CN109988208A - A kind of preparation method and application of metal-scutelloside complex - Google Patents
A kind of preparation method and application of metal-scutelloside complex Download PDFInfo
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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Abstract
The present invention discloses a kind of preparation method and application of metal-scutelloside complex, is related to veterinary drug technical field.The metal-scutelloside complex preparation method obtains the scutelloside solution of pH7~9 the following steps are included: scutelloside is dissolved in triethylamine solution；Under stiring, metal compound solution is added drop-wise in the scutelloside solution, continues to stir, react to obtain mixed liquor；The mixed liquor is stood, sediment is filtered to obtain, it is washed, dry, obtain metal-scutelloside complex；Wherein, the metallic compound for including in the metal compound solution is lanthanum compound, cerium compound or strontium compound.The present invention is intended to provide metal-scutelloside complex preparation method that a kind of yield is high, product purity is high.
Description
Technical field
The present invention relates to veterinary drug technical field, in particular to the preparation method and application of a kind of metal-scutelloside complex.
Background technique
Grice diarrhoea is one of the principal element for influencing pig-breeding industry, and pathogenic factor is complicated, and disease incidence is high, the death rate
Height seriously affects the sound development of pig breeding industry.The treatment most common method of grice diarrhoea is using antibacterials, but presence at present
The strong problem of bacterial drug resistance, in addition, also there is the method using Chinese herbal treatment grice diarrhoea.
Scutelloside is the main function ingredient of radix scutellariae, is a kind of flavone compound, the bacteriostatic test of inside and outside confirms, yellow
A kind of reed mentioned in ancient books glycosides has good bacteriostasis to Escherichia coli, staphylococcus aureus, Pseudomonas aeruginosa.Recent study finds that scutelloside can
With with the compound of part metals (zinc, copper etc.) occur complex reaction, the stable metal of forming properties-scutelloside complex, and
Pharmacological research shows that metal-scutelloside complex drug effect and antioxidant activity are better than scutelloside, can be preferably by animal
Body is utilized, and the nutritive digestibility and utilization rate, the growth for inhibiting pathogenic bacteria of animal is improved, to effectively enhance rare earth
The activity of element and scutelloside.A kind of metal with high-drug-effect-scutelloside complex is found, and improves metal-Huang obtained
The purity and yield of a kind of reed mentioned in ancient books glycosides complex become urgent problem.
Summary of the invention
The main object of the present invention is to propose a kind of preparation method and application of metal-scutelloside complex, it is desirable to provide
Metal-scutelloside complex preparation method that a kind of yield is high, product purity is high.
To achieve the above object, the invention proposes a kind of metal-scutelloside complex preparation method, the metals-
The preparation method of scutelloside complex the following steps are included:
Scutelloside is dissolved in triethylamine solution, the scutelloside solution of pH7~9 is obtained；
Under stiring, metal compound solution is added drop-wise in the scutelloside solution, continues to stir, react to obtain mixing
Liquid；
The mixed liquor is stood, sediment is filtered to obtain, it is washed, dry, obtain metal-scutelloside complex；
Wherein, the metallic compound for including in the metal compound solution is lanthanum compound, cerium compound or strontium chemical combination
Object.
Optionally, the lanthanum compound is any one in lanthanum nitrate, lanthanum acetate, lanthanum chloride, lanthanum sulfate and lanthanum oxalate；
Or,
The cerium compound is any one in cerous nitrate, cerous acetate, cerium chloride and cerous sulfate；Or,
The strontium compound is strontium nitrate or strontium chloride.
Optionally, the mass fraction of metallic compound described in the metal compound solution is 10~30%.
Optionally, when the metallic compound is lanthanum compound or cerium compound, the preparation of the metal compound solution
Method the following steps are included:
Triethylamine is added into distilled water, is stirred, obtains the solution containing triethylamine；
Metallic compound is dissolved in the solution containing triethylamine, the metal compound solution of pH7~9 is obtained；
Wherein, the mass concentration of triethylamine is 1~3% in the metal compound solution.
Optionally, the metallic compound be strontium compound when, the preparation method of the metal compound solution include with
Lower step: being dissolved in water for strontium compound, and strontium compound solution is made.
Optionally, in the step of scutelloside being dissolved in triethylamine solution, obtaining the scutelloside solution of pH7~9,
The mass concentration of triethylamine is 0.8~1.3% in the scutelloside solution.
Optionally, under stiring, metal compound solution is added drop-wise in the scutelloside solution, continues to stir, reacted
In the step of obtaining mixed liquor,
The molar ratio of scutelloside and metal ion is 1:(1.2~1.8)；And/or
The time for continuing stirring is 30~60min；And/or
The temperature of the reaction is 25~55 DEG C.
