CN111096393A - Composite metal cysteamine chelate as well as preparation method and application thereof - Google Patents
Composite metal cysteamine chelate as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite metal cysteamine chelate as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving cysteamine hydrochloride in water, adding metal salt or metal compound, stirring uniformly, adjusting the pH value to 10-11, heating for reaction, and filtering to obtain cysteamine metal chelate; dispersing the cysteamine metal chelate in ethanol, adding ethyl orthosilicate, stirring until the system is turbid, adding dodecyl dimethyl tertiary amine and gamma-chloropropyl trimethoxy silane, heating for reaction, filtering, washing and drying to obtain the composite metal cysteamine chelate. Chelating trace metal elements with cysteamine, and in-situ depositing SiO on the outer layer of chelate2The coating layer is modified by matching with quaternary ammonium salt on the surface, so that the stability and the antibacterial activity are improved, the storage period of the feed is prolonged, the feed is prevented from mildewing, and the application value is quite high.
Description
Technical Field
The invention relates to a cysteamine complex, in particular to a composite metal cysteamine chelate, a preparation method and application thereof.
Background
The cysteamine can be used as feed additive, and can promote animal growth, and increase feed conversion ratio and protein deposition rate. In order to solve the problem of poor stability of the cysteamine, the cysteamine hydrochloride is generally prepared in practical application, and the cysteamine hydrochloride must be dissolved in water and then stirred with feed for feeding, so that the cysteamine hydrochloride is inconvenient to use and has the defects of poor palatability, bad smell and the like.
The cysteamine chelated zinc is a novel feed additive developed in recent years, and the addition of zinc element can promote the growth and development of animals, enhance the immunity of the animals, and improve the stability and palatability of chemical structures. However, the cysteamine chelated zinc has the following defects, which limit its application in feed:
(1) the zinc content is high, so that excessive zinc in the feed is easily caused, and the health of animals is harmed;
(2) the long-term stability is limited, and the feed storage is influenced;
(3) has poor antibacterial activity, and has limited effects in preventing feed from mildewing and improving disease resistance of animals.
Disclosure of Invention
The invention aims to solve at least one of the technical problems in the prior art, and provides a preparation method of a composite metal cysteamine chelate, which comprises the steps of chelating trace metal elements with cysteamine, and depositing SiO in situ on the outer layer of the chelate2The coating layer is modified by matching with quaternary ammonium salt on the surface, so that the stability and the antibacterial activity are improved.
The preparation method of the composite metal cysteamine chelate according to the embodiment of the invention comprises the following steps:
s1, dissolving cysteamine hydrochloride in water, adding a metal compound, uniformly stirring, adjusting the pH value to 10-11, heating for reaction, and filtering to obtain a cysteamine metal chelate;
s2, dispersing the cysteamine metal chelate in ethanol to make the solution alkaline, adding ethyl orthosilicate, stirring until the system is turbid, adding dodecyl dimethyl tertiary amine and gamma-chloropropyl trimethoxy silane, heating for reaction, filtering, washing and drying to obtain the composite metal cysteamine chelate.
The preparation method of the composite metal cysteamine chelate provided by the embodiment of the invention has at least the following beneficial effects:
in-situ deposition of SiO on outer layer of cysteamine metal chelate2The coating layer improves the stability of the cysteamine, leads the sulfhydryl group not to be easily oxidized and decomposed in the storage process of the cysteamine, and prevents the activity of the cysteamine from being lost due to deliquescence and deterioration. The in-situ deposition method can obtain fine-grained SiO2Particles, increasing SiO2The specific surface area and the stacking density of the compound can ensure the protection effect on the cysteamine, prolong the storage life and simultaneously facilitate the full grafting of the quaternary ammonium salt on the SiO2A surface. The organosilicon quaternary ammonium salt can adsorb bacteria and has good antibacterial effect. Due to the excellent characteristics, the feed additive can be used as a feed additive, can promote the growth of animals, inhibit the reproduction of harmful bacteria, improve the disease resistance of the animals, prolong the storage period of the feed, prevent the feed from mildewing, and has considerable application value.
