CN101367885B - Malic acid chitosan oligosaccharide compound salt, preparation and uses thereof - Google Patents
Malic acid chitosan oligosaccharide compound salt, preparation and uses thereof Download PDFInfo
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- Polysaccharides And Polysaccharide Derivatives (AREA)
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Abstract
The invention relates to a malic acid chitosan oligosaccharide compound salt, a preparation method and an application thereof. The malic acid chitosan oligosaccharide compound salt is prepared through the following steps of using DL-malic acid or L-malic acid and the chitosan with deacetylating degree higher than 85% as source materials, suspending the chitosan in pure water, wherein, the addition amount of water is 20 to 200 times of the weight of the chitosan; adding DL-malic acid or L-malic acid to regulate pH between 4.5 and 6.5, adding immobilized chitosanase, mixing and enzyme hydrolyzing, wherein, the temperature is 40 to 60 DEG C, the time is 5 to 48 hours; separating and recycling the immobilized chitosanase after enzyme hydrolyzing, adding certain amount of malic acid to further hydrolyze to be salt, wherein, the temperature is 60 to 100 DEG C; cooling the hydrolyzed liquid at 25 to 30 DEG C, mixing and carrying out alcohol precipitation, wherein, the addition amount is 30 to 200% of the solution amount; centrifugalizing, washing and vacuum-drying the alcohol-precipitated liquid at 50 to 60 DEG C to obtain the high-purity malic acid chitosan oligosaccharide compound salt. The malic acid chitosan oligosaccharide compound salt obtained by using the method has the advantages of good water solubility and excellent bioactivity, and can be applied in fields of foods, functional additives and the like.
Description
Technical field
The present invention relates to a kind of composite salt and its production and application, particularly relate to a kind of malic acid chitosan oligosaccharide compound salt and preparation method thereof with its in the application aspect food and the functional additive.
Background technology
Oxysuccinic acid has another name called the 2-hydroxy-butanedioic acid, owing in the molecule unsymmetrical carbon is arranged, two kinds of steric isomers is arranged, and exists with three kinds of forms: D-oxysuccinic acid, L MALIC ACID and DL body DL-oxysuccinic acid.L MALIC ACID extensively is present in the juice of fruits such as jejune shizandra berry, hawthorn, apple, also can be made through biocatalysis by fumaric acid.It is the important intermediate of human body tricarboxylic acid cycle, plays crucial effect in cellular energy is synthetic, is the necessary composition of synthetic kinetomeres ATP.Verified, the synthetic desired substance shortage of oxysuccinic acid and other ATP is relevant with myalgia and confirmed fatigue.The oxysuccinic acid safety non-toxic easily is absorbed by the body, and mouthfeel is near straight juice and have natural flavor.Compare with citric acid, the heat that oxysuccinic acid produces is lower, and taste is better, therefore as the foodstuff additive and the functional foodstuff of excellent performance, can be widely used in fields such as food, makeup, medical treatment and healthcare products.Oxysuccinic acid can be used in pharmaceutical preparation, tablet, the syrup, can also allocate in the amino acid solution, can obviously improve amino acid whose specific absorption.Oxysuccinic acid also can be used for treating multiple diseases such as hepatopathy, anaemia, hypoimmunity, uremia, hypertension and liver failure, and can alleviate cancer therapy drug to Normocellular toxic action; Oxysuccinic acid can also be used for preparation and synthetic wormer, anticalculus agent etc.
Oligochitosan is meant 2 to 10 glucosamines with β-1, and the chitosan oligomer that the 4-glycosidic link is formed by connecting is made by the chitosan depolymerization.Oligochitosan is to be raw material with common shrimp and crab shells or yeast thalline, after decalcification, deproteinated, decolouring and deacetylation reaction, and utilization enzyme biological or chemical depolymerization and the lower molecular weight poly-glucosamine that obtains.Oligochitosan has different physiological roles: activate immunity strengthens the phagocytic cell ability; Improve insulin receptor susceptibility, obviously lower fasting plasma glucose; Secretion, metabolism and the excretory function of protection normal liver cell, the biotransformation function of enhance hepatocyte directly suppresses the growth of liver cancer cell and ascites tumour cell; Improve useful lipoprotein quantity, blood fat reducing; Promote the propagation of bifidus bacillus, suppress growth of harmful intestinal tract bacteria etc.Therefore oligochitosan is called as " the 6th key element of life ", it is present unique in the world positively charged ion animal fibre material that has the free amine group basic group, has very strong complexing adsorptive power, it can not only excrete hazardous and noxious substances in the body and heavy metal absorption, can also excrete fat unnecessary in the body and cholesterol absorption, be " SafeClean Utilities " of human body.Oligochitosan can also improve the human body sour environment, and the activation cells in vivo is recover for illness without medical help numerous disease, improves quality of life.Because oligochitosan can adsorb lipoidis electronegative in the human body, fat, bile acide etc., and can directly enter blood, act on immunocyte, thereby has tangible mediator's body immunity function, improve the effect of human body disease resistance ability, especially diabetes, the hypertension of the elderly's pilosity and the other diseases that causes because of the immunizing power reduction are had assisting therapy effect preferably, the middle-aged and old health is also had effect preferably.