Optionally, the mixed liquor is stood, filters to obtain sediment, it is washed, dry, obtain metal-scutelloside complex
The step of include:
After the mixed liquor is stood 3~6h, sediment is filtered to obtain；
After the sediment is successively used triethylamine aqueous solution, water, 60% ethanol washing, vacuum is dry at 40~60 DEG C
It is dry, obtain metal-scutelloside complex；
Wherein, the mass concentration of the triethylamine aqueous solution is 0.3~1.0%.
The invention also provides the metal prepared according to above-mentioned preparation method-scutelloside complexs in treatment grice diarrhoea
Application.
In technical solution of the present invention, used solvent is improved when to dissolution scutelloside, is proposed molten using triethylamine
Liquid compares the alkaline solutions such as existing alcohols solvent or sodium hydroxide, sodium bicarbonate as solvent, has preferably dissolution effect
Fruit, scutelloside can be stabilized and be completely dissolved in triethylamine solution, improve the Determination of baicalin for participating in complex reaction,
Meanwhile scutelloside pH value of solution is limited, so that the pH environment of scutelloside solution is easier to complex reaction progress, and then effectively mention
High product purity, promotes reaction forward to carry out, effectively increases yield.In addition, the present invention is also in lanthanum (cerium)-scutelloside cooperation
It on the basis of object has high-drug-effect, further studies, proposes to react strontium compound into the stable strontium-Huang of obtained property with scutelloside
The preparation method of a kind of reed mentioned in ancient books glycosides complex, strontium obtained-scutelloside complex not only have fungistatic effect more better than scutelloside and
Antioxidant activity, and the effect of promote bone cell activity possessed by having both strontium itself, it is provided newly for treatment grice diarrhoea
Approach has also opened up broader space for strontium.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Other relevant attached drawings are obtained according to these attached drawings.
Fig. 1 is the flow diagram of an embodiment of metal proposed by the present invention-scutelloside complex preparation method；
Fig. 2 is the infrared absorption pattern of scutelloside；
Fig. 3 is lanthanum-scutelloside complex infrared absorption pattern made from embodiment 1；
Fig. 4 is cerium-scutelloside complex infrared absorption pattern made from embodiment 6；
Fig. 5 is strontium-scutelloside complex infrared absorption pattern made from embodiment 10.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Recent study finds that scutelloside can be stable with rare earth metal salt (especially lanthanum salt and cerium salt) forming properties
Metal-scutelloside complex, and pharmacological research shows that metal-scutelloside complex drug effect and antioxidant activity are better than Huang
A kind of reed mentioned in ancient books glycosides can utilize preferably by animal body, improve the nutritive digestibility of animal and utilization rate, inhibit pathogenic bacteria
Growth, to effectively enhance the activity of rare earth element and scutelloside.
In consideration of it, the invention proposes a kind of metal-scutelloside complex preparation method, which can be prepared
Metal-scutelloside complex of rate of output height, good product purity, the complex have more than scutelloside on treatment grice diarrhoea
Good drug effect and antioxidant activity.In conjunction with the process of an embodiment of Fig. 1 metal-scutelloside complex preparation method proposed
Schematic diagram, the metal-scutelloside complex preparation method the following steps are included:
Step S10, scutelloside is dissolved in triethylamine solution, obtains the scutelloside solution of pH7~9.
Wherein, the mass concentration of triethylamine is 0.8~1.3% in the scutelloside solution.
In the present embodiment, using triethylamine solution as the solvent for preparing scutelloside solution, the triethylamine solution can be with
For triethylamine aqueous solution or triethylamine alcoholic solution.In existing metal-scutelloside complex preparation method, usually by hydrogen-oxygen
Change the solvent of the alkaline solutions such as sodium, sodium bicarbonate or alcohols solvent as dissolution scutelloside.But in practical operation, it may appear that yellow
A kind of reed mentioned in ancient books glycosides is apt to deteriorate and the problem of cannot being completely dissolved.It is found through inventor's test of many times, when molten using the alcohol containing triethylamine
When liquid or aqueous solution are as solvent, the solute effect of scutelloside more preferably, on this basis, advanced optimizes, obtains and work as scutelloside
When the mass concentration of triethylamine is 0.8~1.3% in solution, there is optimal dissolution effect.Therefore, preparation method of the present invention uses
As the solvent for preparing scutelloside solution, solve that scutelloside in existing preparation method cannot be completely dissolved asks triethylamine solution
Topic improves the Determination of baicalin for participating in complex reaction, promotes reaction forward progress, effectively increases yield.Meanwhile three second
Amine aqueous solution, pH7~9 acid or alkali environment under, be suitable for metal and scutelloside and complex reaction occurs: under the environment, scutelloside structure is steady
It is fixed, it is unlikely to deteriorate, to reduce the generation of by-product, improves yield；Hydroxyl in scutelloside molecule is easy to dissociate, favorably
In the combination of scutelloside and rare earth ion, is carried out to promote to react toward positive direction, effectively increase yield.
