry 16 hours, be crushed to then and can cross 500 purposes sieve at least, copper-loaded chitosan antimicrobial agent.
In this copper-loaded chitosan antimicrobial agent, the mass concentration of mantoquita and chitosan is respectively: the content of copper ion is about 10% (being that copper sulfate is about 25%), and chitosan content is about 75%.
Experiment 3, select the 21 age in days DLY three way cross ablactational baby pig of 72 about 6.5kg of body weight for use, principle close by body weight, male and female half and half is divided into 4 groups at random, every group of 3 repetitions, and each repeats 6 pigs.
Experimental group: the feeding daily ration is: the copper-loaded chitosan antimicrobial agent that adds 100mg embodiment 3 gained in every kg conventional feed;
Blank group: the feeding daily ration is: conventional feed;
Contrast groups 1: the feeding daily ration is: add 25mg copper sulfate and 75mg chitosan (that is same experimental group of addition of assurance copper sulfate and chitosan, in the per kilogram conventional feed.)
Contrast groups 2: according to the disclosed technology of Han Xin swallow of informing in the background technology, adjust the proportionate relationship of copper sulfate and chitosan nano suspension, in the per kilogram conventional feed, add this product, thereby guarantee with respect to adding 25mg copper sulfate and 75mg chitosan in the per kilogram conventional feed.
All the other are equal to experiment 1.
The result is:
Experimental group is organized with respect to blank: ablactational baby pig daily gain and daily ingestion amount have improved 45.65% (P＜0.05), 25.36% (P＜0.05) respectively, material anharmonic ratio 26.68% (P＜0.05) that descended, diarrhea rate 31.25% (P＜0.05) that descended; Serum complement C3 level and lysozyme content have improved 46.35% (P＜0.05), 23.12% (P＜0.05) respectively; Duodenum, jejunum, ileum and caecum escherichia coli quantity have significantly reduced by 22.35%, 18.24%, 15.23% and 10.25% (P＜0.05) respectively, jejunum and caecum lactic acid bacterium number have increased by 15.32% (P＜0.05) and 12.31% (P＜0.05) respectively, and duodenum and caecum bacillus bifidus quantity have increased by 12.13% (P＜0.05) and 15.86% (P＜0.05) respectively; Duodenum intestinal villus height has increased by 10.25% (P＜0.05), and the crypts degree of depth has reduced by 18.36% (P＜0.05).
Contrast groups 1 is with respect to the blank group: the ablactational baby pig daily gain has improved 12.31% (P＜0.05), material anharmonic ratio 8.95% (P＜0.05) that descended, and daily ingestion amount and diarrhea rate do not have significant change; Serum complement C3 level and lysozyme content have improved 12.32% (P＜0.05), 10.25% (P＜0.05) respectively; Duodenum, jejunum, ileum and caecum escherichia coli, lactobacillus and bacillus bifidus quantity do not have significant change; The duodenum intestinal villus height and the crypts degree of depth do not have significant change yet.
Contrast groups 2 is with respect to the blank group: the ablactational baby pig daily gain has improved 20.15% (P＜0.05), material anharmonic ratio 13.4% (P＜0.05) that descended, and daily ingestion amount and diarrhea rate do not have significant change; Serum complement C3 level and lysozyme content have improved 21.12% (P＜0.05), 15.12% (P＜0.05) respectively; Duodenum, jejunum, ileum and caecum escherichia coli, lactobacillus and bacillus bifidus quantity do not have significant change; The duodenum intestinal villus height and the crypts degree of depth do not have significant change yet.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (7)
1. the preparation method of copper-loaded chitosan antimicrobial agent is characterized in that may further comprise the steps successively:
1), in 20～60 ℃, be that 0.1～5% acid solution adds chitosan in mass concentration, the chitosan acid solution; The mass concentration of described chitosan in the chitosan acid solution is 0.1～5%;
2), to utilize mass concentration be that 0.1～5% acid solution is regulated the chitosan acid solution, making its pH value is 3～5; Thereby form the micropartical emulsion;
3), centrifugalize micropartical emulsion, micropartical;
Under stirring condition, micropartical is added in the copper salt solution that copper ion concentration is 100-1000mg/L, mixed liquor, described mantoquita be in the step 1) chitosan weight 5～30%; Utilizing concentration then is that the pH value that the alkaline solution of 0.5～10mol/L is regulated mixed liquor is 4.5～5.5, room temperature reaction 5～10 hours, emulsion;
4), in the emulsion of step 3) gained, add concentration be the alkaline solution of 0.5～10mol/L to regulate pH value be 7～9, wash then 3～7 times, refilter or centrifuge dehydration; Collect solid product;
5), step 4) gained solid product oven dry back is pulverized, copper-loaded chitosan antimicrobial agent.
