CN106146682A - A kind of method of the degraded large molecular weight polysaccharides containing α 1,3 glycosidic bond - Google Patents
A kind of method of the degraded large molecular weight polysaccharides containing α 1,3 glycosidic bond Download PDFInfo
- Publication number
- CN106146682A CN106146682A CN201610571395.XA CN201610571395A CN106146682A CN 106146682 A CN106146682 A CN 106146682A CN 201610571395 A CN201610571395 A CN 201610571395A CN 106146682 A CN106146682 A CN 106146682A
- Authority
- CN
- China
- Prior art keywords
- polysaccharide
- molecular weight
- solution
- passed
- glycosidic bond
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
- A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pharmacology & Pharmacy (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Electrochemistry (AREA)
- Epidemiology (AREA)
- Metallurgy (AREA)
- Biochemistry (AREA)
- Polymers & Plastics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention relates to a kind of degraded containing α 1, the method of the large molecular weight polysaccharides of 3 glycosidic bonds, by concentration be 60 200mg/mL containing α 1, the large molecular weight polysaccharides solution of 3 glycosidic bonds is passed through in the electrolysis bath being provided with cathode and anode, regulation solution is acid, it is passed through oxygen according to the amount of 4.0 7.0L oxygen/L polysaccharide solution to negative electrode, is passed through oxygen to negative electrode, be passed through unidirectional current and to control cathode-current density be 10 12mA/cm2, degraded, collect electrolyte, to obtain final product.The method is to containing α 1, and the polysaccharide of 3 glycosidic bonds has good selectivity, and technological operation is simple, time-saving and efficiency, and reaction condition is gentle, and environmental pollution is little, is conducive to expanding large-scale production;It is essential that compared with acid system degraded and hydrogen peroxide degradation method, Electro-Fenton process is high to the degradation rate of polysaccharide, and the low-molecular-weight polysaccharide molecular weight ranges obtained is narrower.
Description
Technical field
The present invention relates to medical material production field, be specifically related to a kind of degraded and contain α-1, the macromolecule of 3-glycosidic bond is many
The method of sugar.
Background technology
Polysaccharide is to be formed by the condensation of multiple monosaccharide molecule, dehydration, is the complicated and huge glucide of molecule structure,
Active polysaccharide refers to that certain has the compound of polysaccharide of special physiological activity, has the function of regulation Human Physiology rhythm.Polysaccharide
In monosaccharide with glycosidic bond connect, glycosidic bond includes β-Isosorbide-5-Nitrae-glycosidic bond, α-1,3-glycosidic bond, β-1,3-glycosidic bond etc..
Research shows, the biological activity of polysaccharide is closely related with its molecular weight, and molecular weight is the biggest, and molecular volume is the biggest, and
Dissolubility is poor, and along with the increase of molecular weight, the viscosity of polysaccharide solution increases, and is unfavorable for that polysaccharide is crossed over cell multiplex film obstacle and entered
Biologic activity is played in organism.Therefore, large molecular weight polysaccharides is carried out degraded and obtain low-molecular-weight polysaccharide so that it is preferably
Play biologic activity, there is important value.
The Degradation of Polysaccharides of prior art report has physical degradation methods, chemical degradation method and enzymatic degradation method.Mechanical degradation
Method such as supercritical ultrasonics technology, can degrade the polysaccharide of macromolecule, but this method is higher to equipment requirements, it is impossible to reach industry metaplasia
Produce.Enzymatic degradation method is to disconnect a glycosidic bond in polysaccharide molecule with narrow spectrum glycosidase to reach the purpose of degradation of polysaccharide,
Or with other non-specific enzymes, polysaccharide is degraded.Enzymatic degradation method reaction condition is gentle, it is not necessary to add other reaction reagents,
And do not have by-product to generate, but currently without ripe enzyme, it is possible to degrade for industrialization;Chemical degradation method mainly includes acid fall
Solution and hydrogen peroxide degradation method.Acid degradation method is to utilize the hydrolysis of glycoside bond of polysaccharide molecule under acid condition to cause sugar chain to break
The method split, typically uses hydrochloric acid, sulphuric acid hydrolysis, additionally, the most useful trifluoroacetic acid, acetic acid, the Polysaccharides such as Fluohydric acid., is relatively
Method for classical degradation of polysaccharide.But, the fracture of acid degradation method glycosidic bond is random, and molecular weight of product distribution is relatively
Extensively, structure and activity to product have destructiveness.Hydrogen peroxide degradation method needs to use hydrogen peroxide, and hydrogen peroxide is in storage
With transportation also exists potential danger and degradation rate is low, be not suitable for industrialization expanding production.