Furthermore, various metal elements such as calcium, zinc, iron, copper, manganese and the like are complexed with cysteamine, so that the nutritive value can be improved, the problem that a single metal element exceeds the standard is avoided, and the growth requirement of animals is better met. Meanwhile, the mode can also improve the stability and the bacteriostatic activity of the cysteamine to a certain extent.
In a second aspect, a composite metal cysteamine chelate is provided, which comprises a cysteamine metal chelate and a silicon dioxide coating layer coated on the surface of the cysteamine metal chelate, wherein quaternary ammonium salt is grafted on the surface of the silicon dioxide coating layer. In the cysteamine metal chelate, the metal element preferably comprises at least one of calcium, zinc, iron, copper and manganese, more preferably comprises calcium and zinc, and most preferably comprises calcium, zinc, iron, copper and manganese.
In a third aspect, the application of the composite metal cysteamine chelate or the composite metal cysteamine chelate prepared by the method in a feed additive is provided.
Drawings
FIG. 1 shows the antimicrobial properties of some of the examples and comparative examples of the present invention against different bacterial species.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the following detailed description is further provided in conjunction with specific embodiments. The embodiments described herein are only some of the embodiments of the present application and should not be construed as limiting the scope of the present application.
The preparation method of the composite metal cysteamine chelate provided by the embodiment of the invention comprises the following steps:
s1, dissolving cysteamine hydrochloride in water, adding a metal compound, uniformly stirring, adjusting the pH value to 10-11, heating for reaction, and filtering to obtain a cysteamine metal chelate;
s2, dispersing the cysteamine metal chelate in ethanol to make the solution alkaline, adding ethyl orthosilicate, stirring until the system is turbid, adding dodecyl dimethyl tertiary amine and gamma-chloropropyl trimethoxy silane, heating for reaction, filtering, washing and drying to obtain the composite metal cysteamine chelate.
In-situ generation of SiO by hydrolysis of tetraethoxysilane2In-situ deposition of SiO on the outer layer of cysteamine metal chelate by electrostatic adsorption2Coating layer, and grafting the organosilicon quaternary ammonium salt onto SiO by the reaction of dodecyl dimethyl tertiary amine and gamma-chloropropyl trimethoxy silane2And (5) obtaining a three-layer shell-core structure. Wherein the core layer is cysteamine metal chelate which is SiO2The coating improves the stability of the cysteamine, leads the sulfydryl not to be easily oxidized and decomposed in the storage process of the cysteamine, and prevents the activity of the cysteamine from being lost due to deliquescence and deterioration. In situThe deposition method can obtain SiO with fine granularity2Particles, increasing SiO2The specific surface area and the stacking density of the compound can ensure the protection effect on the cysteamine, prolong the storage life and simultaneously facilitate the full grafting of the quaternary ammonium salt on the SiO2A surface. The quaternary ammonium salt organic compound on the outermost layer can adsorb bacteria and has a good antibacterial effect. Due to the excellent characteristics, the feed additive can be used as a feed additive, can promote the growth of animals, inhibit the reproduction of harmful bacteria, improve the disease resistance of the animals, prolong the storage period of the feed, prevent the feed from mildewing, and has considerable application value.
In step S1, the metal compound may be at least one of a calcium compound, a zinc salt, a manganese salt, a copper salt, and a ferric salt, preferably a calcium compound and a zinc salt, and the calcium compound is added first, stirred for a period of time, for example, for more than 30min, until completely dissolved, so that calcium is fully complexed with cysteamine, and then the zinc salt is added. More preferably, after adding the zinc salt, the manganese salt, the copper salt and the iron salt can be sequentially added, after each metal salt is added, the mixture is stirred until the dissolution is completed, and then the next metal salt is added. The calcium compound is selected from at least one of calcium carbonate, calcium oxide and calcium hydroxide, and the zinc salt, manganese salt, copper salt and iron salt are independently at least one of sulfate, nitrate, hydrochloride and hydrate thereof. The proportion of each metal element is preferably controlled to be calcium: zinc: iron: copper: the weight ratio of the total weight of the metal elements to the cysteamine is 10-25: 75-90.
