CN105061636B - A kind of preparation method of chitosan citrate rare earth compounding - Google Patents
A kind of preparation method of chitosan citrate rare earth compounding Download PDFInfo
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- CN105061636B CN105061636B CN201510529937.2A CN201510529937A CN105061636B CN 105061636 B CN105061636 B CN 105061636B CN 201510529937 A CN201510529937 A CN 201510529937A CN 105061636 B CN105061636 B CN 105061636B
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- chitosan
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- lanthanum
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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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Abstract
The present invention provides a kind of preparation method of chitosan citrate 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 (cerium) ion precursor liquid;Take chitosan powder with 5%~10% acetate dissolution, add absolute ethyl alcohol, and adjust pH to 4.0~8.5, be prepared into the chitosan-acetic acid solution containing 50% 90% ethanol;Into chitosan-acetic acid solution, citric acid is added, under magnetic stirring lanthanum (cerium) ion precursor liquid is slowly added to, carried out complex reaction, obtain fluid,matching;The fluid,matching obtained in S3 is evaporated under conditions of frozen water or rotary evaporation, suction filtration precipitation will precipitate drying, chitosan citrate rare earth compounding finished product is made.Reaction time of the invention is short, process is simpler, it is easy to obtain product, yield rate and chelation percent are higher, and product property is stable, easy to maintain, is had broad application prospects in medicine, health products and animal productiong.
Description
Technical field
The present invention relates to a kind of preparation method of chitosan-citric acid-rare earth (lanthanum, cerium) 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, the structure to rat liver has certain infringement but is deposited on liver
Lanthanum can gradually excrete.Yang Weidong etc. observes 3 pairs of viscera in rats tissues of Ce (NO3) 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.
The chelating technique of rare earth (lanthanum, cerium) on the whole, can be divided into liquid phase chelating and solid phase chelates 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 citric acid and lanthanum (cerium)
Lanthanum (cerium) chelate of a stable ternary is 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.
Specifically, the present invention provides a kind of preparation method of chitosan-citric acid-rare earth compounding, and it includes following step
Suddenly:
S1, prepare lanthanum ion precursor liquid:Take lanthanum compound La2O3, La2CO3, LaCl3 or La (Ac) 3 or cerium compound
Ce2O3, Ce2CO3, CeCl3 and Ce (Ac) 3 with 1~10% acetate dissolution, heating evaporation to contain a small amount of water, add it is a certain amount of
Ethanol solution 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
PH to 4.0~8.5 is adjusted, the chitosan-acetic acid solution of the ethanol containing 50%-90% is prepared into;
S3, obtain in chitosan-acetic acid solution into S2, add citric 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 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-citric acid-lanthanum
Precipitation or chitosan-citric acid-cerium precipitation, chitosan-citric acid-lanthanum precipitation or chitosan-citric acid-cerium are deposited in 50~
Dried under 80 DEG C of vacuum conditions, chitosan-citric acid-rare earth compounding finished product is made.
Preferably, the percentage of acetic acid is 5% in S1.
Preferably, 5mmol.L is utilized in S2-1NaOH solution pH value is adjusted.
Preferably, the percentage of ethanol contained by chitosan-acetic acid solution is 90% in S2.
Preferably, the citric acid added in S3 is 0.1~1.0g.
Preferably, mixing time is 24 hours in S4, and the sedimentation time is 6~12 hours, and vacuum drying temperature is 80 DEG C.
The present invention is that part and La (Ce) (III) have prepared chitosan-citric acid-lanthanum (cerium) using chitosan, citric acid
Complex.The complex is water insoluble, alkali and organic solvent, is soluble in acid.The more conventional chelating amino acids reaction of the chelatropic reaction
Time is short, process is simpler, it is easy to obtain product, yield rate and chelation percent are higher, and product property is stable, easy to maintain, in doctor
Had broad application prospects in medicine, health products and animal productiong.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
Embodiment
Below in conjunction with the accompanying drawings and embodiment to the present invention structure and working principle be further explained:
As shown in figure 1, the present invention provides a kind of preparation method of chitosan-citric acid-rare earth compounding, it includes following
Step:
S1, prepare lanthanum ion precursor liquid:Take lanthanum compound La2O3, La2CO3, LaCl3 or La (Ac) 3 or cerium compound
Ce2O3, Ce2CO3, CeCl3 and Ce (Ac) 3 with 1~10% acetate dissolution, heating evaporation to contain a small amount of water, add it is a certain amount of
Ethanol solution 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
PH to 4.0~8.5 is adjusted, the chitosan-acetic acid solution of the ethanol containing 50%-90% is prepared into;
S3, obtain in chitosan-acetic acid solution into S2, add citric 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 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-citric acid-lanthanum
Precipitation or chitosan-citric acid-cerium precipitation, chitosan-citric acid-lanthanum precipitation or chitosan-citric acid-cerium are deposited in 50~
Dried under 80 DEG C of vacuum conditions, chitosan-citric acid-rare earth compounding finished product is made.