Therefore, for specific monosaccharide connected mode, such as α-1,3-glycosidic bond, a kind of more general polysaccharide degraded side is proposed
Method is highly significant.
Summary of the invention
It is an object of the invention to the defect existed for prior art, it is provided that a kind of degraded is containing α-1, big point of 3-glycosidic bond
The method of son amount polysaccharide, the method can be good at the defect overcoming prior art to exist, has and be prone to industrialization, degradation rate
Height, the advantage of the product molecule weight range narrowly distributing that degraded obtains.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of degraded, containing α-1, the method for the large molecular weight polysaccharides of 3-glycosidic bond, uses Electro-Fenton process degraded, described electricity
The operation of Fenton method is:
The large molecular weight polysaccharides solution containing α-1,3-glycosidic bond that concentration is 60-200mg/mL is passed through and is provided with cathode and anode
Electrolysis bath in, regulation solution be acidity, be passed through oxygen to negative electrode, to negative electrode according to the amount of 4.0-7.0L oxygen/L polysaccharide solution
It is passed through oxygen, is passed through unidirectional current and to control cathode-current density be 10-12mA/cm2, with this understanding, degrade, collect electricity
Solve liquid, to obtain final product.
Preferably, described α-1, the large molecular weight polysaccharides solution of 3-glycosidic bond is the most formulated: with quite
In described α-1, the ethanol dispersion polysaccharide of the 0.8-2.0 times of weight of large molecular weight polysaccharides of 3-glycosidic bond, it is subsequently adding water and makes polysaccharide
It is 60-200mg/mL relative to the concentration of water, to obtain final product.
Polysaccharide is first disperseed in ethanol by the present invention, can form uniform polysaccharide suspension, then add water, this kind
In the case of, polysaccharide can be dispersed in water, solves low the asking of dissolubility owing to polysaccharide molecular weight is big, viscosity causes greatly
Topic, has been greatly facilitated the carrying out of follow-up electrolysis.
Polysaccharide solution in 60-200mg/mL concentration range is had good by the Electro-Fenton process condition using the present invention
Degradation effect, when concentration is higher than this scope, degradation rate is relatively low, and the mean molecule quantity of gained low-molecular-weight polysaccharide relatively this concentration model
Enclose the product mean molecule quantity obtained of degrading big;When concentration is less than this scope, although low-molecular-weight polysaccharide can be obtained, but degrade
Inefficient, enterprise energy consumption is relatively big, relatively costly.
Inventor further study show that, pH value is to containing α-1, and the degraded of the polysaccharide of 3-glycosidic bond has a major impact, pH value
Time higher or on the low side, polysaccharide degradation rate is low.When pH is 2-4, degradation rate is higher;When pH is 2.5-3.5, when being especially 3, degraded
Efficiency is the highest, and therefore, currently preferred pH value is 2-4, more preferably 2.5-3.5, and most preferably 3.
In process of production, aerator can be used to blast oxygen in electrolysis bath.Preferably, use containing at least one
The aerator of individual passage is passed through oxygen to described negative electrode, depending on the quantity of the passage scale according to electrolysis, i.e. works as electrolysis
Polysaccharide solution amount big time, multiple passage can be used simultaneously to blast the mode of oxygen, when the polysaccharide solution of electrolysis is few, can use
Less passage blasts the mode of oxygen simultaneously.The air-blowing simultaneously of multiple passages contributes to oxygen and is evenly distributed on cathode sheet week
Enclose and uniformly produce HO.It is further preferred that the speed that is passed through of oxygen is 0.2-1.0L/min (preferably 0.6-in each passage
0.8L/min, most preferably 0.7L/min).