The feeding sequence and the proportion of the metal compound are designed according to the chelating capacity of different metal elements and cysteamine and the stability of a chelate, so that the complexation of various trace metal elements and cysteamine is facilitated, the nutritive value is improved, and the problem that a single metal element exceeds the standard is avoided. Except zinc, calcium, iron, manganese and copper can all participate in the composition of the body, and the iron element is a raw material for synthesizing hemoglobin in the maturation process of erythrocytes in the body of an animal; copper element is an important element for composing protein in an animal body, and has important influence on blood and an immune system; manganese affects the activity of some key enzymes in protein metabolism, for example, activation of aminoacyl prolidase must involve manganese to function. In addition, the trace elements are also important components of various biological enzymes, and can promote the growth of animals and improve the conversion efficiency of the feed. The traditional method is to directly add the metal compound to prepare a mixture, which easily causes excessive anions, and the method enables metal elements to be fully complexed with cysteamine, thereby well overcoming the defect, and simultaneously, the method can also improve the stability and the bacteriostatic property of the cysteamine to a certain extent (which will be explained by specific examples later).
In the step S1, the pH value can be adjusted by using a sodium hydroxide aqueous solution or solid sodium hydroxide, the pH value is controlled to be 10-11, the complexation of each metal ion and cysteamine is facilitated, and the product yield can be greatly improved. The heating reaction temperature can be 70-80 ℃, and the reaction time is more than 1 h.
In order to promote the dissolution and dispersion of the cysteamine hydrochloride and the metal compound, a small amount of first dispersing agent, such as polyvinylpyrrolidone, may be added after the cysteamine hydrochloride is added and/or after all the metal compound is added, and the amount of the first dispersing agent added each time is preferably 0.1-1% of the weight of the cysteamine hydrochloride.
Step S2 is mainly used for coating SiO on the surface of cysteamine metal chelate2And grafting quaternary ammonium salt on the outermost layer. TEOS hydrolysis needs to be performed in alkaline aqueous solution, the cysteamine metal chelate obtained after filtration in step 1 of this example usually contains about 35% of alkaline aqueous solution, and the wet filter cake can be added into ethanol solution. After the ethyl orthosilicate is added, the stirring reaction time is preferably more than 2 hours, more preferably more than 5 hours, so as to ensure that the reaction is fully carried out. A second dispersant, such as Tween 80, can also be added to facilitate SiO2The second dispersing agent is preferably used in an amount of 0.1 to 1% by weight based on the total weight of the solid components. The addition amount of the tetraethoxysilane is SiO coated according to the requirement2Selecting the content, preferably controlling the weight ratio of cysteamine metal chelate to tetraethoxysilane to be 4-5: 2 to 8. More preferably, the amount of ethyl orthosilicate added is such that SiO is2Control of weight ratio of coating layer to cysteamine metal chelate10-20: 80-90.
The dodecyl dimethyl tertiary amine and the gamma-chloropropyl trimethoxy silane are selected according to the content of the quaternary ammonium salt to be grafted, and in a preferred embodiment, the weight ratio of the ethyl orthosilicate to the dodecyl dimethyl tertiary amine to the gamma-chloropropyl trimethoxy silane is 2-8: 1-2: 3-5. In order to promote the quaternization reaction of the dodecyl dimethyl tertiary amine and the gamma-chloropropyl trimethoxyl silane, a small amount of sodium iodide can be added into a reaction system, and the addition amount of the sodium iodide can be 0.01-0.05% of the total weight of the dodecyl dimethyl tertiary amine and the gamma-chloropropyl trimethoxyl silane. The reaction temperature is preferably 55-65 ℃, and the reaction time is 4-6 h. After the reaction is finished, the drying temperature of the obtained product is preferably 70-80 ℃.
The composite metal cysteamine chelate provided by the embodiment of the invention comprises cysteamine metal chelate and a silicon dioxide coating layer coated on the surface of the cysteamine metal chelate, wherein quaternary ammonium salt is grafted on the surface of the silicon dioxide coating layer. The composite metal cysteamine chelate can be prepared by the method examples, and for the selection, the proportion and the functions of the components, the previous preparation method examples can be referred, and the discussion is not repeated here.
