CN107216409A - A kind of preparation method of chitosan L malic acid rare earth compoundings - Google Patents

A kind of preparation method of chitosan L malic acid rare earth compoundings Download PDF

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CN107216409A
CN107216409A CN201710570606.2A CN201710570606A CN107216409A CN 107216409 A CN107216409 A CN 107216409A CN 201710570606 A CN201710570606 A CN 201710570606A CN 107216409 A CN107216409 A CN 107216409A
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chitosan
malic acid
rare earth
lanthanum
cerium
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程先忠
任莹
赵胜军
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Wuhan Polytechnic University
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Wuhan Polytechnic University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The present invention provides a kind of preparation method of chitosan L malic acid rare earth compoundings, and it comprises the following steps：Take lanthanum compound La2O3、La2(CO3)3、LaCl3、La(Ac)3Or cerium compound Ce2O3、Ce2(CO3)3、CeCl3、Ce(Ac)3With 1~10% acetate dissolution, heating evaporation simultaneously adds ethanol solution and is prepared into lanthanum or cerium ion precursor liquid；Take chitosan with 5%~10% acetate dissolution, adjust pH to 4.0~8.5, add absolute ethyl alcohol and be prepared into the chitosan-acetic acid solution containing 50% 90% ethanol；Into chitosan-acetic acid solution, L malic acid is added, lanthanum or cerium ion precursor liquid are added under magnetic stirring, complex reaction is carried out, obtains fluid,matching；The fluid,matching obtained in S3 is evaporated under conditions of frozen water or rotary evaporation, suction filtration, drying will be precipitated, chitosan L malic acid rare earth compounding finished products are made.Reaction time of the invention is short, process simple, is easy to get to product, and yield rate and chelation percent are higher, and property is stable, easy to maintain, is had broad application prospects in medicine, health products and animal feeding.

Description

A kind of preparation method of chitosan-L MALIC ACID-rare earth compounding
Technical field
The present invention relates to a kind of chitosan-L MALIC ACID-rare earth（Lanthanum, cerium）The preparation method of complex.
Background technology
Rare earth element is due to special outer-shell electron configuration, with unique chemical and physical features, while also having fine Anti-inflammatory, sterilization, anticancer, anticoagulation, analgesic activity.The sixties to the eighties, people just regard inorganic rare earth as a kind of feed Additive application in animal productiong, research find rare earth be a kind of physiologic activators, by adjust hormonal readiness, enzymatic activity, The various ways such as albumen and lipid metabolism influence intermediate supersession process, can activate the somatomedin in animal body, improve internal Metabolism, improves food conversion ratio, and accelerates growth of animal and production.Wherein, lanthanum, Ce elements are often sharp in the form of various salt With they are mostly colourless granules shape crystal, and fusing point is low, and hygroscopicity is strong, the easy deliquescence in humid air.Recent study is sent out Existing rare earth shows antitumor activity with oxyacid, chitosan and amino acids formed complex, and property is stable, not only exists Application effect in animal productiong is better than inorganic lanthanum, cerium, and solves the unstable shortcoming of inorganic lanthanum, cerium property.
Rare earth element enter animal body after, can be absorbed, be enriched with and redistributed in each tissue, can cause including The system wide influence such as nervous centralis, digestion, endocrine, motion and reproduction.Early in nineteen thirty-five Steiale just delivered on The toxicity of rare earth and the monograph of pharmacological action.Rare earth belongs to low toxicity or Poisoning material, than many organic compounds or transition metal The toxicity of compound is much lower.Research shows that the coup injury of the lanthanum nitrate of higher dosage can make mouse heart lipid peroxidation Strengthen, the ability for removing free radical declines；And during relatively low-dose, the generation and removing on mouse heart free radical are without influence.Most It is near to there is research to confirm：20.0mg/kg lanthanum nitrate long terms, have certain infringement, but be deposited on liver to the structure of rat liver Lanthanum can gradually excrete.Yang Weidong etc. observes Ce (NO3)3To viscera in rats tissue and brain nitric oxide and synzyme Influence.As a result show, after the rare earth that high concentration is injected intraperitoneally, nitric oxide, one in rat liver, heart, kidney, skeletal muscle The level of nitric oxide synthase substantially increases.And inject after the rare earth of low concentration, liver, kidney intracellular nitric oxide amount it is then notable Reduction.Prompting rare earth can influence the level of body nitric oxide, nitricoxide synthase extensively.Blood rare earth load level and resident The research of health status relation shows：Rare earth exposure group is compared with blank control group.Lung capacity, triglycerides, cholesterol, GPT, The testing result difference no statistical significances such as GOT, HBsAg, citrus orchards, trick portion change of skin, electrocardiogram, urea nitrogen, are pointed out at this In the case of planting low dosage exposure for a long time, rare earth is also not enough to respiratory system, lipid-metabolism, liver, the heart, renal function and skin production Raw harmful effect.