Step S20, under stiring, metal compound solution is added drop-wise in the scutelloside solution, continues to stir, is reacted
Obtain mixed liquor.
Wherein, the metallic compound for including in the metal compound solution is lanthanum compound, cerium compound or strontium chemical combination
Object.That is, preparation method of the present invention can be used conveniently to prepare lanthanum-scutelloside complex, cerium-scutelloside complex or strontium-Huang
A kind of reed mentioned in ancient books glycosides complex.
Lanthanum and cerium are rare earth metal, and rare earth has effects that physiological activation, can activate the intracorporal somatomedin of animal,
Improve metabolism in vivo, improve food conversion ratio, accelerates growth of animal and production, but rare earth itself has one to organism again
Fixed toxic effect.Rare earth and scutelloside are cooperated, the toxicity of rare earth ion can be reduced, is also had more preferable than scutelloside
Drug effect and antioxidant activity.Above-mentioned lanthanum compound, cerium compound can be the various inorganic salts of lanthanum or cerium, it is contemplated that different
Lanthanum salt, the solubility property of cerium salt are different, and the present invention is preferably easier to the lanthanum for dissolving, being easier in conjunction with scutelloside, cerium compound,
Therefore, in one embodiment of this invention, the lanthanum compound can be La (NO3)3(lanthanum nitrate), La (Ac)3(lanthanum acetate),
LaCl3(lanthanum chloride), La2(SO4)3(lanthanum sulfate) and La2(C2O4)3Any one in (lanthanum oxalate), it is molten preparing lanthanum compound
When liquid, the mass fraction of lanthanum compound is 10~30% in the lanthanum compound solution；In another embodiment of the invention, institute
Stating cerium compound can be Ce (NO3)3(lanthanum nitrate), Ce (Ac)3(lanthanum acetate), CeCl3(lanthanum chloride) and Ce2(SO4)3(sulfuric acid
Lanthanum) in any one, when preparing cerium compound solution, in the cerium compound solution mass fraction of cerium compound be 10~
30%.
Due to lanthanum compound and cerium compound facile hydrolysis in aqueous solution, and precipitating is also easy to produce in alcohols solvent, therefore,
When preparing lanthanum compound solution or cerium compound solution, may include steps of:
Step S210, triethylamine is added into distilled water, is stirred, obtains the solution containing triethylamine；
Step S220, metallic compound is dissolved in the solution containing triethylamine, obtains the metal compound of pH7~9
Object solution.
Wherein, the metallic compound is lanthanum compound or cerium compound；Triethylamine in the metal compound solution
Mass concentration is 1~3%.
Lanthanum compound or cerium compound can be stabilized and will not precipitate in the solution containing triethylamine, be conducive to
Complex reaction occurs for lanthanum ion or cerium ion and scutelloside molecule, reaction yield is improved, moreover, triethylamine molecule does not participate in cooperation
Reaction, therefore, will not generate by-product.
Strontium is a kind of intracorporal microelement of people, and most strontiums are all stored in bone tissue.Its adjustable bone tissue
Structure improves the intensity of bone, promotes the physiological activity of osteocyte.Experimental study confirms that strontium salt has anti-bone resorption and increases bone shape
At effect, strontium salt can inhibit the activity of osteoclast, promote the activity of osteoblast, promote the deposition of bone salts.Inventor
On the basis of lanthanum (cerium)-scutelloside complex has high-drug-effect, further studies, be put forward for the first time strontium compound and scutelloside
React and the stable strontium-scutelloside complex preparation method of property be made, strontium obtained-scutelloside complex not only have than
The better fungistatic effect of scutelloside and antioxidant activity, and the effect of promote bone cell activity possessed by having both strontium itself,
New way is provided for treatment grice diarrhoea, has also opened up broader space for strontium.Above-mentioned strontium compound can
To be the various inorganic salts of strontium, it is contemplated that the solubility property of different strontium salts is different, and the present invention is preferably easier to dissolve, be easier to
Strontium compound in conjunction with scutelloside, therefore, in one embodiment of this invention, the strontium compound can be Sr (NO3)2(nitre
Sour strontium) or SrCl2(strontium chloride), when preparing strontium compound solution, the mass fraction of strontium compound in the strontium compound solution
It is 10~30%., can be soluble in water by strontium compound and since strontium is soluble easily in water, strontium compound solution is made.