The invention is illustrated in detail below by way of exemplary embodiments, in which the various reagents used are analytical grade.
In each example, the test method for the content of the product components is as follows:
determination of cysteamine content: GB/T24832-2009;
and (3) determination of zinc content: GB/T5009.14-2003;
determination of calcium content: GB 5009.92-2016;
determination of manganese content: GB 5009.242-2017;
and (3) determination of iron content: GB 5009.90-2016;
and (3) determination of copper content: GB 5009.13-2017.
Example 1
(1) And (3) preparing a cysteamine metal chelate. Dissolving 5g of cysteamine hydrochloride in water, stirring at room temperature until the cysteamine hydrochloride is completely dissolved, sequentially adding 1.6g of calcium carbonate, 2.2g of zinc sulfate heptahydrate, 0.6g of ferric sulfate heptahydrate, 0.5g of copper sulfate pentahydrate and 0.4g of manganese sulfate heptahydrate, and stirring for about 30min after adding one substance each time until the substances are completely dissolved; adding solid sodium hydroxide, and adjusting the pH value to 10 to obtain a turbid solution; stirring for 1h at 80 ℃; carrying out suction filtration to obtain cysteamine metal chelate, wherein the dry weight of the cysteamine metal chelate is about 4.6 g;
(2)SiO2and (3) preparing a cysteamine-coated metal chelate. Adding the cysteamine metal chelate (wet filter cake) prepared in the step (1) into 100mL of ethanol, stirring for 30min until the cysteamine metal chelate is uniformly dispersed, testing that the pH value is alkaline, adding 3mL of ethyl orthosilicate, adding 0.01 g of dispersing agent Tween 80, and stirring the mixed solution for 5h at room temperature;
(3) amino-modified SiO2And (3) preparing a cysteamine-coated metal chelate. Adding 1mL of dodecyl dimethyl tertiary amine and 3mL of gamma-chloropropyl trimethoxyl silane into the reaction system in the step (2), heating to 60 ℃ for reaction for 5 hours to obtain a suspension after the reaction is finished, filtering, washing and drying at 80 ℃ to obtain the SiO modified by the quaternary ammonium salt derivative2Coating cysteamine metal chelate. The detection shows that the cysteamine in the obtained product accounts for about 78%, the mass ratio of each metal is about 4.4% of calcium, 3.6% of zinc, 0.9% of iron, 0.5% of copper, 0.6% of manganese and 12% of silicon dioxide coating layer.
Example 2
(1) And (3) preparing a cysteamine metal chelate. Dissolving 5g of cysteamine hydrochloride in water, adding 0.1 g of dispersant polyvinylpyrrolidone, and stirring at room temperature until the cysteamine hydrochloride is completely dissolved; sequentially adding 0.9g of calcium oxide, 2.7g of zinc sulfate heptahydrate, 0.86g of iron sulfate heptahydrate, 0.4g of copper sulfate pentahydrate, 0.3g of manganese sulfate pentahydrate and 0.02 g of polyvinylpyrrolidone, and stirring for about 30min after adding each substance until the substances are completely dissolved; adding 35% sodium hydroxide aqueous solution, and adjusting the pH value to 11 to obtain turbid solution; stirring for 1h at 80 ℃; carrying out suction filtration to obtain cysteamine metal chelate, wherein the dry weight of the cysteamine metal chelate is about 4.75 g;
(2)SiO2and (3) preparing a cysteamine-coated metal chelate. Adding the cysteamine metal chelate prepared in the step (1) into 100mL of ethanolStirring the mixture (wet filter cake) for 30min until the mixture is uniformly dispersed, testing the pH value to be alkaline, adding 2mL of tetraethoxysilane, adding 0.01 g of dispersant Tween 80, and stirring the mixed solution at room temperature for 5 h;
(3) preparing amino modified SiO2 coated cysteamine metal chelate. Adding 1.2mL of dodecyl dimethyl tertiary amine and 4mL of gamma-chloropropyl trimethoxyl silane into the reaction system in the step (2), heating to 60 ℃ for reaction for 5 hours to obtain a suspension after the reaction is finished, filtering, washing and drying at 80 ℃ to obtain the SiO modified by the quaternary ammonium salt derivative2Coating cysteamine metal chelate. The detection shows that the cysteamine in the obtained product accounts for about 80%, the silicon oxide coating layer accounts for about 10%, and the mass ratio of each metal is respectively about 3.6% of calcium, 4.1% of zinc, 1.4% of iron, 0.5% of copper and 0.4% of manganese.
