CN107325201A - A kind of preparation method of chitosan salicylic acid rare earth compounding - Google Patents

A kind of preparation method of chitosan salicylic acid rare earth compounding Download PDF

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Publication number
CN107325201A
CN107325201A CN201710559534.1A CN201710559534A CN107325201A CN 107325201 A CN107325201 A CN 107325201A CN 201710559534 A CN201710559534 A CN 201710559534A CN 107325201 A CN107325201 A CN 107325201A
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chitosan
salicylic acid
rare earth
lanthanum
cerium
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程先忠
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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
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Abstract

The present invention provides a kind of preparation method of chitosan salicylic acid rare earth compounding, and it comprises the following steps：Take lanthanum compound La2O3、La2CO3、LaCl3、La(Ac)3Or cerium compound Ce2O3、Ce2CO3、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, salicylic 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 salicylic acid rare earth compounding finished product is 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 productiong.

Description

A kind of preparation method of chitosan-salicylic acid-rare earth compounding
Technical field
The present invention relates to the synthesis of rare earth compounding, particularly a kind of chitosan-salicylic acid-rare earth（Lanthanum, cerium）Match somebody with somebody The preparation method of compound.
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 design to utilize chitosan and salicylic acid and lanthanum or cerium The lanthanum or cerium chelate of a stable ternary are formed, the inventive method is simple, and chelate settling velocity is fast, and yield is high, production Cost is low, can large-scale industrial production, the product of preparation is more conducive to bio-absorbable.Salicylic acid is a kind of fat-soluble organic Acid, mainly as the raw material of medical industry, for preparing aspirin, sodium salicylate, salicylamide, ethoxybenzamide, salicylic acid benzene The medicines such as ester, Niclosamide, are a kind of complexing agent in addition, can be with rare earth element formation complex.
Specifically, the present invention provides a kind of preparation method of chitosan-salicylic acid-rare earth compounding, and it includes following step Suddenly：.
S1, prepare lanthanum or cerium ion precursor liquid：Take lanthanum compound such as La2O3、La2CO3、LaCl3、La(Ac)3Or cerium Compound Ce2O3、Ce2CO3、CeCl3、Ce(Ac)3With 1~10% acetate dissolution, heating evaporation is added certain to a small amount of water is contained The ethanol solution of amount 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 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 salicylic acid, will be obtained under magnetic stirring in S1 Lanthanum 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 suction filtration precipitation is washed for several times with 95% ethanol, obtains chitosan-bigcatkin willow Acid-lanthanum or chitosan-salicylic acid-cerium precipitation, chitosan-salicylic acid-lanthanum or chitosan-salicylic acid-cerium are deposited in 50~ Dried under 80 DEG C of vacuum conditions, chitosan-salicylic 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 salicylic 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, salicylic acid as part and La (III）Or Ce (III) ion precursor liquid has been prepared shell and gathered Sugar-salicylic acid-lanthanum (cerium) complex.The complex is water insoluble, alkali and organic solvent, is soluble in acid.The chelatropic reaction compared with The conventional chelating amino acids reaction time is short, process is simpler, it is easy to obtain product, yield rate and chelation percent are higher, and product Matter is stable, easy to maintain, is had broad application prospects in medicine, health products and animal productiong.
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-salicylic acid-rare earth compounding, it include with Lower step：
S1, prepare lanthanum（Cerium）Ion precursor liquid：Take lanthanum compound La2O3、La2CO3、LaCl3、La(Ac)3Or cerium chemical combination Thing Ce2O3、Ce2CO3、CeCl3、Ce(Ac) 3With 1~10% acetate dissolution, heating evaporation is added certain to a small amount of water is contained The ethanol solution of amount 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, salicylic acid is added, under magnetic stirring by the lanthanum obtained in S1 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 suction filtration is precipitated 6~12 hours, is washed for several times, obtained with 95% ethanol Chitosan-salicylic acid-lanthanum precipitation or chitosan-salicylic acid-cerium precipitation, chitosan-salicylic acid-lanthanum precipitation or shell are gathered Sugar-salicylic acid-cerium is deposited under 50~80 DEG C of vacuum conditions and dried, and chitosan-salicylic 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 salicylic acids and mix Stirring is closed, 5 mmolL are used-1NaOH solution regulation pH to 6.5, be prepared into containing 50% ethanol solution；Under heating stirring, 5 mmolL are added into above-mentioned solution-1Lanthanum acetate solution, that is, obtain crystal；Room temperature continues to stir 10 hours, filtering, with 95% Ethanol is washed for several times, is dried, that is, is obtained chitosan-salicylic acid-lanthanum precipitated products under 75 DEG C of vacuum conditions.
With the content of Trace La in inductively coupled plasma-mass spectrography measurement product, yield and chelation percent are calculated.Through surveying It is 83.65% to determine product yield, and chelation percent is 86.53%.
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 salicylic acids mixings are added, use 5 mmolL-1NaOH solution regulation pH to 5.0, magnetic agitation heating The settled solution that flows back to obtain is put, under heating stirring, 5 mmolL are added into above-mentioned solution-1The acetum of lanthanum chloride, plus Thermal agitation 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 washing 5 times, under 65 DEG C of vacuum conditions dry, that is, obtain chitosan-salicylic 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 83.48% to determine product yield, and chelation percent is 88.76%.
Embodiment 3：
7% acetate dissolution of Chitosan powder is taken, 1 mmolL is made-1Chitosan solution, and add 5 grams of salicylic acids and mix Stirring is closed, 20 mL absolute ethyl alcohols is added, uses 5 mmolL-1NaOH solution regulation pH to 7.5, be prepared into containing the molten of ethanol Liquid；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 heating water bath stirring stirring 15 hours, crystal is concentrated to give by gained reaction solution rotary evaporation, suction filtration, with 95% ethanol and- Respectively washing 5 times of 10 DEG C of frozen water, dry under 55 DEG C of vacuum conditions, that is, obtain chitosan-salicylic 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 84.91% to determine product yield, and chelation percent is 88.12%.
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-salicylic acid-cerium precipitated products；Above-described embodiments are merely to illustrate the technical scheme, and It is non-that it is limited；Although the present invention is described in detail with reference to the foregoing embodiments, one of ordinary skill in the art should Work as understanding：It can still modify to the technical scheme described in previous embodiment, or to which part or whole skills Art feature carries out equivalent substitution；And these modifications or substitutions, the essence of appropriate technical solution is departed from each implementation of the present invention The scope of example technical scheme.