Rare earth（Lanthanum, cerium）Chelating technique on the whole, can be divided into liquid phase chelating and solid phase chelate two kinds.Liquid phase chelates method It is relatively simple, it is easy to operation, can be mass produced, be a kind of common chelating process.Solid-phase synthesis is typically right The requirement of temperature conditionss is higher, and time-consuming, so, it is more few in production to use.
The content of the invention
The problem of existing for prior art, it is an object of the invention to designing using chitosan and L MALIC ACID and lanthanum or The lanthanum or cerium chelate of cerium one stable ternary of formation, the inventive method are simple, and chelate settling velocity is fast, and yield is high, raw Produce cost it is low, can large-scale industrial production, the product of preparation is more conducive to bio-absorbable.Malic acid is 2- hydroxysuccinic acids, again Claim hydroxysuccinic acid, maleic acid, be a dicarboxylic acids, chemical formula is HO2CCH2CHOHCO2H；It is asymmetric containing one in molecule Carbon atom, therefore have two kinds of optical isomers and a kind of racemic modification, exist in the Nature in three kinds of forms, i.e. D- apples Acid, L MALIC ACID and its mixture D L MALIC ACID.Malic acid is widely present in the fruits such as apple, grape, hawthorn, and it is first Separated from cider, be the source of cider tart flavour, and hence obtained one's name.Malic acid be inside of human body circulation it is important in Between product, be easily absorbed by the body, therefore be commonly used for the food additives and functional food of excellent performance, be widely used in food The fields such as product, cosmetics, medical treatment and health products.Wherein, L MALIC ACID has important physiological function, and it can be directly entered tricarboxylic Acid circulation, participates in body metabolism；L MALIC ACID can be also used for treatment hepatopathy, anaemia, hypoimmunity, uremia, hypertension, A variety of diseases such as hepatic failure, and toxic action of the cancer therapy drug to normal cell can be mitigated；Other L MALIC ACID is also a kind of excellent Good complexing agent, can be with rare earth element formation complex compound.In this patent using L MALIC ACID and chitosan as part, prepare A kind of ternary complex of chitosan-L MALIC ACID-rare earth, for medicine, health products and animal feeding industry.
Specifically, the present invention provides a kind of preparation method of chitosan-L MALIC ACID-rare earth compounding, and it includes following Step：.
S1, prepare lanthanum or cerium ion precursor liquid：Take lanthanum compound such as La2O3、La2(CO3)3、LaCl3、La(Ac)3Or Cerium compound Ce2O3、Ce2(CO3)3、CeCl3、Ce(Ac)3With 1~10% acetate dissolution, heating evaporation extremely contains a small amount of water, Add a certain amount of ethanol solution and be prepared into lanthanum ion precursor liquid or cerium ion precursor liquid.
S2, prepare chitosan-acetic acid solution：Take Chitosan powder with 5%~10% acetate dissolution, add anhydrous second Alcohol, and pH to 4.0~8.5 is adjusted, it is prepared into the chitosan-acetic acid solution containing 50%~90% ethanol.
S3, obtain in chitosan-acetic acid solution into S2, add L MALIC ACID, will be obtained under magnetic stirring in S1 Lanthanum or cerium ion precursor liquid be slowly added to, carry out complex reaction, obtain fluid,matching.
S4, the fluid,matching obtained in S3 is evaporated under conditions of frozen water or rotary evaporation, obtains crystal, and Low temperature continues to stir 10~24 hours at room temperature, and filtering washs precipitation with 95% ethanol for several times, obtains chitosan-L- apples Tartaric acid-lanthanum or chitosan-L MALIC ACID-cerium precipitation, chitosan-L MALIC ACID-lanthanum or chitosan-L MALIC ACID-cerium are precipitated Dried under 50~80 DEG C of vacuum conditions, chitosan-L MALIC ACID-rare earth compounding finished product is made.
Preferably, the percentage of acetic acid is 5% in S1.
Preferably, 5mmolL is utilized in S2-1NaOH solution pH values are adjusted.
Preferably, the percentage of ethanol contained by chitosan-acetic acid solution is 90% in S2.
Preferably, the L MALIC ACID added in S3 is 0.1~1.0 g.