Give full play to the physiological function of oxysuccinic acid, need every day and take in 1 to 5 gram oxysuccinic acid.But oxysuccinic acid is stronger organic acid, and tart flavour is extremely strong, and 5% solution ph reaches 1.5, and a large amount of high densitys take that not only mouthfeel is very poor, and can burn oral cavity and esophagus, can cause simultaneously that hydrochloric acid in gastric juice is too high in a short time.If with alkali neutralization, then can bring positively charged ion such as a large amount of sodium potassium into and influence the biological activity of oxysuccinic acid.Therefore chitosan is water insoluble, can not be mixed with the aqueous solution or adds in other liquid products, can only take with solid form, not only take inconvenience, and influence absorbs.Though the degraded product oligochitosan of chitosan can be water-soluble, but dissolution rate is slower, add hydrochloric acid or sulfuric acid and can increase dissolution rate, but can bring chlorion or sulfate ion into, therefore need good water solubility and don't bring the oligochitosan fill-in of other harmful anions (example hydrochloric acid salt can be brought chlorion into, and vitriol can be brought sulfate ion into) into.
Summary of the invention
The purpose of this invention is to provide a kind of malic acid chitosan oligosaccharide compound salt.
Another object of the present invention provides a kind of preparation method of above-mentioned malic acid chitosan oligosaccharide compound salt.
A further object of the invention provides the application of a kind of above-mentioned compound malic acid chitosan oligosaccharide salt in food and functional additive field.
The invention provides a kind of malic acid chitosan oligosaccharide compound salt, its structure is as follows:
Wherein: R is H or protonated amido glucose unit, and n is 1-50.
The composite salt of amido glucose unit formation 1:1 in oxysuccinic acid and oligochitosan when R is H, its 5% aqueous ph value is 3.4-3.8; When R is protonated amido glucose unit in oxysuccinic acid and the oligochitosan amido glucose unit form the composite salt of 1:2, its 5% aqueous ph value is 5.2-5.6.
Oxysuccinic acid and oligochitosan are made malic acid chitosan oligosaccharide compound salt of the present invention, the acidity of oxysuccinic acid has not only neutralized, solve the solubility problem of oligochitosan simultaneously, and oxysuccinic acid and oligochitosan show very strong collaborative physiological function, and the malic acid chitosan oligosaccharide compound salt of gained has good water-solubility and superior bioactive.
The preparation method of malic acid chitosan oligosaccharide compound salt provided by the invention may further comprise the steps: at first deacetylation is suspended in a certain amount of pure water greater than 85% chitosan, the add-on of water be chitosan weight 20-200 doubly, be preferably 20-100 doubly; Add DL-oxysuccinic acid or L MALIC ACID, add-on is 0.3-0.6 a times of chitosan weight, is heated to 40-60 ℃ of dissolving or swelling under stirring, and makes system PH between 3.8-7.0, preferably between 4.5-6.5; Immobilization chitoanase (the Batillus punits BN-262) hydrolysis that adds chitosan weight 5-10% then, temperature 30-60 ℃, be preferably 40-50 ℃, hydrolysis time is 5-48 hour; The filtered and recycled immobilized enzyme is that the composite salt that forms 1:1 or 1:2 is added the oxysuccinic acid of 0.1-1.5 times of chitosan weight according to the finished product again, continues the hydrolysis salify 2-8 hour down at 60-100 ℃; Then the liquid cooling after the hydrolysis is arrived 25-30 ℃, under agitation add alcohol and carry out alcohol and analyse, it can be methyl alcohol, ethanol, propyl alcohol, Virahol or butanols that alcohol is analysed used alcohol, preferred alcohol and Virahol, add-on is the 30-200% (volume) of solution amount, is preferably 50-150% (volume); Alcohol is analysed liquid through centrifugation, washing, obtains the high purity malic acid chitosan oligosaccharide compound salt after 50-60 ℃ of following vacuum-drying 6-10 hour.