In addition, to advanced optimize preparation method to prepare the metal of higher purity, more high yield-scutelloside cooperation
Object, in step S20, rate of addition is 1.0~2.1mL/min；The molar ratio of scutelloside and metal ion is 1:(1.2~1.8)；
The time for continuing stirring is 30~60min；The temperature of the reaction is 25~55 DEG C.
I.e. when specific operation, step S20 can be carried out in the steps below: at 25~55 DEG C, while stirring by metal
Compound solution is added drop-wise in the scutelloside solution, and rate of addition is 1.0~2.1mL/min, after completion of dropwise addition, continues to stir
30~60min obtains mixed liquor.When due to scutelloside excess, scutelloside molecule is polymerize by hydrogen bond, and it is molten that fluid,matching will form colloid
Liquid is not easy to crystallize out so as to cause precipitating, not only reduces yield, nor the reaction process that easily follows up, therefore, in this reality
It applies in example, the molar ratio of scutelloside and metal ion is 1:(1.2~1.8).
Further, since metal ion can generate complex precipitating in conjunction with scutelloside, by control rate of addition and not
Disconnected stirring can make precipitating formation speed moderate, and distribution is not assembled, and then the progress that reacts fully.
Step S30, the mixed liquor is stood, filters to obtain sediment, it is washed, dry, obtain metal-scutelloside cooperation
Object.
When it is implemented, above-mentioned steps S40 may include:
Step S410, after the mixed liquor being stood 3~6h, sediment is filtered to obtain；
Step S420, after the sediment successively being used the triethylamine aqueous solution, water, 60% ethanol washing, in 40~
It is dried in vacuo at 60 DEG C, obtains metal-scutelloside complex.
Wherein, the mass concentration of the triethylamine aqueous solution is 0.3~1.0%.
It is separated by solid-liquid separation again after sufficient standing, precipitating can be made sufficiently to improve the yield precipitated when being separated by solid-liquid separation,
In, there are many ways to separation of solid and liquid, can using filtering, filter, centrifugation etc..
Preparation method simple process proposed by the present invention, easily controllable, production metal-scutelloside complex finished product production
Rate can achieve 99.31~99.87%, and purity can achieve 99.18~99.92%.
In addition, the invention also provides the metal prepared according to above-mentioned preparation method-scutelloside complexs in treatment piglet
Application in diarrhea.
The bacteriostatic test of inside and outside confirms that scutelloside has Escherichia coli, staphylococcus aureus, Pseudomonas aeruginosa good
Bacteriostasis.And rare earth is a kind of less toxic or Poisoning substance, has effects that physiological activation.Strontium is that the intracorporal one kind of people is micro
Element, the structure of adjustable bone tissue improve the intensity of bone, promote the physiological activity of osteocyte.Lanthanum, cerium, strontium and scutelloside
The complex property of formation is stablized, and has drug effect more better than scutelloside and antioxidant activity, and have metal ion institute itself
The effect of having, can preferably be utilized by animal body, improve the nutritive digestibility of animal and utilization rate, inhibition to cause
The growth of germ can be used for treating grice diarrhoea to effectively enhance the activity of scutelloside.Its application mode can be directly
It is taken as therapeutic agent, dosage is daily 50~100mg/kg.bw, is used in conjunction 3~5；It can also be used as additive
It is used to prepare pig starter feed, veterinary drug or premix etc..
Technical solution of the present invention is described in further detail below in conjunction with specific embodiments and the drawings, it should be understood that
Following embodiment is only used to explain the present invention, is not intended to limit the present invention.
Embodiment 1
Weigh 10.1mmol La (NO3)3·6H21% triethylamine aqueous solution is added in 100mL small beaker in O, stirs molten
Solution, obtains the lanthanum solution of 10%, pH7；
100mL distilled water is placed in 250mL there-necked flask, 0.8g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 8；
In 35 DEG C, above-mentioned lanthanum solution is slowly dropped to the speed of 1.5mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, lanthanum ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 30min at 35 DEG C, reacts to obtain mixed liquor；
By mixed liquor stand 3h after, filter to obtain sediment, sediment is successively used 0.3% triethylamine aqueous solution, distilled water,
60% ethanol solution respectively washs 3-5 times, then dry under 40 DEG C of vacuum conditions, and brick-red lanthanum-scutelloside complex is made
Finished product.