Embodiment 1:
5% acetate dissolution of Chitosan powder is taken, 1mmol.L-1 chitosan solution is made, and adds 2 grams of citric acids and mixes
Stirring is closed, pH to 6.5 is adjusted with 5mmol.L-1 NaOH solution, is prepared into containing 50% ethanol solution;Under heating stirring,
5mmol.L-1 lanthanum acetate solution is added into above-mentioned solution, that is, obtains crystal;Room temperature continues to stir 10 hours, filtering, with 95%
Ethanol is washed for several times, is dried, that is, is obtained chitosan-citric 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 rate and chelation percent are calculated.Through
It is 78.94% to determine finished product rate, and chelation percent is 83.02%.
Embodiment 2:
10% acetate dissolution of Chitosan powder is taken, 0.5mmol.L-1 chitosan solution is made, the anhydrous second of 20mL is added
Alcohol, and 5 grams of citric acids mixings are added, pH to 5.0 is adjusted with 5mmol.L-1 NaOH solution, in magnetic agitation heating mantle
On flow back to obtain a settled solution, under heating stirring, the acetum of 5mmol.L-1 lanthanum chlorides is added into above-mentioned solution, 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-citric acid-lanthanum precipitated products.
With the content of Trace La in inductively coupled plasma-mass spectrography measurement product, yield rate and chelation percent, warp are calculated
It is 81.94% to determine finished product rate, and chelation percent is 90.12%.
Embodiment 3:
7% acetate dissolution of Chitosan powder is taken, 1mmol.L-1 chitosan solution is made, and adds 5 grams of citric acids and mixes
Stirring is closed, 20mL absolute ethyl alcohols are added, pH to 7.5 is adjusted with 5mmol.L-1 NaOH solution, is prepared into the solution containing ethanol;
Add the dissolving precursor aqueous solution of 5mmol.L-1 lanthanum carbonates into above-mentioned solution, heating stirring allows after it fully reacts, in 60 DEG C of water
Bathe heating stirring to stir 15 hours, gained reaction solution rotary evaporation is concentrated to give crystal, suction filtration, with 95% ethanol and -10 DEG C
Frozen water respectively washing 5 times, under 55 DEG C of vacuum conditions dry, that is, obtain chitosan-citric acid-lanthanum precipitated products.
With the content of Trace La in inductively coupled plasma-mass spectrography measurement product, yield rate and chelation percent are calculated.Through
It is 81.74% to determine finished product rate, and chelation percent is 85.32%.
Finally it should be noted that:Above-described embodiments are merely to illustrate the technical scheme, rather than to it
Limitation;Although the present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that:
It can still modify to the technical scheme described in previous embodiment, or which part or all technical characteristic are entered
Row equivalent substitution;And these modifications or substitutions, the essence of appropriate technical solution is departed from various embodiments of the present invention technical side
The scope of case.
Claims (6)
1. a kind of preparation method of chitosan-citric acid-rare earth compounding, it is characterised in that:It comprises the following steps:
S1, prepare lanthanum ion precursor liquid:Take lanthanum compound La2O3、La2CO3、LaCl3Or La (Ac)3Or cerium compound Ce2O3、
Ce2CO3、CeCl3And Ce (Ac)3With 1~10% acetate dissolution, heating evaporation adds a certain amount of ethanol molten to a small amount of water is contained
Liquid 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 prepared into the chitosan-acetic acid solution of the ethanol containing 50%-90%;
S3, obtain in chitosan-acetic acid solution into S2, citric acid is added, under magnetic stirring by before the lanthanum ion obtained in S1
Drive liquid or cerium ion precursor liquid is 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 in low temperature or
Continue to stir 10~24 hours at room temperature, suction filtration precipitation is washed for several times with 95% ethanol, obtain chitosan-citric acid-lanthanum precipitation
Or chitosan-citric acid-cerium precipitation, chitosan-citric acid-lanthanum precipitation or chitosan-citric acid-cerium are deposited in 50~80 DEG C
Dried under vacuum condition, chitosan-citric acid-rare earth compounding finished product is made.