It will be understood by those skilled in the art that substituting oxygen with air equally realizes above-mentioned purpose, in concrete application
Time, the means increasing air intake can be used to reach the purpose identical with being passed through pure oxygen tolerance.
Preferably, when electrolysis, can add electrolyte in described polysaccharide solution, adding electrolyte can increase leading of solution
Electrically, being smoothed out of electrolysis is contributed to.It is directed to the 60-200mg/mL acidity of the present invention polysaccharide containing α-1,3-glycosidic bond molten
Liquid, it is preferred to use sodium sulfate or sodium chloride are as electrolyte, and the concentration working as electrolyte is 0.01-0.3mol/L (preferably 0.02-
Time 0.1mol/L), electrolysis effectiveness is optimal.
Preferably, described anode material is ferrum, and described negative electrode material is graphite.Negative electrode material more preferably porous stone
Ink.
Preferably, the operation of above-mentioned Fenton is carried out under agitation, and it is more abundant that stirring contributes to polysaccharide molecule
Contact with HO, promote degraded.Mixing speed is preferably 100-600rpm.
The operation of the present invention preferably Fenton comprises the steps:
(1) preparation polysaccharide solution: first by the 0.8-2.0 times of weight of large molecular weight polysaccharides being equivalent to described α-1,3-glycosidic bond
Ethanol dispersion polysaccharide, be subsequently adding water and make polysaccharide be 60-200mg/mL relative to the concentration of water, regulation pH value is 2-4, i.e.
?;
(2) electrolysis: with ferrum as anode, graphite is negative electrode, adds in electrolysis bath by the polysaccharide solution prepared, adds sulphuric acid
Sodium or sodium chloride, and to regulate its concentration be 0.02-0.1mol/L;Lead to negative electrode according to the amount of 4.0-7.0L oxygen/L polysaccharide solution
Enter oxygen, and to control cathode-current density be 10-12mA/cm2, under stirring, it is electrolysed, collects electrolyte, to obtain final product.
Method of the present invention is applicable to degrade any containing α-1, and the large molecular weight polysaccharides of 3-glycosidic bond, especially to silver
Fungus polysaccharides has splendid degradation effect.Tremella polysaccharide is a kind of acid heteroglycan obtained from Tremella fructification, and its main chain is tied
Structure is that the mannan that 3-glycosidic bond connects, side chain is made up of glucuronic acid and xylose by α-1.Now there are some researches show, Tremella is many
Sugar have improve body's immunity and promote leukocyte effect;Wheat Protein, can remove the destruction of radical pair body,
Anti-senility;Tremella polysaccharide is at treatment hyperlipidemia, and high-cholesterol disease aspect also has good effect;The shape of thrombosis can be obviously prolonged
The one-tenth time, reduce platelet adhesion rate and blood viscosity, have the effect of prevention and cure of cardiovascular disease.Therefore, molecular weight distribution is obtained
Narrower low-molecular-weight tremella polysaccharide, has great meaning for prevention and treatment of diseases.
Polysaccharide of the present invention can use common commercially available prod, or, can extract according to means disclosed in prior art
Obtain.It is said that in general, the molecular weight of polysaccharide is not particularly limited by Electro-Fenton process condition of the present invention, to the most commercially available
The molecular weight that product or the product obtained according to the extraction of prior art overt means have is respectively provided with good degradation effect.Especially
Ground, Electro-Fenton process condition of the present invention has good degradation effect to the polysaccharide that molecular weight is 400-560KDa, tool
There is degradation rate high, the narrow molecular weight distribution of the low-molecular-weight polysaccharide that degraded obtains, the feature that pharmacologically active is good.More particularly, originally
Method described in invention has splendid degradation effect to the tremella polysaccharide that molecular weight is 400-560KDa.
Inventor finds through numerous studies, for different polysaccharide types, by the further optimization to reaction condition,
Optimal degradation effect can be obtained.Such as, for tremella polysaccharide, during electrolysis, controlling polysaccharide solution concentration is 180-
200mg/mL, the amount being passed through oxygen is: 4.0-7.0L/L polysaccharide solution, and cathode-current density is 10-12mA/cm2, it is possible to obtain
Optimal electrolysis effectiveness.