With the content of lanthanum in inductance Coupled Plasma-Emission spectroscopic methodology (ICP-OES) measurement product, calculating yield is
99.54%, product purity 99.87%.
Embodiment 2
Weigh 8.7mmol LaCl3·7H22% triethylamine aqueous solution is added in 100mL small beaker in O, and stirring and dissolving obtains
15%, the lanthanum solution of pH9；
100mL distilled water is placed in 250mL there-necked flask, 1.3g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 9；
In 30 DEG C, above-mentioned lanthanum solution is slowly dropped to the speed of 1.0mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, lanthanum ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 60min at 30 DEG C, reacts to obtain mixed liquor；
By mixed liquor stand 5h after, filter to obtain sediment, sediment is successively used 1% triethylamine aqueous solution, distilled water,
60% ethanol solution respectively washs 3-5 times, then dry under 60 DEG C of vacuum conditions, and brick-red lanthanum-scutelloside complex is made
Finished product.
With the content of lanthanum in inductance Coupled Plasma-Emission spectroscopic methodology (ICP-OES) measurement product, calculating yield is
99.69%, product purity 99.92%.
Embodiment 3
Weigh 8.04mmol La (Ac)3·5H21.5% triethylamine aqueous solution is added in 100mL small beaker in O, stirs molten
Solution, obtains the lanthanum solution of 30%, pH8；
100mL distilled water is placed in 250mL there-necked flask, 1.0g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 8.3；
In 25 DEG C, above-mentioned lanthanum solution is slowly dropped to the speed of 2.1mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, lanthanum ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 45min at 25 DEG C, reacts to obtain mixed liquor；
After mixed liquor is stood 6h, sediment is filtered to obtain, it will be successively with 0.7% triethylamine aqueous solution, distilled water, 60% second
Alcoholic solution respectively washs 3-5 times, then dry under 45 DEG C of vacuum conditions, and brick-red lanthanum-scutelloside complex finished product is made.
With the content of lanthanum in inductance Coupled Plasma-Emission spectroscopic methodology (ICP-OES) measurement product, calculating yield is
99.54%, product purity 99.78%.
Embodiment 4
Weigh 6.1mmol La2(SO4)3·8H23% triethylamine aqueous solution is added in 100mL small beaker in O, stirs molten
Solution, obtains the lanthanum solution of 18%, pH7.5；
100mL distilled water is placed in 250mL there-necked flask, 1.2g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 7.5；
In 55 DEG C, above-mentioned lanthanum solution is slowly dropped to the speed of 1.2mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, lanthanum ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 40min at 55 DEG C, reacts to obtain mixed liquor；
By mixed liquor stand 4h after, filter to obtain sediment, sediment is successively used 0.5% triethylamine aqueous solution, distilled water,
60% ethanol solution respectively washs 3-5 times, then dry under 50 DEG C of vacuum conditions, and brick-red lanthanum-scutelloside complex is made
Finished product.
With the content of lanthanum in inductance Coupled Plasma-Emission spectroscopic methodology (ICP-OES) measurement product, calculating yield is
99.78%, product purity 99.86%.
Embodiment 5
Weigh 9.38mmol La2(C2O4)3In 100mL small beaker, 2.5% triethylamine aqueous solution of addition, stirring and dissolving,
Obtain the lanthanum solution of 23%, pH8.3；
100mL distilled water is placed in 250mL there-necked flask, 0.9g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 7.5；
In 34 DEG C, above-mentioned lanthanum solution is slowly dropped to the speed of 2.0mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, lanthanum ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 50min at 34 DEG C, reacts to obtain mixed liquor；
After mixed liquor is stood 4.5h, sediment is filtered to obtain, sediment is successively used to the aqueous solution of 0.8% triethylamine, is steamed
Distilled water, 60% ethanol solution respectively wash 3-5 times, and then dry under 55 DEG C of vacuum conditions, the lanthanum-scutelloside for being made brick-red is matched
Close object finished product.
With the content of lanthanum in inductance Coupled Plasma-Emission spectroscopic methodology (ICP-OES) measurement product, calculating yield is
99.63%, product purity 99.72%.
Embodiment 6
Weigh 10.1mmol Ce (NO3)3·5H21% triethylamine aqueous solution is added in 100mL small beaker in O, stirs molten
Solution, obtains the cerium solution of 10%, pH7；
100mL distilled water is placed in 250mL there-necked flask, 0.8g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 8；
In 35 DEG C, above-mentioned cerium solution is slowly dropped to the speed of 1.5mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, cerium ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 30min at 35 DEG C, reacts to obtain mixed liquor；
By mixed liquor stand 3h after, filter to obtain sediment, sediment is successively used 0.3% triethylamine aqueous solution, distilled water,
60% ethanol solution respectively washs 3-5 times, then dry under 40 DEG C of vacuum conditions, and brick-red cerium-scutelloside complex is made
Finished product.