2. the preparation method of chitosan-citric acid-rare earth compounding according to claim 1, it is characterised in that:Vinegar in S1
The percentage of acid is 5%.
3. the preparation method of chitosan-citric acid-rare earth compounding according to claim 1, it is characterised in that:It is sharp in S2
Use 5mmol.L-1NaOH solution pH value is adjusted.
4. the preparation method of chitosan-citric acid-rare earth compounding according to claim 3, it is characterised in that:Shell in S2
The percentage of ethanol contained by glycan acetum is 90%.
5. the preparation method of chitosan-citric acid-rare earth compounding according to claim 1, it is characterised in that:Add in S3
The citric acid entered is 0.1~1.0g.
6. the preparation method of chitosan-citric acid-rare earth compounding according to claim 1, it is characterised in that:Stirred in S4
It is 24 hours to mix the time, and the sedimentation time is 6~12 hours, and vacuum drying temperature is 80 DEG C.
Priority Applications (6)
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CN201710559525.2A CN107141371A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan L cysteine rare earth compoundings |
CN201510529937.2A CN105061636B (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan citrate rare earth compounding |
CN201710569213.XA CN107163166B (en) | 2015-08-27 | 2015-08-27 | Preparation method of chitosan-citric acid-rare earth complex |
CN201710559542.6A CN107177008A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan lactic acid rare earth compounding |
CN201710570606.2A CN107216409A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan L malic acid rare earth compoundings |
CN201710559534.1A CN107325201A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan salicylic acid rare earth compounding |
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CN201510529937.2A CN105061636B (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan citrate rare earth compounding |
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CN201710559542.6A Division CN107177008A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan lactic acid rare earth compounding |
CN201710559525.2A Division CN107141371A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan L cysteine rare earth compoundings |
CN201710570606.2A Division CN107216409A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan L malic acid rare earth compoundings |
CN201710559534.1A Division CN107325201A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan salicylic acid rare earth compounding |
CN201710569213.XA Division CN107163166B (en) | 2015-08-27 | 2015-08-27 | Preparation method of chitosan-citric acid-rare earth complex |
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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 |
CN201710570606.2A Pending CN107216409A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan L malic acid rare earth compoundings |
CN201710559542.6A Pending CN107177008A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan lactic acid rare earth compounding |
CN201510529937.2A Expired - Fee Related CN105061636B (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan citrate rare earth compounding |
CN201710569213.XA Active CN107163166B (en) | 2015-08-27 | 2015-08-27 | Preparation method of chitosan-citric acid-rare earth complex |
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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CN201710570606.2A Pending CN107216409A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan L malic acid rare earth compoundings |
CN201710559542.6A Pending CN107177008A (en) | 2015-08-27 | 2015-08-27 | A kind of preparation method of chitosan lactic acid rare earth compounding |
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CN108956551B (en) * | 2018-03-22 | 2021-05-28 | 山东大学 | Rare earth europium-chitosan film for detecting hydrogen peroxide based on fluorescence quenching and detection method thereof |
CN111205312B (en) * | 2020-03-31 | 2021-03-16 | 榫卯科技服务(温州)有限公司 | Antibacterial rare earth complex material and preparation method thereof |
CN111728981A (en) * | 2020-06-09 | 2020-10-02 | 佳木斯大学 | Quercetin rare earth complex and preparation method thereof |
CN113208004B (en) * | 2021-05-31 | 2022-10-18 | 湖南奇力莱生物科技有限公司 | Rare earth chelate and preparation method and application thereof |
CN114874358B (en) * | 2022-04-11 | 2023-05-02 | 上海师范大学 | Synthesis method and application of polynuclear cerium nano material |
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- 2015-08-27 CN CN201710570606.2A patent/CN107216409A/en active Pending
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- 2015-08-27 CN CN201510529937.2A patent/CN105061636B/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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CN107163166A (en) | 2017-09-15 |
CN107141371A (en) | 2017-09-08 |
CN107163166B (en) | 2020-08-14 |
CN107177008A (en) | 2017-09-19 |
CN107325201A (en) | 2017-11-07 |
CN107216409A (en) | 2017-09-29 |
CN105061636A (en) | 2015-11-18 |
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