In hydrolysing step, the selective hydrolysis temperature was 80-100 ℃ when oxysuccinic acid was the DL-oxysuccinic acid, and the selective hydrolysis temperature was 60-80 ℃ when oxysuccinic acid was L MALIC ACID.
Analyse in the step at alcohol, also can separate out described composite salt step by step, determining alcohol obtains the bigger malic acid chitosan oligosaccharide compound salt of molecular weight when low, obtain the less malic acid chitosan oligosaccharide compound salt of molecular weight when determining alcohol is high, therefore adopt preparation method of the present invention can also obtain different molecular weight fractionated malic acid chitosan oligosaccharide compound salt.
Malic acid chitosan oligosaccharide compound salt of the present invention can be widely used in food and functional additive field, has antifatigue, protects the liver detoxifcation, strengthening immunity and fat-reducing, effects such as hypotensive and reducing blood-fat.
Mode by embodiment can further specify the present invention, but does not therefore limit the present invention among the described scope of embodiments.
Description of drawings
Fig. 1 is the process flow sheet of preparation malic acid chitosan oligosaccharide compound salt provided by the invention
Embodiment
Embodiment 1
16 gram chitosans (degree of deacetylation is greater than 85%) are suspended in the 1600ml distilled water, add 8 gram DL-oxysuccinic acid earlier, be heated to 50 ℃ of dissolvings; PH4.8; add 1 gram immobilization chitoanase (Batillus punitsBN-262), stir hydrolysis 8 hours, filtered and recycled enzyme down at 50 ℃.Add 12 gram DL-oxysuccinic acid, be heated to 90-95 ℃ of reaction under stirring and continue hydrolysis 2 hours, obtain transparent solution, be cooled to 25-30 ℃, add 1600ml ethanol, separate out white solid, filter, use twice of 20ml washing with alcohol, 60 ℃ of following vacuum-dryings obtained DL-malic acid chitosan oligosaccharide compound salt 25.3 grams in 6 hours, ultimate analysis shows that this composite salt contains C:41.62%, H:4.92%, N:5.07%.The theoretical percentage composition of C, H, O element was when amido glucose unit in known oxysuccinic acid and the oligochitosan formed the composite salt of 1:1: C:40.9%, H:5.7%, N:4.8%, the theoretical percentage composition of C, H, O element was when amido glucose unit in oxysuccinic acid and the oligochitosan formed the composite salt of 1:2: C:42.6%, H:6.3%, N:6.1%.Therefore ultimate analysis shows the composite salt of the amido glucose unit formation 1:1 in the DL-oxysuccinic acid and oligochitosan in this embodiment.
Embodiment 2
16 gram chitosans (degree of deacetylation is greater than 85%) are suspended in the 800ml distilled water, add 7 gram L MALIC ACIDs earlier, be heated to 50 ℃ of dissolvings; PH5.2; add 1 gram immobilization chitoanase (Batillus punitsBN-262), stir hydrolysis 8 hours, filtered and recycled enzyme down at 50 ℃.Add 23 gram L MALIC ACIDs, be heated to 60-65 ℃ of reaction under stirring and continue hydrolysis 8 hours, obtain transparent solution, be cooled to 25-30 ℃, add the 1200ml Virahol, separate out white solid and filter, obtained L MALIC ACID chitosan oligosaccharide compound salt 25.1 grams in 6 hours with twice, 60 ℃ of following vacuum-drying of 20ml washed with isopropyl alcohol.Ultimate analysis shows that this composite salt contains C:41.24%, H:4.85%, and N:5.19% shows that the amido glucose unit in the L MALIC ACID and oligochitosan in this embodiment forms the composite salt of 1:1.
Embodiment 3
15 gram chitosans (degree of deacetylation is greater than 85%) are suspended in the 3000ml distilled water, add 5 gram DL-oxysuccinic acid earlier, be heated to 50 ℃ of dissolvings; PH5.5; add 1 gram immobilization chitoanase (Batillus punitsBN-262), stir hydrolysis 8 hours, filtered and recycled enzyme down at 50 ℃.Add 2 gram DL-oxysuccinic acid, be heated to 90-95 ℃ of reaction under stirring and continue hydrolysis 4 hours, obtain transparent solution, be cooled to 25-30 ℃, add 3000ml ethanol, separating out white solid filters, with twice of 20ml washing with alcohol, 60 ℃ of following vacuum-dryings obtained DL-malic acid chitosan oligosaccharide compound salt 22.6 grams in 6 hours, ultimate analysis shows that this composite salt contains C:42.07%, H:5.44%, N:5.47% shows that amido glucose unit in the DL-oxysuccinic acid and oligochitosan in this embodiment also has the composite salt of 1:2 to exist when forming the composite salt of 1:1.