Example 3
(1) And (3) preparing a cysteamine metal chelate. 5g of cysteamine hydrochloride is dissolved in water and stirred at room temperature until the cysteamine hydrochloride is completely dissolved; sequentially adding 1.8g of calcium carbonate, 2.7g of zinc sulfate heptahydrate, 0.7g of iron sulfate heptahydrate, 0.08g of copper sulfate pentahydrate and 0.05g of manganese sulfate pentahydrate, and stirring for about 30min after adding each substance until the substances are completely dissolved; adding 35% sodium hydroxide aqueous solution, and adjusting the pH value to 10 to obtain turbid solution; stirring for 1h at 80 ℃; carrying out suction filtration to obtain cysteamine metal chelate, wherein the dry weight of the cysteamine metal chelate is about 4.1 g;
(2)SiO2and (3) preparing a cysteamine-coated metal chelate. Adding the cysteamine metal chelate (wet filter cake) prepared in the step (1) into 100mL of ethanol, stirring for 30min until the cysteamine metal chelate is uniformly dispersed, testing that the pH value is alkaline, adding 2mL of ethyl orthosilicate, adding 0.01 g of dispersing agent Tween 80, and stirring the mixed solution for 5h at room temperature;
(3) amino-modified SiO2And (3) preparing a cysteamine-coated metal chelate. Adding 2mL of dodecyl dimethyl tertiary amine and 3mL of gamma-chloropropyl trimethoxyl silane into the reaction system in the step (2), adding 0.015 g of sodium iodide, heating to 60 ℃ for reaction for 4h to obtain a suspension after the reaction is finished, filtering, washing and drying at 80 ℃ to obtain the SiO modified by the quaternary ammonium salt derivative2Coating cysteamine metal chelate. Detecting to obtain the productThe cysteamine accounts for about 77 percent, the silicon oxide coating layer accounts for about 13 percent, and the mass ratio of each metal is respectively about 5.4 percent of calcium, 3.6 percent of zinc, 0.8 percent of iron, 0.1 percent of copper and 0.1 percent of manganese.
Comparative example 1
Commercially available zinc cysteamine.
Comparative example 2
The cysteamine metal chelate compound prepared by the method of step (1) of example 1 was washed, dried and ground into powder.
Comparative example 3
SiO prepared by the method of Steps (1) and (2) of example 12Coating cysteamine metal chelate, filtering, washing, drying and grinding into powder.
Comparative example 4
Commercial silica powder (average particle size 500nm) was blended with the product of comparative example 2 in a ratio equivalent to the composition of comparative example 3.
Test example
For testing the stability and antibacterial properties of the product.
Test example 1: stability test
For each example and comparative example, equal weight of each product was taken, each product was equally divided into 2 parts, each product was placed in an open container having the same volume, the container was placed in air at room temperature for 72 days, 2 samples of each product were used for measuring the retention amount of cysteamine on days 20 and 72, and the ratio of the retention amount to the initial weight was calculated, i.e., the retention rate.
The retention rates of the examples are comparable, and the results of example 1 are only used as an example, and the retention rates at different stages in comparison with the respective ratios are shown in table 1:
TABLE 1
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Standing for 20 days | 99.8％ | 97.5％ | 98.6％ | 99.8％ | 99.3％ |
| Standing for 72 days | 99.1％ | 91.0％ | 95.5％ | 98.9％ | 96.1％ |
From the results, compared with a physical mixing mode, the mode of in-situ deposition of silicon dioxide is used for coating the cysteamine metal chelate, so that the degradation rate of cysteamine can be greatly reduced, and quaternary ammonium salt is further grafted outside the silicon dioxide coating layer, so that the long-term stability can be slightly improved. In addition, various metal elements are adopted to be complexed with the cysteamine, so that the stability of the cysteamine can be improved to a certain extent.