With the content of cerium in inductance Coupled Plasma-Emission spectroscopic methodology (ICP-OES) measurement product, calculating yield is
99.54%, product purity 99.87%.
Embodiment 7
Weigh 8.7mmol CeCl3·7H22% triethylamine aqueous solution is added in 100mL small beaker in O, and stirring and dissolving obtains
15%, the cerium solution of pH9；
100mL distilled water is placed in 250mL there-necked flask, 1.3g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 9；
In 30 DEG C, above-mentioned cerium solution is slowly dropped to the speed of 1.0mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, cerium ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 60min at 30 DEG C, reacts to obtain fluid,matching；
By fluid,matching stand 5h after, filter to obtain sediment, sediment is successively used 1% triethylamine aqueous solution, distilled water,
60% ethanol solution respectively washs 3-5 times, then dry under 60 DEG C of vacuum conditions, and brick-red cerium-scutelloside complex is made
Finished product.
With the content of cerium in inductance Coupled Plasma-Emission spectroscopic methodology (ICP-OES) measurement product, calculating yield is
99.69%, product purity 99.92%.
Embodiment 8
Weigh 8.04mmol Ce (Ac)3·4H21.5% triethylamine aqueous solution is added in 100mL small beaker in O, stirs molten
Solution, obtains the cerium solution of 30%, pH8；
100mL distilled water is placed in 250mL there-necked flask, 1.0g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 8.3；
In 55 DEG C, above-mentioned cerium solution is slowly dropped to the speed of 2.1mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, cerium ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 45min at 55 DEG C, reacts to obtain fluid,matching；
After fluid,matching is stood 6h, sediment is filtered to obtain, it will be successively with 0.7% triethylamine aqueous solution, distilled water, 60% second
Alcoholic solution respectively washs 3-5 times, then dry under 45 DEG C of vacuum conditions, and brick-red cerium-scutelloside complex finished product is made.
With the content of cerium in inductance Coupled Plasma-Emission spectroscopic methodology (ICP-OES) measurement product, calculating yield is
99.54%, product purity 99.78%.
Embodiment 9
Weigh 6.1mmol Ce2(SO4)3·8H23% triethylamine aqueous solution is added in 100mL small beaker in O, stirs molten
Solution, obtains the cerium solution of 18%, pH7.5；
100mL distilled water is placed in 250mL there-necked flask, 1.2g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 7.3；
In 25 DEG C, above-mentioned cerium solution is slowly dropped to the speed of 1.2mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, cerium ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 40min at 25 DEG C, reacts to obtain mixed liquor；
By mixed liquor stand 4h after, filter to obtain sediment, sediment is successively used 0.5% triethylamine aqueous solution, distilled water,
60% ethanol solution respectively washs 3-5 times, then dry under 50 DEG C of vacuum conditions, and brick-red cerium-scutelloside complex is made
Finished product.
With the content of cerium in inductance Coupled Plasma-Emission spectroscopic methodology (ICP-OES) measurement product, calculating yield is
99.78%, product purity 99.86%.
Embodiment 10
Weigh 12.06mmol Sr (NO3)2It in 100mL small beaker, is dissolved in water, obtains 10% strontium solution；
100mL distilled water is placed in 250mL there-necked flask, 0.8g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 7；
In 35 DEG C, above-mentioned strontium solution is slowly dropped to the speed of 1.5mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, strontium ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 30min at 35 DEG C, reacts to obtain mixed liquor；
By mixed liquor stand 3h after, filter to obtain sediment, sediment is successively used 0.3% triethylamine aqueous solution, distilled water,
60% ethanol solution respectively washs 3-5 times, then dry under 40 DEG C of vacuum conditions, and brick-red strontium-scutelloside complex is made
Finished product.
With the content of strontium in atomic absorption spectrography (AAS) (AAS) measurement product, calculating yield is 99.55%, and product purity is
99.88%.
Embodiment 11
Weigh 8.7mmol SrCl2·6H2O is added water dissolution, obtains 15% strontium solution in 100mL small beaker；
100mL distilled water is placed in 250mL there-necked flask, 1.3g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 9；
In 55 DEG C, above-mentioned strontium solution is slowly dropped to the speed of 1.0mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, strontium ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 45min at 55 DEG C, reacts to obtain fluid,matching；
By fluid,matching stand 5h after, filter to obtain sediment, sediment is successively used 1% triethylamine aqueous solution, distilled water,
60% ethanol solution respectively washs 3-5 times, then dry under 60 DEG C of vacuum conditions, and brick-red strontium-scutelloside complex is made
Finished product.