Preferably, mixing time is 24 hours in S4, and the sedimentation time is 6~12 hours, and vacuum drying temperature is 80 ℃。
The present invention is using chitosan, L MALIC ACID as part and La (III）Or Ce (III) ion precursor liquid has prepared shell Glycan-L MALIC ACID-lanthanum (cerium) complex.The complex is water insoluble, alkali and organic solvent, is soluble in acid.The chelating is anti- Should the more conventional chelating amino acids reaction time be short, process is simpler, it is easy to obtain product, yield rate and chelation percent are higher, and production Moral character matter is stable, easy to maintain, is had broad application prospects in medicine, health products and animal feeding.
Brief description of the drawings
Fig. 1 is preparation technology flow chart of the present invention.
Embodiment
Below in conjunction with the accompanying drawings and embodiment to the present invention structure and working principle be further explained：.
As shown in Fig. 1, the present invention provides a kind of preparation method of chitosan-L MALIC ACID-rare earth compounding, and it includes Following steps：.
S1, prepare lanthanum（Cerium）Ion precursor liquid：Take lanthanum compound La2O3、La2(CO3)3、LaCl3、La(Ac)3Or cerium Compound Ce2O3、Ce2(CO3)3、CeCl3、Ce(Ac) 3With 1~10% acetate dissolution, heating evaporation is added to a small amount of water is contained A certain amount of ethanol solution is prepared into lanthanum ion precursor liquid or cerium ion precursor liquid.
S2, prepare chitosan-acetic acid solution：Take chitosan powder with 5%~10% acetate dissolution, add absolute ethyl alcohol, And pH to 4.0~8.5 is adjusted, it is prepared into the chitosan-acetic acid solution of the ethanol containing 50%-90%.
S3, obtain in chitosan-acetic acid solution into S2, add L MALIC ACID, will be obtained under magnetic stirring in S1 Lanthanum ion precursor liquid or cerium ion precursor liquid are slowly added to, and are carried out complex reaction, are obtained fluid,matching.
S4, the fluid,matching obtained in S3 is evaporated under conditions of frozen water or rotary evaporation, obtains crystal, and Low temperature continues to stir 10~24 hours at room temperature, and filtering washs crystal for several times with 95% ethanol, obtains chitosan-L- apples Tartaric acid-lanthanum precipitation or chitosan-L MALIC ACID-cerium precipitation, by chitosan-L MALIC ACID-lanthanum precipitation or chitosan-L- apples Tartaric acid-cerium is deposited under 50~80 DEG C of vacuum conditions and dried, and chitosan-L MALIC ACID-rare earth compounding finished product is made.
Embodiment 1：
5% acetate dissolution of Chitosan powder is taken, 1 mmolL is made-1Chitosan solution, and add 2 grams of L- apples Acid is mixed, and uses 5 mmolL-1NaOH solution regulation pH to 6.5, be prepared into containing 50% ethanol solution；In heating stirring Under, add 5 mmolL into above-mentioned solution-1Lanthanum acetate solution, that is, obtain crystal；Room temperature continues to stir 10 hours, filters, and uses 95% ethanol washing crystal for several times, is dried under 75 DEG C of vacuum conditions, that is, obtained chitosan-L MALIC ACID-lanthanum precipitated products.
With the content of Trace La in inductively coupled plasma-mass spectrography measurement product, yield and chelation percent are calculated.Through surveying It is 83.94% to determine product yield, and chelation percent is 88.21%.
Embodiment 2：
10% acetate dissolution of Chitosan powder is taken, 0.5 mmolL is made-1Chitosan solution, add 20 mL it is anhydrous Ethanol, and 5 grams of L MALIC ACIDs mixings are added, use 5 mmolL-1NaOH solution regulation pH to 5.0, in magnetic agitation plus Flowed back to obtain settled solution on hot jacket, under heating stirring, and 5 mmolL are added into above-mentioned solution-1The acetum of lanthanum chloride, Heating stirring is allowed after it fully reacts, and crystal is separated out under cold, continues to stir 20 hours, filtering, with 95% ethanol and -5 DEG C frozen water respectively wash crystal 5 times, dry, that is, obtained the precipitation production of chitosan-L MALIC ACID-lanthanum under 65 DEG C of vacuum conditions Product.
With the content of Trace La in inductively coupled plasma-mass spectrography measurement product, yield and chelation percent are calculated, through surveying It is 82.76% to determine product yield, and chelation percent is 87.49%.