Method of the present invention also includes the step extracting low-molecular-weight polysaccharide from electrolyte, and described " extraction " can adopt
By this area routine techniques means, present invention preferably employs ultrafiltration membrance filter method and extract, further preferably use and retain point
Electrolyte described in the ultrafilter membrane ultrafiltration of son amount 10KDa-50KDa.After ultra filtration, collect concentrated solution, freeze-dried, to obtain final product.
Preferably, in order to reduce loss, before ultrafiltration is extracted, first regulation electrolyte is neutral.
The present invention is directed to containing α-1, the polysaccharide of 3-glycosidic bond, by groping its biodegrading process, it is determined that optimal fall
Solution method, the method technological operation is simple, and time-saving and efficiency is conducive to expanding large-scale production;And reaction condition is gentle, dirty to environment
Contaminate little;It is essential that compared with acid system degraded and hydrogen peroxide degradation method, Electro-Fenton process to the degradation rate of polysaccharide up to 30-
32%, in the case of the polysaccharide that degraded molecular weight is suitable, the molecular weight ranges of the low-molecular-weight polysaccharide obtained is narrower, physiologically active
More preferably.
On the basis of meeting common sense in the field, above-mentioned each optimum condition, can be mutually combined, obtain the present invention each preferably
Embodiment.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.The raw material related to or reagent
Being known substance, the operation related to is this area routine operation if no special instructions.
Embodiment 1
A kind of method using Electro-Fenton process degraded tremella polysaccharide: weigh 3000g tremella polysaccharide (molecular weight 560KDa),
Being distributed in 3.0Kg dehydrated alcohol, join in 15L distilled water, make the sugar juice that concentration is 200mg/ml, loading volume is
In the electrolysis bath of 24L, weigh 149.1g sodium sulfate and be dissolved in polysaccharide solution, with 1mol/L hydrochloric acid adjust pH to 3, with 30cm ×
30cm wire gauze is anode, and 30cm × 30cm porous graphite is negative electrode, and two anode-cathode distances are 5cm, are passed through 12V unidirectional current, electric current
Density is 12mA/cm2, and it is passed through purification air (or the speed with 0.58L/min with aerator with the speed of 1.74L/min
Being passed through oxygen, aerator contains three passages, and three passages blast oxygen simultaneously), every liter of tremella polysaccharide solution is passed through sky
The amount of gas is about 20.8L (amount that every liter of tremella polysaccharide solution is passed through air is about 6.96L), and agitator stirs with the speed of 250rpm
Mix, after being electrolysed 60min under room temperature condition, stop energising ventilation, after the sodium hydroxide solution of electrolyte 1M is neutralized to neutrality
With the ultrafilter membrane ultrafiltration of molecular cut off 30KDa-50KDa, collect concentrated solution, lyophilization, obtain tremella polysaccharide 973.5g, with solidifying
It is 33.6KDa that glue exclusion chromatography measures mean molecule quantity, and degradation rate is 32.45%.
Embodiment 2
A kind of method using Electro-Fenton process degraded tremella polysaccharide: weigh 900g tremella polysaccharide (molecular weight 400KDa),
Being distributed in 3.0Kg dehydrated alcohol, join in 15L distilled water, make the sugar juice that concentration is 60mg/ml, loading volume is
In the electrolysis bath of 24L, weigh 106.5g sodium sulfate and be dissolved in polysaccharide solution, with 1mol/L hydrochloric acid adjust pH to 3, with 30cm ×
30cm wire gauze is anode, and 30cm × 30cm porous graphite is negative electrode, and two anode-cathode distances are 8cm, are passed through 10V unidirectional current, electric current
Density is 10mA/cm2, and (aerator contains two passages, and two passages are simultaneously to be passed through oxygen with the speed of 0.6L/min
Blast oxygen), the amount that every liter of tremella polysaccharide solution is passed through air is about 4.0L, and agitator stirs with the speed of 250rpm, room temperature
Under the conditions of be electrolysed after 50min, stop energising ventilation, with retaining point after the sodium hydroxide solution of electrolyte 1M is neutralized to neutrality
The ultrafilter membrane ultrafiltration of son amount 10KDa-30KDa, collects concentrated solution, lyophilization, obtains tremella polysaccharide 278.28g, use gel exclusion
Chromatography determination mean molecule quantity is 14.7KDa, and degradation rate is 30.92%.