With the content of strontium in atomic absorption spectrography (AAS) (AAS) measurement product, calculating yield is 99.74%, and product purity is
99.89%.
Embodiment 12
Weigh 10.1mmol Sr (NO3)2It in 100mL small beaker, is dissolved in water, obtains 30% strontium solution；
100mL distilled water is placed in 250mL there-necked flask, 1.0g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 8；
In 25 DEG C, above-mentioned strontium solution is slowly dropped to the speed of 1.5mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, strontium ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 30min at 25 DEG C, reacts to obtain mixed liquor；
By mixed liquor stand 6h after, filter to obtain sediment, sediment is successively used 0.5% triethylamine aqueous solution, distilled water,
60% ethanol solution respectively washs 3-5 times, then dry under 45 DEG C of vacuum conditions, and brick-red strontium-scutelloside complex is made
Finished product.
With the content of strontium in atomic absorption spectrography (AAS) (AAS) measurement product, calculating yield is 99.39%, and product purity is
99.76%.
Embodiment 13
Weigh 8.04mmol SrCl2·6H2O is added water dissolution, obtains 15% strontium solution in 100mL small beaker；
100mL distilled water is placed in 250mL there-necked flask, 1.1g triethylamine is added, is mixed evenly, is then added
6.7mmol scutelloside obtains the scutelloside solution that pH is 8.3；
In 40 DEG C, above-mentioned strontium solution is slowly dropped to the speed of 1.0mL/min equipped with scutelloside by addition funnel
In the there-necked flask of solution, under stiring, strontium ion precipitates immediately after complex reaction occurs with scutelloside, after being added dropwise,
Continue to stir 60min at 40 DEG C, reacts to obtain fluid,matching；
By fluid,matching stand 5h after, filter to obtain sediment, sediment is successively used 0.8% triethylamine aqueous solution, distilled water,
60% ethanol solution respectively washs 3-5 times, then dry under 53 DEG C of vacuum conditions, and brick-red strontium-scutelloside complex is made
Finished product.
With the content of strontium in atomic absorption spectrography (AAS) (AAS) measurement product, calculating yield is 99.17%, and product purity is
99.82%.
Comparative example 1
Scutelloside is dissolved in 5% sodium carbonate liquor and obtains a brown-red solution (A liquid)；Lanthanum nitrate is dissolved in methanol
(B liquid)；By A liquid and B liquid in different mol ratio 1:1.5 ratio 50 DEG C at a temperature of be stirred to react 3 hours, obtain yellowish-brown production
Product are washed repeatedly with dehydrated alcohol, drying；Yield is 63.31%, purity 75.3%, hence it is evident that is lower than above-described embodiment 1~5.
Comparative example 2
Scutelloside is dissolved in 5% sodium carbonate liquor and obtains a brown-red solution (A liquid)；Cerous acetate is dissolved in methanol
(B liquid)；By A liquid and B liquid in different mol ratio 1:1.5 ratio 50 DEG C at a temperature of be stirred to react 3 hours, it is heavy to obtain brown
It forms sediment, is washed repeatedly with dehydrated alcohol, dried；Yield is 65.82%, purity 73.51%, hence it is evident that lower than above-described embodiment 6~
9。
Respectively to cerium-scutelloside made from lanthanum made from scutelloside, embodiment 1-scutelloside complex finished product, embodiment 6
Strontium made from complex finished product and embodiment 10-scutelloside complex finished product carries out infrared detection, as shown in Figures 2 to 5, figure
2 into Fig. 5, abscissa Wavenumber (cm-1) indicate wave number (cm-1)；Ordinate Transmittance (%) indicates light transmission
Rate (%).
4-C=O absorption peaks of scutelloside are in 1661.9cm in Fig. 2-1Place.After scutelloside and metal ion form complex,
Hydroxyl (- OH) on C=O and 5 of scutelloside can be coordinated with metallic element, shift electron cloud, and then lead to C
=O absorption peak red shift.As shown in Figures 3 to 5, C=O absorption peak is by 1661.9cm-1Red shift is to 1619.7cm-1(lanthanum, cerium),
1610.94cm-1(strontium), explanation
Lanthanum, cerium, strontium ion form stable complex with scutelloside respectively in embodiment 1,6,10.
Respectively to cerium-scutelloside made from lanthanum made from scutelloside, embodiment 1-scutelloside complex finished product, embodiment 6
Strontium made from complex finished product and embodiment 10-scutelloside complex finished product carries out fungistatic effect detection.