Claims (6)

1. a kind of preparation method of chitosan-salicylic 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、La2CO3、LaCl3、La(Ac)3Or cerium Compound Ce2O3、Ce2CO3、CeCl3、Ce(Ac)3With 1~10% acetate dissolution, heating evaporation is added certain to a small amount of water is contained The ethanol solution of amount 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 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, salicylic acid is added, under magnetic stirring by the lanthanum ion obtained in S1 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 in low temperature Or at room temperature continue stir 10~24 hours, suction filtration precipitation, washed for several times with 95% ethanol, obtain chitosan-salicylic acid- Lanthanum is precipitated or chitosan-salicylic acid-cerium precipitation, and chitosan-salicylic acid-lanthanum precipitation or chitosan-salicylic acid-cerium are precipitated Dried under 50~80 DEG C of vacuum conditions, chitosan-salicylic acid-rare earth compounding finished product is made.
2. the preparation method of chitosan-salicylic acid-rare earth compounding according to claim 1, it is characterised in that：In S1 The percentage of acetic acid is 5%.
3. the preparation method of chitosan-salicylic acid-rare earth compounding according to claim 1, it is characterised in that：In S2 Utilize 5mmolL-1NaOH solution pH values are adjusted.
4. the preparation method of chitosan-salicylic acid-rare earth compounding according to claim 3, it is characterised in that：In S2 The percentage of ethanol contained by chitosan-acetic acid solution is 90%.
5. the preparation method of chitosan-salicylic acid-rare earth compounding according to claim 1, it is characterised in that：In S3 The salicylic acid of addition is 0.1~1.0 g.
6. the preparation method of chitosan-salicylic acid-rare earth compounding according to claim 1, it is characterised in that：In S4 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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CN201710559542.6A Pending CN107177008A (en) 2015-08-27 2015-08-27 A kind of preparation method of chitosan lactic acid rare earth compounding
CN201710569213.XA Active CN107163166B (en) 2015-08-27 2015-08-27 Preparation method of chitosan-citric acid-rare earth complex
CN201710570606.2A Pending CN107216409A (en) 2015-08-27 2015-08-27 A kind of preparation method of chitosan L malic acid rare earth compoundings
CN201710559534.1A Pending CN107325201A (en) 2015-08-27 2015-08-27 A kind of preparation method of chitosan salicylic acid rare earth compounding
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