Test example 2: and (3) antibacterial property test:
escherichia coli, staphylococcus aureus and bacillus subtilis are selected as experimental strains, and the specific experimental operations are as follows:
(1) preparation of Luria-Bertani (LB) culture medium
Preparing an LB liquid culture medium: 3g of tryptone, 1.5g of sodium chloride and 1.5g of yeast extract were weighed into a 500mL clean Erlenmeyer flask, 300mL of redistilled water was added, the mixture was stirred on a stirrer to be mixed uniformly, and the pH was adjusted to 7.5 with NaOH solution. Then sterilizing with high pressure steam, naturally cooling to room temperature after sterilization, screwing the bottle cap, sealing, and storing in a refrigerator at 4 deg.C for use.
Preparing an LB solid culture medium: the solid medium was supplemented with 1.5% agarose more than the liquid medium. And (3) autoclaving the culture medium, immediately taking out the culture medium when the temperature is reduced to 80 ℃, and pouring the culture medium into a biological safety cabinet. The thickness of the solidified culture medium in each culture dish is 4mm, the culture dish is sealed by a sealant and is placed in a refrigerator at the temperature of 4 ℃.
(2) Recovery and freezing storage of bacteria
And (3) recovering bacteria: and (3) placing the frozen tube in a water bath kettle at 37 ℃ for heating for 5-10 min, then placing the tube in a centrifugal tube for balancing, and then centrifuging for 3min at the rotating speed of 5000 rpm. The supernatant was discarded, and the bacteria were aspirated with a pipette and blown evenly. A small amount of the inoculum was dipped with an inoculating loop and placed in a bacterial culture tube containing 5mL of medium. The tube was then placed on a shaker at 180rpm and left at 37 ℃ for 10 hours.
And (3) freezing and storing bacteria: sucking 1mL of bacterial liquid into each centrifuge tube, centrifuging at 1000rpm for 2min, discarding supernatant, adding a proper amount of frozen stock solution into the centrifuge tube, blowing uniformly, and storing in a refrigerator at-80 ℃.
(3) Preparation of sample solution
And (3) putting 60mg of sample powder into a 4mL centrifuge tube, adding 4mL of secondary deionized water, preparing a proper amount of 15mg/mL sample, and stirring and dispersing to prepare a suspension. Filtering and sterilizing with sterilized microporous filter membrane.
(4) Antibacterial performance of composite material measured by bacteriostatic loop method
The antibacterial circle is measured by a filter paper diffusion method, the filter paper is cut into small round paper sheets with the diameter of 10mm by a puncher, the paper sheets are placed in a 1mL EP tube and are dried in a drying oven at 37 ℃, and the paper sheets are sterilized for 30min at 120 ℃ when in use. In a clean bench, an appropriate amount of escherichia coli, staphylococcus aureus and bacillus subtilis are respectively selected from an inoculating loop sterilized by alcohol lamp flame to prepare bacterial suspension with the bacterial liquid concentration of 1 × 104CFU/mL (4.5 mL of physiological saline is put into a 10mL EP tube, 0.5mL of bacterial suspension cultured overnight is added and mixed uniformly, so that primary dilution is completed, and the primary dilution is carried out for 4 times to obtain 1 × 104CFU/mL bacterial suspension).
Coating bacteria by ball method: and (3) placing about 8 glass beads on a flat plate, uniformly dispersing 0.2mL of bacterial suspension on each glass bead, and slightly shaking the flat plate to uniformly distribute the bacterial liquid as much as possible to obtain the bacterial-containing flat plate. Then, filter paper pieces were attached to the plate containing the bacteria using sterilized tweezers, five filter paper pieces were placed in equal distances on each petri dish, see fig. 1, 30 μ L of the sample solution prepared in step (3) of this test example 2 was pipetted on each filter paper piece, and each treated petri dish was placed in a constant temperature incubator for culture. The solid medium was cultured in an inverted state in a constant temperature incubator at 37 ℃ for 12 hours. At the same time, at 0.1mg/mLAgNO3The solution and sterile water are respectively a positive control group and a negative control group. The effect was observed, and the size (mm) of the zone of inhibition diameter was measured using a common ruler, and the bacteriostatic efficacy of the sample solutions of example 1, comparative example 2, and comparative example 3 for each test strain was shown in fig. 1 and table 2. In FIG. 1, a Escherichia coli, b Staphylococcus aureus, c Bacillus subtilis; samples No. 1-5 represent sterile water, comparative example 3, comparative example 2, example 1, 0.1mg/mL AgNO, respectively3And (3) solution.