Embodiment 4
20 gram chitosans (degree of deacetylation is greater than 85%) are suspended in the 400ml distilled water, add 10 gram DL-oxysuccinic acid earlier, be heated to 50 ℃ of dissolvings; PH4.8; add 1 gram immobilization chitoanase (Batillus punitsBN-262), stir hydrolysis 8 hours, filtered and recycled enzyme down at 50 ℃.Add 15 gram DL-oxysuccinic acid, be heated to 90-95 ℃ of reaction under stirring and continue hydrolysis 4 hours, obtain transparent solution, be cooled to 25-30 ℃, add 200ml ethanol earlier, separate out white solid, filter, obtained DL-malic acid chitosan oligosaccharide compound salt 6.8 grams, amido glucose unit average out to 15-16 after measured in 6 hours with twice, 60 ℃ of following vacuum-drying of 10ml washing with alcohol.Ultimate analysis shows that this composite salt contains C:41.32%, H:5.30%, and N:4.96% shows the composite salt of the amido glucose unit formation 1:1 in this moment DL-oxysuccinic acid and oligochitosan.Continue to add 600ml ethanol, separate out white solid and filter, obtained DL-malic acid chitosan oligosaccharide compound salt 18.6 grams, amido glucose unit average out to 8-9 after measured in 6 hours with twice, 60 ℃ of following vacuum-drying of 20ml washing with alcohol.Ultimate analysis shows that this composite salt contains C:41.62%, H:5.35%, and N:5.07%, what show amido glucose unit formation in this moment DL-oxysuccinic acid and oligochitosan also is the composite salt of 1:1.
Embodiment 5
15 gram chitosans (degree of deacetylation is greater than 85%) are suspended in the 1500ml distilled water, add 6 gram DL-oxysuccinic acid earlier, be heated to 50 ℃ of dissolvings; PH5.5; add 1 gram immobilization chitoanase (Batillus punitsBN-262), stir hydrolysis 8 hours, filtered and recycled enzyme down at 50 ℃.Add 4 gram DL-oxysuccinic acid, be heated to 90-95 ℃ of reaction under stirring and continue hydrolysis 4 hours, obtain transparent solution, with 10% sodium hydroxide solution PH is transferred to 5 with the excessive oxysuccinic acid that neutralizes, be cooled to 25-30 ℃, add 750ml ethanol, separating out white solid filters, with twice of 20ml washing with alcohol, 60 ℃ of following vacuum-dryings obtained DL-malic acid chitosan oligosaccharide compound salt 8.2 grams in 6 hours, and ultimate analysis shows that this composite salt contains C:42.07%, H:6.14%, therefore N:6.27%, the composite salt of the amido glucose unit formation 1:2 in DL-oxysuccinic acid and the oligochitosan in this embodiment.
Water-soluble and the acid experiment 1 of test example 1 malic acid chitosan oligosaccharide compound salt
Resulting DL-malic acid chitosan oligosaccharide compound salt 5 grams (the amido glucose unit forms the composite salt of 1:1 in oxysuccinic acid and the oligochitosan) among the embodiment 1 are added in the 100ml distilled water, composite salt is dissolved rapidly under stirring, the PH of solution is 3.8, and the malic acid solution PH of same concentrations is 1.7.
This test shows the malic acid chitosan oligosaccharide compound salt good water solubility of the 1:1 that the present invention makes, its acidity reduces greatly with the malic acid solution of concentration, improved the mouthfeel of oligochitosan simultaneously, can be used for preparing buccal tablet, drinks etc., comparable oxysuccinic acid are applied to food and functional additive field widely.
Water-soluble and the acid experiment 2 of test example 2 malic acid chitosan oligosaccharide compound salts
Resulting DL-malic acid chitosan oligosaccharide compound salt 5 among the embodiment 5 (the amido glucose unit forms the composite salt of 1:2 in oxysuccinic acid and the oligochitosan) gram is added in the 100ml distilled water, stir composite salt dissolving down, but dissolution rate is slower than experimental example 1, the PH of solution is 5.5, and the malic acid solution PH1.7 of same concentrations.