Comparative example 1 acid system degraded tremella polysaccharide
Weigh tremella polysaccharide 225g (molecular weight 560KDa), be distributed in 225g dehydrated alcohol, join 15L distilled water
In, make the sugar juice that concentration is 15mg/ml, with the hydrochloric acid conditioning solution pH to 2 of 1mol/L, stirring hydrolysis under room temperature condition
3.5h, after solution viscosity significantly reduces, with the ultrafilter membrane ultrafiltration of molecular cut off 10KDa-50KDa, collects concentrated solution, freezing dry
Dry, measure mean molecule quantity with gel exclusion chromatography.
Comparative example 2 hydrogen peroxide method degraded tremella polysaccharide
Weigh tremella polysaccharide 225g (molecular weight 560KDa), be distributed in 225g dehydrated alcohol, join 15L distilled water
In, making the sugar juice that concentration is 20mg/ml, add 66.05g ascorbic acid, (density is 1.13g/ to hydrogen peroxide 45.15ml
Ml), ferrous sulfate 104.26g, stirring reaction 2h under room temperature condition, with the ultrafilter membrane ultrafiltration of molecular cut off 10KDa-50KDa,
Collect concentrated solution, lyophilization, measure mean molecule quantity with gel exclusion chromatography.
Comparative example 3
A kind of method using Electro-Fenton process degraded tremella polysaccharide: weigh 300g tremella polysaccharide (molecular weight 560KDa),
Being distributed in 3.0Kg dehydrated alcohol, join in 15L distilled water, make the sugar juice that concentration is 20mg/ml, loading volume is
In the electrolysis bath of 24L, weigh 149.1g sodium sulfate and be dissolved in polysaccharide solution, with 1mol/L hydrochloric acid adjust pH to 3, with 30cm ×
30cm wire gauze is anode, and 30cm × 30cm porous graphite is negative electrode, and two anode-cathode distances are 5cm, are passed through 12V unidirectional current, electric current
Density is 12mA/cm2, and it is passed through purification air (or the speed with 0.58L/min with aerator with the speed of 1.74L/min
Being passed through oxygen, aerator contains three passages, and three passages blast oxygen simultaneously), every liter of tremella polysaccharide solution is passed through sky
The amount of gas is about 20.8L (amount that every liter of tremella polysaccharide solution is passed through air is about 6.96L), and agitator stirs with the speed of 250rpm
Mix, after being electrolysed 60min under room temperature condition, stop energising ventilation, after the sodium hydroxide solution of electrolyte 1M is neutralized to neutrality
With the ultrafilter membrane ultrafiltration of molecular cut off 5000Da, collect concentrated solution, lyophilization, tremella polysaccharide 15.03g, use gel exclusion
Chromatography determination mean molecule quantity is 6.4KDa, and degradation rate is 5.01%.
Comparative example 4
A kind of method using Electro-Fenton process degraded tremella polysaccharide: weigh 3000g tremella polysaccharide (molecular weight 560KDa),
Being distributed in 3.0Kg dehydrated alcohol, join in 15L distilled water, make the sugar juice that concentration is 200mg/ml, loading volume is
In the electrolysis bath of 24L, weigh 149.1g sodium sulfate and be dissolved in polysaccharide solution, with 1mol/L hydrochloric acid adjust pH to 5, with 30cm ×
30cm wire gauze is anode, and 30cm × 30cm porous graphite is negative electrode, and two anode-cathode distances are 5cm, are passed through 12V unidirectional current, electric current
Density is 12mA/cm2, and it is passed through purification air (or the speed with 0.58L/min with aerator with the speed of 1.74L/min
Being passed through oxygen, aerator contains three passages, and three passages blast oxygen simultaneously), every liter of tremella polysaccharide solution is passed through sky
The amount of gas is about 20.8L (amount that every liter of tremella polysaccharide solution is passed through air is about 6.96L), and agitator stirs with the speed of 250rpm
Mix, after being electrolysed 60min under room temperature condition, stop energising ventilation, after the sodium hydroxide solution of electrolyte 1M is neutralized to neutrality
With the ultrafilter membrane ultrafiltration of molecular cut off 30KDa-50KDa, collect concentrated solution, lyophilization, tremella polysaccharide 44.4g, use gel
It is 46.9KDa that exclusion chromatography measures mean molecule quantity, and degradation rate is 1.48%.