Choose 20 plants of escherichia coli for pigs and Escherichia coli type strain ATCC25922 by Serotype Identification.
The external minimal inhibitory concentration of Escherichia coli (MIC) is measured using 96 orifice plate coubling dilutions, made from scutelloside and each embodiment
Metal-scutelloside complex finished product is as shown in table 1 to the external minimal inhibitory concentration value of 21 plants of swine Escherichia colis.
The MIC value (μ g/mL) of 1 scutelloside of table and rare earth-scutelloside to Escherichia coli
As can be seen from the above table, lanthanum produced by the present invention-scutelloside complex, cerium -- scutelloside complex and strontium-cooperation
Object is significantly better than that scutelloside for the In Vitro Bacteriostasis effect of drug-resistant type and sensitive swine Escherichia coli.Illustrate preparation of the present invention
Metal-scutelloside complex can be used as it is a kind of efficiently, the drug of low toxicity is for treating early-weaned piglets diarrhea.
The above is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, for this field
For technical staff, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any
Modification, equivalent replacement, improvement etc. should all be included within the scope of the present invention.
Claims (9)
1. a kind of metal-scutelloside complex preparation method, which comprises the following steps:
Scutelloside is dissolved in triethylamine solution, the scutelloside solution of pH7~9 is obtained；
Under stiring, metal compound solution is added drop-wise in the scutelloside solution, continues to stir, react to obtain mixed liquor；
The mixed liquor is stood, sediment is filtered to obtain, it is washed, dry, obtain metal-scutelloside complex；
Wherein, the metallic compound for including in the metal compound solution is lanthanum compound, cerium compound or strontium compound.
2. metal as described in claim 1-scutelloside complex preparation method, which is characterized in that the lanthanum compound is
Any one in lanthanum nitrate, lanthanum acetate, lanthanum chloride, lanthanum sulfate and lanthanum oxalate；Or,
The ce metal compound is any one in cerous nitrate, cerous acetate, cerium chloride and cerous sulfate；Or,
The strontium compound is strontium nitrate or strontium chloride.
3. metal as described in claim 1-scutelloside complex preparation method, which is characterized in that the metallic compound
The mass fraction of metallic compound described in solution is 10~30%.
4. metal as described in claim 1-scutelloside complex preparation method, which is characterized in that the metallic compound
When for lanthanum compound or cerium compound, the preparation method of the metal compound solution the following steps are included:
Triethylamine is added into distilled water, is stirred, obtains the solution containing triethylamine；
Metallic compound is dissolved in the solution containing triethylamine, the metal compound solution of pH7~9 is obtained；
Wherein, the mass concentration of triethylamine is 1~3% in the metal compound solution.
5. metal as described in claim 1-scutelloside complex preparation method, which is characterized in that the metallic compound
When for strontium compound, strontium is made the following steps are included: strontium compound is dissolved in water in the preparation method of the metal compound solution
Compound solution.
6. metal as described in claim 1-scutelloside complex preparation method, which is characterized in that scutelloside is dissolved in three
In ethylamine solution, in the step of obtaining the scutelloside solution of pH7~9,
The mass concentration of triethylamine is 0.8~1.3% in the scutelloside solution.
7. metal as described in claim 1-scutelloside complex preparation method, which is characterized in that under stiring, by metal
Compound solution is added drop-wise in the scutelloside solution, continues to stir, react mixed liquor the step of in,
The speed of the dropwise addition is 1.0~2.1mL/min；And/or
The molar ratio of scutelloside and metal ion is 1:(1.2~1.8)；And/or
The time for continuing stirring is 30~60min；And/or
The temperature of the reaction is 25~55 DEG C.
8. metal as described in claim 1-scutelloside complex preparation method, which is characterized in that the mixed liquor is quiet
It sets, filters to obtain sediment, washed, dry, the step of obtaining metal-scutelloside complex includes:
After the mixed liquor is stood 3~6h, sediment is filtered to obtain；
After the sediment is successively used triethylamine aqueous solution, water, 60% ethanol washing, it is dried in vacuo, obtains at 40~60 DEG C
Metal-scutelloside complex；
Wherein, the mass concentration of the triethylamine aqueous solution is 0.3~1.0%.
9. a kind of metal-scutelloside that the preparation method of metal as described in claim 1-scutelloside complex is prepared is matched
Close application of the object in treatment grice diarrhoea.
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| CN117946143A (en) * | 2024-03-27 | 2024-04-30 | 中国人民解放军军事科学院军事医学研究院 | Metal coordination nano-enzyme and application thereof |
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