This test shows that the malic acid chitosan oligosaccharide compound salt of the 1:2 that the present invention makes also has good water-solubility, but dissolution rate is poor slightly than the composite salt of 1:1, its acid composite salt solution with the 1:1 of concentration is low, reduce greatly than malic acid solution especially with concentration, can be used for the product of compounding high concentration oxysuccinic acid or can directly take and can not damage esophagus, also can not change the acidity of stomach, thus influence digestion.The composite use of malic acid chitosan oligosaccharide compound salt of 1:1 and 1:2 simultaneously can be regulated acidity, thereby further broadened application is in the field.
Test example 3 reducing cholesterol and triglyceride level test
30 routine simple obesity people are observed, be divided into two groups of each 15 people, take 1.6 gram oligochitosans (content that is equivalent to oligochitosan in the 3 gram 1:1 malic acid chitosan oligosaccharide compound salts) for each person every day for first group; Second group of malic acid chitosan oligosaccharide compound salt of taking gained among the 3 gram embodiment 2 for each person every day taken 30 days, and test-results sees Table one.This experimental result shows that malic acid chitosan oligosaccharide compound salt has the effect of obvious reducing cholesterol and triglyceride level, and has obvious synergistic effect.
Table 1
Claims (7)
1. the preparation method of a malic acid chitosan oligosaccharide compound salt, the structure of described malic acid chitosan oligosaccharide compound salt is as follows
Wherein: R is H or protonated amido glucose unit, and n is 1-50;
1: 1 composite salt of amido glucose unit formation in oxysuccinic acid and oligochitosan when R is H, its 5% pH value of water solution is 3.4-3.8; When R is protonated amido glucose unit in oxysuccinic acid and the oligochitosan amido glucose unit form 1: 2 composite salt, its 5% pH value of water solution is 5.2-5.6;
It is characterized in that:
With DL-oxysuccinic acid or L MALIC ACID and the chitosan of degree of deacetylation more than 85% is raw material, may further comprise the steps preparation:
(1) chitosan of degree of deacetylation more than 85% is suspended in the pure water, wherein the add-on of water be chitosan weight 20-200 doubly;
(2) add DL-oxysuccinic acid or L MALIC ACID in the chitosan suspension of step (1), add-on is 0.3-0.6 a times of chitosan weight, is heated to 40-60 ℃ of dissolving or swelling under stirring, and makes system pH between 3.8-7.0;
(3) the immobilization chitoanase Batillus punits BN-262 of adding chitosan weight 5-10%, 30-60 ℃ of following hydrolysis, hydrolysis time 5-48 hour;
(4) filtered and recycled immobilized enzyme; Add chitosan weight 0.1-1.5 DL-oxysuccinic acid or L MALIC ACID doubly again, further hydrolysis salify, temperature 60-100 ℃, time 2-8 hour;
(5) with the liquid cooling after the hydrolysis to 25-30 ℃, under agitation add alcohol and carry out alcohol and analyse, it is methyl alcohol, ethanol, propyl alcohol, Virahol or butanols that alcohol is analysed used alcohol, add-on is the 30-200% (volume) of solution amount;
(6) alcohol was analysed liquid through centrifugation, washing, obtained the high purity malic acid chitosan oligosaccharide compound salt at 50-60 ℃ of following vacuum-drying 6-10 hour.
2. the preparation method of malic acid chitosan oligosaccharide compound salt according to claim 1 is characterized in that: in the step (1) add-on of water be chitosan weight 20-100 doubly.
3. the preparation method of malic acid chitosan oligosaccharide compound salt according to claim 1 is characterized in that: regulate the add-on of oxysuccinic acid in step (2), make system pH between 4.5-6.5.
4. the preparation method of malic acid chitosan oligosaccharide compound salt according to claim 1 is characterized in that: hydrolysis temperature is 40-50 ℃ in the step (3).
5. the preparation method of malic acid chitosan oligosaccharide compound salt according to claim 1 is characterized in that: add oxysuccinic acid in the step (4) when being the DL-oxysuccinic acid, hydrolysis temperature is 80-100 ℃; When the oxysuccinic acid that adds was L MALIC ACID, hydrolysis temperature was 60-80 ℃.
6. the preparation method of malic acid chitosan oligosaccharide compound salt according to claim 1 is characterized in that: to analyse used alcohol be ethanol or Virahol to alcohol in the step (5).
7. the preparation method of the described malic acid chitosan oligosaccharide compound salt of claim 1, it is characterized in that: pure add-on is the 50-150% (volume) of solution amount in the step (5).
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