2. the preparation method of copper-loaded chitosan antimicrobial agent according to claim 1, it is characterized in that: the chitosan in the described step 1) is that molecular weight is the chitosan of 2～80kDa.
3. the preparation method of copper-loaded chitosan antimicrobial agent according to claim 1 and 2, it is characterized in that: the mantoquita in the described step 3) is copper chloride, copper nitrate, copper sulfate, copper chloride hydrate, copper nitrate hydrate or copper sulfate hydrate.
4. the preparation method of copper-loaded chitosan antimicrobial agent according to claim 3 is characterized in that: described step 1) and step 2) in acid be acetic acid or hydrochloric acid.
5. the preparation method of copper-loaded chitosan antimicrobial agent according to claim 4, it is characterized in that: alkali is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate in described step 3) and the step 4).
6. the preparation method of copper-loaded chitosan antimicrobial agent according to claim 5, it is characterized in that: the bake out temperature of described step 5) is 50～70 ℃, is crushed to and can crosses 300 purposes sieve at least.
7. the purposes of the copper-loaded chitosan antimicrobial agent that utilizes any one method preparation in the claim 1～6 and get is characterized in that: as the feed additive of poultry or aquatic animal.
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| CN103446629A (en) * | 2013-08-28 | 2013-12-18 | 中国科学院理化技术研究所 | anti-infection material for intrauterine device and preparation method thereof |
| CN105851692A (en) * | 2016-04-20 | 2016-08-17 | 广州市海维饲料有限公司 | Large-scale grass carp compound feed |
| CN109169706A (en) * | 2018-07-19 | 2019-01-11 | 大美泰康（天津）生态科技有限公司 | Complex antimicrobials and antibacterial bacteriostatic type multifunctional inorganic ecologic coating obtained |
| CN109265750A (en) * | 2018-08-28 | 2019-01-25 | 安徽江淮汽车集团股份有限公司 | A kind of antibacterial agent and preparation method thereof |
| CN112140680A (en) * | 2020-09-14 | 2020-12-29 | 北京鉴真保鲜科技有限公司 | Corrugated paper for adsorbing pesticide residues on fruits and vegetables and preparation method thereof |
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| CN103446629A (en) * | 2013-08-28 | 2013-12-18 | 中国科学院理化技术研究所 | anti-infection material for intrauterine device and preparation method thereof |
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| CN105851692A (en) * | 2016-04-20 | 2016-08-17 | 广州市海维饲料有限公司 | Large-scale grass carp compound feed |
| CN109169706A (en) * | 2018-07-19 | 2019-01-11 | 大美泰康（天津）生态科技有限公司 | Complex antimicrobials and antibacterial bacteriostatic type multifunctional inorganic ecologic coating obtained |
| CN109265750A (en) * | 2018-08-28 | 2019-01-25 | 安徽江淮汽车集团股份有限公司 | A kind of antibacterial agent and preparation method thereof |
| CN112140680A (en) * | 2020-09-14 | 2020-12-29 | 北京鉴真保鲜科技有限公司 | Corrugated paper for adsorbing pesticide residues on fruits and vegetables and preparation method thereof |
| CN114711253A (en) * | 2021-01-06 | 2022-07-08 | 合肥杰事杰新材料股份有限公司 | Antibacterial agent, preparation method thereof and antibacterial composition |
| CN114711253B (en) * | 2021-01-06 | 2024-02-20 | 合肥杰事杰新材料股份有限公司 | Antibacterial agent, preparation method thereof and antibacterial composition |
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