Comparative example 5
A kind of method using Electro-Fenton process degraded tremella polysaccharide: weigh 3000g tremella polysaccharide (molecular weight 560KDa),
Being distributed in 3.0Kg dehydrated alcohol, join in 15L distilled water, make the sugar juice that concentration is 200mg/ml, loading volume is
In the electrolysis bath of 24L, weigh 149.1g sodium sulfate and be dissolved in polysaccharide solution, with 1mol/L hydrochloric acid adjust pH to 3, with 30cm ×
30cm wire gauze is anode, and 30cm × 30cm porous graphite is negative electrode, and two anode-cathode distances are 5cm, are passed through 12V unidirectional current, electric current
Density is 12mA/cm2, and it is passed through purification air (or the speed with 0.58L/min with aerator with the speed of 1.74L/min
Being passed through oxygen, aerator contains a passage), the amount that every liter of tremella polysaccharide solution is passed through air is about 6.93L (every liter of Tremella
Polysaccharide solution is passed through the amount of air and is about 2.32L), agitator stirs with the speed of 250rpm, is electrolysed 60min under room temperature condition
After, stop energising ventilation, after the sodium hydroxide solution of electrolyte 1M is neutralized to neutrality, use molecular cut off 30KDa-50KDa
Ultrafilter membrane ultrafiltration, collect concentrated solution, lyophilization, tremella polysaccharide 754.2g, measure mean molecule with gel exclusion chromatography
Amount is 44.2KDa, and degradation rate is 25.14%.
By embodiment 1-2, the result of comparative example 1-5 is as shown in table 1:
Table 1: embodiment 1-2, the result data contrast of comparative example 1-5
From the above it can be seen that degrade relative to acid system degraded and hydrogen peroxide method, the polysaccharide fall of gained of the present invention
Solution rate is high, and mean molecule quantity is low, and the used time is shorter, has more preferable industrial application value.
Although, used general explanation, detailed description of the invention and test, the present invention made detailed retouching
Stating, but on the basis of the present invention, can make some modifications or improvements it, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Scope.
Claims (10)
1. a degraded is containing α-1, the method for the large molecular weight polysaccharides of 3-glycosidic bond, it is characterised in that use Electro-Fenton process fall
Solving, the operation of described Electro-Fenton process is:
The large molecular weight polysaccharides solution containing α-1,3-glycosidic bond that concentration is 60-200mg/mL is passed through the electricity being provided with cathode and anode
Solving in groove, regulation solution is acid, is passed through oxygen according to the amount of 4.0-7.0L oxygen/L polysaccharide solution to negative electrode, is passed through unidirectional current
And to control cathode-current density be 10-12mA/cm2, with this understanding, degrade, collect electrolyte, to obtain final product.
Method the most according to claim 1, it is characterised in that described containing α-1, the large molecular weight polysaccharides solution of 3-glycosidic bond
The most formulated: by the second of the 0.8-2.0 times of weight of large molecular weight polysaccharides being equivalent to described α-1,3-glycosidic bond
Alcohol dispersion polysaccharide, is subsequently adding water and makes polysaccharide be 60-200mg/mL relative to the concentration of water, to obtain final product.
Method the most according to claim 1 and 2, it is characterised in that described containing α-1, the large molecular weight polysaccharides of 3-glycosidic bond
The pH value of solution is 2-4, preferably 2.5-3.5, most preferably 3.
Method the most according to claim 3, it is characterised in that: described electrolysis bath is added with electrolyte, described electrolyte
For sodium chloride or sodium sulfate, the concentration of the most described electrolyte is 0.01-0.3mol/L.