Comparative AgNO3The solution, the final product prepared in the embodiment 1 of the invention has good antibacterial performance, and especially has the most obvious antibacterial effect on staphylococcus aureus.
TABLE 2
| Test sample | Escherichia coli | Staphylococcus aureus | Bacillus subtilis |
| Comparative example 2 | 11.5 | 17.9 | 13.5 |
| Comparative example 3 | 10 | 12 | 10 |
| Example 1 | 12.5 | 19.6 | 16.0 |
| 0.1mg/mLAgNO3 | 23.8 | 15.7 | 22.9 |
| Sterile water | 10 | 10 | 10 |
Claims (10)
1. A preparation method of a composite metal cysteamine chelate is characterized by comprising the following steps:
s1, dissolving cysteamine hydrochloride in water, adding a metal compound, uniformly stirring, adjusting the pH value to 10-11, heating for reaction, and filtering to obtain a cysteamine metal chelate;
s2, dispersing the cysteamine metal chelate in ethanol to make the solution alkaline, adding ethyl orthosilicate, stirring until the system is turbid, adding dodecyl dimethyl tertiary amine and gamma-chloropropyl trimethoxy silane, heating for reaction, filtering, washing and drying to obtain the composite metal cysteamine chelate.
2. The method for preparing a composite metal cysteamine chelate according to claim 1, wherein in step S1, the metal compound comprises at least one of a compound of calcium, a zinc salt, a manganese salt, a copper salt and an iron salt.
3. The method for preparing a composite metal cysteamine chelate according to claim 2, wherein in step S1, the metal compounds include calcium compound, zinc salt, manganese salt, copper salt and iron salt, which are sequentially added and respectively dissolved by stirring.
4. The method for preparing a composite metal cysteamine chelate according to claim 1, wherein in step S2, the weight ratio of the cysteamine metal chelate to ethyl orthosilicate is 4-5: 2 to 8.
5. The method for preparing the composite metal cysteamine chelate according to claim 1, wherein the weight ratio of the ethyl orthosilicate, the dodecyl dimethyl tertiary amine and the gamma-chloropropyl trimethoxy silane is 2-8: 1-2: 3-5.
6. The composite metal cysteamine chelate is characterized by comprising cysteamine metal chelate and a silicon dioxide coating layer coated on the surface of the cysteamine metal chelate, wherein quaternary ammonium salt is grafted on the surface of the silicon dioxide coating layer.
7. The metal cysteamine chelate according to claim 6, wherein the metallic element in the cysteamine metal chelate comprises at least one of calcium, zinc, iron, copper and manganese.
8. The composite metal cysteamine chelate according to claim 6 or 7, wherein the weight ratio of the total weight of metal elements to cysteamine in the cysteamine metal chelate is 10-25: 75-90.
9. The composite metal cysteamine chelate complex according to claim 6, wherein the weight ratio of the silicon dioxide coating layer to the cysteamine metal chelate complex is 10-20: 80-90.
10. Use of a composite metal cysteamine chelate according to any one of claims 6 to 9 in a feed additive.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114588938A (en) * | 2022-03-17 | 2022-06-07 | 浙江肯特催化材料科技有限公司 | Preparation method of silicon dioxide loaded quaternary ammonium salt phase transfer catalyst |
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| CN114588938A (en) * | 2022-03-17 | 2022-06-07 | 浙江肯特催化材料科技有限公司 | Preparation method of silicon dioxide loaded quaternary ammonium salt phase transfer catalyst |
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