Embodiment 3：
7% acetate dissolution of Chitosan powder is taken, 1 mmolL is made-1Chitosan solution, and add 5 grams of L- apples Acid is mixed, and is added 20 mL absolute ethyl alcohols, is used 5 mmolL-1NaOH solution regulation pH to 7.5, be prepared into containing ethanol Solution；5 mmolL are added into above-mentioned solution-1The dissolving precursor aqueous solution of lanthanum carbonate, heating stirring allows after it fully reacts, 60 DEG C of heating water baths stirring stirring 15 hours, crystal is concentrated to give by gained reaction solution rotary evaporation, suction filtration, with 95% ethanol and- 10 DEG C of frozen water respectively washs crystal 5 times, is dried under 55 DEG C of vacuum conditions, that is, obtains chitosan-L MALIC ACID-lanthanum precipitation production Product.
With the content of Trace La in inductively coupled plasma-mass spectrography measurement product, yield and chelation percent are calculated.Through surveying It is 85.07% to determine product yield, and chelation percent is 89.58%.
Finally it should be noted that：Lanthanum acetate, lanthanum carbonate, lanthanum chloride in above example can be replaced with cerium compound, system It is standby into chitosan-L MALIC ACID-cerium precipitated products；Above-described embodiments are merely to illustrate the technical scheme, Rather than its limitations；Although the present invention is described in detail with reference to the foregoing embodiments, one of ordinary skill in the art It should be understood that：It can still modify to the technical scheme described in previous embodiment, or to which part or whole Technical characteristic carries out equivalent substitution；And these modifications or substitutions, the essence of appropriate technical solution is departed from each reality of the invention Apply the scope of a technical scheme.

Claims (6)

1. a kind of preparation method of chitosan-L MALIC ACID-rare earth compounding, it is characterised in that：It comprises the following steps：
S1, prepare lanthanum ion or cerium ion precursor liquid：Take lanthanum compound La2O3、La2(CO3)3、LaCl3、La(Ac)3Or cerium Compound Ce2O3、Ce2(CO3)3、CeCl3、Ce(Ac)3With 1~10% acetate dissolution, heating evaporation extremely contains a small amount of water, plus Enter a certain amount of ethanol solution and be prepared into lanthanum ion precursor liquid or cerium ion precursor liquid；
S2, prepare chitosan-acetic acid solution：Take chitosan powder with 5%~10% acetate dissolution, add absolute ethyl alcohol, and adjust PH to 4.0~8.5 is saved, the chitosan-acetic acid solution containing 50%~90% ethanol is prepared into；
S3, obtain in chitosan-acetic acid solution into S2, add L MALIC ACID, under magnetic stirring by the lanthanum obtained in S1 from Sub- precursor liquid or cerium ion precursor liquid is slowly added to, and is carried out complex reaction, is obtained fluid,matching；
S4, the fluid,matching obtained in S3 is evaporated under conditions of frozen water or rotary evaporation, obtains crystal, and in low temperature Or continue to stir 10~24 hours at room temperature, suction filtration washs crystal for several times with 95% ethanol, obtains chitosan-L- apples Acid-lanthanum precipitation or chitosan-L MALIC ACID-cerium precipitation, by chitosan-L MALIC ACID-lanthanum precipitation or chitosan-L- apples Acid-cerium is deposited under 50~80 DEG C of vacuum conditions and dried, and chitosan-L-malic acid-rare earth compounding finished products are made.
2. the preparation method of chitosan-L MALIC ACID-rare earth compounding according to claim 1, it is characterised in that：S1 The percentage of middle acetic acid is 5%.
3. the preparation method of chitosan-L MALIC ACID-rare earth compounding according to claim 1, it is characterised in that：S2 Middle utilization 5mmolL-1NaOH solution pH values are adjusted.
4. the preparation method of chitosan-L MALIC ACID-rare earth compounding according to claim 3, it is characterised in that：S2 The percentage of ethanol contained by middle chitosan-acetic acid solution is 90%.
5. the preparation method of chitosan-L MALIC ACID-rare earth compounding according to claim 1, it is characterised in that：S3 The L MALIC ACID of middle addition is 0.1~1.0 g.
6. the preparation method of chitosan-L MALIC ACID-rare earth compounding according to claim 1, it is characterised in that：S4 Middle mixing time is 24 hours, and the sedimentation time is 6~12 hours, and vacuum drying temperature is 80 DEG C.
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CN201710559525.2A Pending CN107141371A (en) 2015-08-27 2015-08-27 A kind of preparation method of chitosan L cysteine rare earth compoundings
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CN201510529937.2A Expired - Fee Related CN105061636B (en) 2015-08-27 2015-08-27 A kind of preparation method of chitosan citrate rare earth compounding
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