Method the most according to claim 1, it is characterised in that: described anode material is ferrum, and described negative electrode material is graphite;
And/or,
Described degraded is carried out under agitation, and preferably mixing speed is 100-600rpm.
Method the most according to claim 1, it is characterised in that described Electro-Fenton process comprises the steps:
(1) preparation polysaccharide solution: first by the second of the 0.8-2.0 times of weight of large molecular weight polysaccharides being equivalent to described α-1,3-glycosidic bond
Alcohol dispersion polysaccharide, is subsequently adding water and makes polysaccharide be 60-200mg/mL relative to the concentration of water, and regulation pH value is 2-4, to obtain final product;
(2) electrolysis: with ferrum as anode, graphite is negative electrode, adds in electrolysis bath by the polysaccharide solution that prepare, add sodium sulfate or
Sodium chloride, and to regulate its concentration be 0.02-0.1mol/L;It is passed through oxygen to negative electrode according to the amount of 4.0-7.0L oxygen/L polysaccharide solution
Gas, and to control cathode-current density be 10-12mA/cm2, under stirring, it is electrolysed, collects electrolyte, to obtain final product.
7. according to the method described in any one of claim 1-6, it is characterised in that: described containing α-1, the macromolecule of 3-glycosidic bond
The molecular weight of polysaccharide is 400-560KDa.
Method the most according to claim 7, it is characterised in that: described containing α-1, the large molecular weight polysaccharides of 3-glycosidic bond is silver
Fungus polysaccharides.
Method the most according to claim 8, it is characterised in that: during electrolysis, controlling polysaccharide solution concentration is 180-200mg/
ML, the amount being passed through oxygen is: 4.0-7.0L/L polysaccharide solution, and cathode-current density is 10-12mA/cm2。
10. according to the method described in any one of claim 1-9, it is characterised in that: also include using electricity described in ultrafilter membrane ultrafiltration
Solve liquid to extract the step of low-molecular-weight polysaccharide;
Preferably, before extraction, regulation electrolyte is neutral.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810734728.5A CN109053919B (en) | 2016-07-19 | 2016-07-19 | Method for degrading tremella polysaccharide |
CN201610571395.XA CN106146682B (en) | 2016-07-19 | 2016-07-19 | A method of the large molecular weight polysaccharides of the degradation glycosidic bonds of -1,3- containing α |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610571395.XA CN106146682B (en) | 2016-07-19 | 2016-07-19 | A method of the large molecular weight polysaccharides of the degradation glycosidic bonds of -1,3- containing α |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810734728.5A Division CN109053919B (en) | 2016-07-19 | 2016-07-19 | Method for degrading tremella polysaccharide |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106146682A true CN106146682A (en) | 2016-11-23 |
CN106146682B CN106146682B (en) | 2018-07-31 |
Family
ID=58060317
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610571395.XA Active CN106146682B (en) | 2016-07-19 | 2016-07-19 | A method of the large molecular weight polysaccharides of the degradation glycosidic bonds of -1,3- containing α |
CN201810734728.5A Active CN109053919B (en) | 2016-07-19 | 2016-07-19 | Method for degrading tremella polysaccharide |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810734728.5A Active CN109053919B (en) | 2016-07-19 | 2016-07-19 | Method for degrading tremella polysaccharide |
Country Status (1)
Country | Link |
---|---|
CN (2) | CN106146682B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108264574A (en) * | 2016-12-30 | 2018-07-10 | 上海绿谷制药有限公司 | The ozone degradation method of polysaccharide |
CN111647093A (en) * | 2020-06-10 | 2020-09-11 | 苏州大学 | Preparation method of tremella polysaccharide |
CN112545928A (en) * | 2019-09-25 | 2021-03-26 | 华南协同创新研究院 | Tremella compound extract and preparation method and application thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110590968B (en) * | 2019-09-05 | 2021-09-28 | 浙江工业大学 | Preparation method and application of tremella oligosaccharide |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101962415A (en) * | 2010-10-28 | 2011-02-02 | 中国海洋大学 | Method for preparing low molecular weight brown seaweed fucoidan sulfate |
CN104530254A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院天津工业生物技术研究所 | Method for producing sodium alginate by applying brown algae |
-
2016
- 2016-07-19 CN CN201610571395.XA patent/CN106146682B/en active Active
- 2016-07-19 CN CN201810734728.5A patent/CN109053919B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101962415A (en) * | 2010-10-28 | 2011-02-02 | 中国海洋大学 | Method for preparing low molecular weight brown seaweed fucoidan sulfate |
CN104530254A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院天津工业生物技术研究所 | Method for producing sodium alginate by applying brown algae |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108264574A (en) * | 2016-12-30 | 2018-07-10 | 上海绿谷制药有限公司 | The ozone degradation method of polysaccharide |
US11155569B2 (en) | 2016-12-30 | 2021-10-26 | Green Valley (Shanghai) Pharmaceuticals Co., Ltd. | Method of degrading polysaccharide using ozone |
CN112545928A (en) * | 2019-09-25 | 2021-03-26 | 华南协同创新研究院 | Tremella compound extract and preparation method and application thereof |
CN111647093A (en) * | 2020-06-10 | 2020-09-11 | 苏州大学 | Preparation method of tremella polysaccharide |
Also Published As
Publication number | Publication date |
---|---|
CN109053919B (en) | 2020-06-30 |
CN106146682B (en) | 2018-07-31 |
CN109053919A (en) | 2018-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106146682A (en) | A kind of method of the degraded large molecular weight polysaccharides containing α 1,3 glycosidic bond | |
EP3730623A1 (en) | Small-molecule hyaluronic acid or salt thereof, and preparation method therefor | |
CN111040048A (en) | Ultra-low molecular weight hyaluronic acid and preparation method thereof | |
CN104263666B (en) | A kind of recombinant yeast pichia pastoris and its construction method for producing micromolecule hyaluronic acid | |
CN103233053B (en) | Production method for recombinant human granulocyte colony-stimulating factor | |
CN104178539B (en) | A kind of method of prepare with scale specified molecular weight micromolecule hyaluronic acid | |
CN106188327A (en) | A kind of method of the degraded large molecular weight polysaccharides containing β 1,4 glycosidic bond | |
CN104120158A (en) | Method for improving fermentation yield of low-molecular hyaluronic acid (HA) by adding hyaluronidase | |
CN114288308A (en) | Hyaluronic acid oligosaccharide composition mainly containing tetrasaccharide and preparation method and application thereof | |
EP2321419A2 (en) | Process for the co-production of chitin, its derivatives and polymers containing glucose, mannose and/or galactose, by the fermentation of the yeast pichia pastoris | |
KR101132114B1 (en) | Method of molecular weight control of hyaluronic acid | |
CN112646055A (en) | Preparation method of low-molecular-weight hyaluronic acid | |
CN102911887A (en) | Method for producing hyaluronic acids with different molecular weights through pichia pastoris gene-regulation fermentation | |
CN106146683A (en) | A kind of method of the degraded large molecular weight polysaccharides containing β 1,3 glycosidic bond | |
CN107236054B (en) | Preparation method and application of low-molecular-weight ascophyllan | |
CN106191914B (en) | A method of preparing low-molecular-weight polysaccharide | |
CN1786180A (en) | Method of improving byaluronic acid yield and molecular weight by fermentation process | |
CN106084085B (en) | A kind of preparation method and application of low-molecular-weight algal polysaccharide sulfate | |
CN106146579B (en) | Method for purifying avilamycin | |
CN109867721B (en) | Recombinant stichopus japonicus collagen polypeptide, preparation method and application thereof | |
CN1445245A (en) | Dermatan sulfate with low molecule and its preparing method | |
CN106512080A (en) | Preparation method for sericin protein hydrogel | |
CN113831421A (en) | Combined preparation method of grifola frondosa mycelium polypeptide and beta-glucan | |
CN1844161A (en) | Beta-1,4-glucan-6,2,3-sulfate and its preparation method and use | |
CN115820766A (en) | Method for preparing chondroitin oligosaccharide by enzyme method and chondroitin oligosaccharide composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |