CN105418790A - Preparation method of LMWF (Low Molecular Weight Fucoidan) - Google Patents
Preparation method of LMWF (Low Molecular Weight Fucoidan) Download PDFInfo
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- CN105418790A CN105418790A CN201610050718.0A CN201610050718A CN105418790A CN 105418790 A CN105418790 A CN 105418790A CN 201610050718 A CN201610050718 A CN 201610050718A CN 105418790 A CN105418790 A CN 105418790A
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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
- C08B37/006—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
- C08B37/0063—Glycosaminoglycans or mucopolysaccharides, e.g. keratan sulfate; Derivatives thereof, e.g. fucoidan
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Abstract
The invention belongs to the field of fine chemical engineering, and in particular relates to a preparation method of LMWF (Low Molecular Weight Fucoidan). The preparation method comprises the steps of dissolving HMWF (High Molecular Weight Fucoidan) into water to prepare a fucoidan solution, and heating the fucoidan solution to reaction temperature for standby use; then adding a prepared sodium persulfate solution of which the concentration is 10 to 1000 mM in the fucoidan solution, setting constant reaction temperature to be 50 to 100 DEG C, and reacting for 10 to 120 minutes; then concentrating after desalting through a dialysis method or an ultrafiltration method, and preparing the LMWF after carrying out spray drying, freeze drying or alcohol precipitation. According to the preparation method disclosed by the invention, the LMWF is quickly prepared through a heat-activated persulphate oxidation method; persulfate can be reduced into sulfate, so that more fucoidan can be obtained from a chemical equilibrium angle; through the preparation method, new chemical components are not introduced in during and after a preparation process, so that the preparation method is environment-friendly, and industrialization can be easily realized.
Description
Technical field
The invention belongs to Green Fine Chemical production field, be specifically related to a kind of preparation method of low-molecular-weight algal polysaccharide sulfuric acid ester.
Background technology
Fucoidan is a kind of sulfation mixed polysaccharide coming from brown alga and echinoderms, is also called fucoidin, laminarin, fucoidan, fucosan etc.There is the various clinical special efficacys such as inhibition tumor cell growth, Therapeutic cancer, treatment cardiovascular and cerebrovascular diseases, treatment renal failure.Directly come from biological fucoidan molecular weight large, easily produce antigenicity and obvious side effect, but after being converted into the right fucoidan of low molecular weight oligomeric, antigenicity and toxic side effect also decrease or disappear.The clinical efficacy of document display fucoidan and its polymerization degree negative correlation.
The fucoidan coarse-grain coming from brown alga or echinoderms often presents very large unhomogeneity in molecular structure and the polymerization degree, usually needs to make it oligomerization and homogenization by Physical, enzymolysis process, chemical method.Physical is degraded mainly through radiation method, molecular mill method, supersonic method, rarely seen relevant report.Enzymolysis process is subject to people's attention due to reaction conditions gentleness, such as: the people such as Cai Jingmin 2004 utilize a kind of fucoidan degrading enzyme be separated from a kind of thalassiomycetes, can enzymolysis sea-tangle fucoidin, obtain the low polymerization degree fucoidan that molecular mass is 8000-50000Da.But the acquisition of relevant enzyme is unsuitable and with high costs, does not have business-like relevant enzyme product to occur so far.Chemical method mainly contains hydrolysis method and oxidation style.Hydrolysis method mainly contains nitrite hydrolysis method and dilute acid hydrolysis method, and the method cost is low, but destroys more relative to oxidation style to the polysaccharide structures of fucoidan.Traditional oxidation style mainly adopts hydrogen peroxide or hypochlorous acid, and reaction is violent, and apparatus and process is complicated, and subsequent disposal is loaded down with trivial details.
This patent, by the persulfate oxidation method of thermal activation, prepares low-molecular-weight fucoidan fast.Be vitriol after persulphate is reduced, therefore the angle that can chemically balance obtain more fucoidan.And this method does not introduce new chemical composition in preparation process and after preparation, therefore environmental protection, easily realize industrialization.
Summary of the invention
In order to solve the problem, the invention provides a kind of degrade fucoidan of high polymerization state of the persulphate of thermal activation that adopts and preparing the method for low-molecular-weight algal polysaccharide sulfuric acid ester.
(1) fucoidan of high molecular is dissolved in the water, fully stirs, make fucoidan solution, be heated to temperature of reaction stand-by.
(2) compound concentration is 10-1000mM Sodium Persulfate (Na
2s
2o
8) solution.
(3) added by Sodium Persulfate solution prepared by step (2) in the obtained fucoidan solution of step (1), mechanical stirring, constant temperature of reaction is 50-100 DEG C, reaction 10-120min.
(4) gained solution in (3) will be reacted, after dialysis method or ultrafiltration process desalination, concentrated, after spray-dried or lyophilize or alcohol precipitation, obtained low-molecular-weight fucoidan.
In fucoidan reaction soln in step (1), the weight percent of fucoidan is 0.1-5.0%, preferred 1.0-2.0%
Obtained low-molecular-weight algal polysaccharide sulfuric acid ester weight-average molecular weight is 22-210kDa fucoidan (these data can be different according to raw material counterpoise difference).
The fucoidan of high molecular refers to that weight-average molecular weight is 240-2400kDa fucoidan (these data can be different according to raw material counterpoise difference).
Alcohol particular methanol described in step (4) or ethanol.
The invention has the advantages that:
(1) adopt the persulfate oxidation method degraded fucoidan of thermal activation, greatly can improve the efficiency of degraded and the amount of low-molecular-weight algal polysaccharide sulfuric acid ester;
(2) the degradation of polysaccharide molecule uniformity obtained is good, is beneficial to separation and the use in later stage;
(3) present invention process is simple, flow process is short, with low cost, subsequent disposal simple, and environmentally safe, is beneficial to expanding production.
Accompanying drawing explanation
Fig. 1 is fucoidan degraded schema involved in the present invention.
Embodiment
Below in conjunction with specifically implementing example, set forth the present invention further.It should be noted that these examples are only for illustration of the present invention, and be not used in and limit the scope of the invention.In addition should understand, after having read content of the present invention, those skilled in the art can make various change or amendment to the present invention, such as: change temperature of reaction and adopt different fucoidan raw materials etc., these equivalent form of values fall within the scope of the attached claims restriction of the application institute equally.
Fucoidan degraded flow process in following embodiment 1-4 is as Fig. 1.
Embodiment 1, differing temps is on the impact of degraded fucoidan
Get the fucoidan that weight-average molecular weight is 240-2400kDa, add the fucoidan solution 6 parts that distilled water solution preparation mass concentration is 1% respectively, constant temperature is 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C respectively.6 parts of solution are put into reactor respectively, add concentrated persulfate solution, controlling persulphate concentration is 100mM, and rapid stirring carries out DeR, and after 60min, cooling order reaction stops, be after the dialysis tubing dialysis desalting of 2000Da with the molecular weight that dams by gained solution, after dialyzate is concentrated, adding dehydrated alcohol to final concentration is that 75-80% leaves standstill more than 12 hours, filters, by the vacuum-drying of gained solid, low-molecular-weight algal polysaccharide sulfuric acid ester can be obtained.As can be seen from Table I, temperature has a great impact persulfate oxidation method degraded fucoidan, and the higher degradation effect of temperature is better.
Regarding assay data in table one embodiment 1
| Sequence number | Temperature | Productive rate | Product weight-average molecular weight | The product sulfur acid groups content |
| 1 | 50℃ | 95％ | 210-2400kDa | 31.5％ |
| 2 | 60℃ | 92％ | 190-2400kDa | 31.6％ |
| 3 | 70℃ | 90％ | 185-2400kDa | 32.0％ |
| 4 | 80℃ | 90％ | 145-2400kDa | 32.3％ |
| 5 | 90℃ | 87％ | 90-1900kDa | 33.0％ |
| 6 | 100℃ | 85％ | 75-1600kDa | 34.5％ |
Embodiment 2, the impact of differential responses time solution fucoidan
Get the fucoidan that weight-average molecular weight is 240-2400kDa, add the fucoidan solution 4 parts that distilled water solution preparation mass concentration is 1% respectively, constant temperature 100 DEG C.4 parts of solution are put into reactor respectively, add concentrated persulfate solution, controlling persulphate concentration is 100mM, rapid stirring carries out DeR, after 10min, 30min, 60min, 120min, cooling order reaction stops respectively, be after the dialysis tubing dialysis desalting of 2000Da with the molecular weight that dams by gained solution, after dialyzate is concentrated, adding dehydrated alcohol to final concentration is that 75-80% leaves standstill 12 hours, suction filtration, by the vacuum-drying of gained solid, low-molecular-weight algal polysaccharide sulfuric acid ester can be obtained.As can be seen from Table II, the productive rate of persulfate oxidation method degraded fucoidan is large along with the increase of time in 60min, but more than transformation efficiency Slow lifting after 60min, to carry out in 60min reacting comparatively suitable.
Regarding assay data in table two embodiment 2
| Sequence number | Reaction times | Productive rate | Product weight-average molecular weight | The product sulfur acid groups content |
| 1 | 10 minutes | 93％ | 190-2400kDa | 31.9％ |
| 2 | 30 minutes | 89％ | 150-2300kDa | 33.2％ |
| 3 | 60 minutes | 85％ | 75-1600kDa | 34.5％ |
| 4 | 120 minutes | 79％ | 70-1550kDa | 35.3％ |
Embodiment 3, different persulphate concentration is on the impact of microwave degradation fucoidan
Get the fucoidan that weight-average molecular weight is 240-2400kDa, add the fucoidan solution 7 parts that distilled water solution preparation mass concentration is 1% respectively, constant temperature 100 DEG C, add concentrated persulfate solution respectively, control persulphate concentration and be respectively 10mM, 20mM, 50mM, 100mM, 200mM, 500mM, 1000mM rapid stirring carries out DeR, after 60min, cooling order reaction stops, be after the dialysis tubing dialysis desalting of 2000Da with the molecular weight that dams by gained solution, after dialyzate is concentrated, concentrated solution obtains low-molecular-weight algal polysaccharide sulfuric acid ester through spraying dry.As can be seen from Table III, the degraded of persulphate concentration to fucoidan has a great impact, and generally the higher degradation effect of concentration is better, but usually occurs over oxidation phenomenon when considering that concentration is too large, and general selection 100-200mM is easy.
Regarding assay data in table three embodiment 3
| Sequence number | Persulphate concentration | Productive rate | Product weight-average molecular weight | The product sulfur acid groups content |
| 1 | 10mM | 88％ | 200-2300kDa | 31.8％ |
| 2 | 20mM | 87％ | 110-2000kDa | 32.2％ |
| 3 | 50mM | 87％ | 90-1800kDa | 32.5％ |
| 4 | 100mM | 85％ | 75-1600kDa | 34.5％ |
| 5 | 200mM | 82％ | 49-1300kDa | 35.3％ |
| 6 | 500mM | 79％ | 35-950kDa | 38.9％ |
| 7 | 1000mM | 68％ | 30-900kDa | 43.5％ |
Embodiment 4, different algal polysaccharide sulfate concentration is on the impact of degraded fucoidan
Get the fucoidan that weight-average molecular weight is 240-2400kDa, add distilled water solution preparation mass concentration respectively and be respectively 0.1%, 0.5%, 1.0%, the fucoidan solution of 2.0% 4 parts, constant temperature 100 DEG C, stir, add concentrated persulfate solution respectively, control persulphate concentration and be respectively 100mM, rapid stirring carries out DeR, after 60 minutes, cooling order reaction stops, be after the dialysis tubing dialysis desalting of 2000Da with the molecular weight that dams by gained solution, after dialyzate is concentrated, concentrated solution can obtain low-molecular-weight algal polysaccharide sulfuric acid ester through low-temp low-pressure drying.
Regarding assay data in table four embodiment 4
| Sequence number | Algal polysaccharide vitriol mass concentration | Productive rate | Product weight-average molecular weight | The product sulfur acid groups content |
| 1 | 0.1％ | 79％ | 22-1100kDa | 44.3％ |
| 2 | 0.5％ | 84％ | 45-1400kDa | 38.3％ |
| 3 | 1.0％ | 85％ | 75-1600kDa | 34.5％ |
| 4 | 2.0％ | 93％ | 130-1900kDa | 30.9％ |
Present invention process is simple, flow process is short, cost is low.The fucoidan with specified molecular weight section can be obtained in conjunction with dialysis by this method.The drug effect of fucoidan product can be increased substantially after being prepared into related drugs, and reduce antigenicity and toxic side effect.
Claims (6)
1. a preparation method for low-molecular-weight algal polysaccharide sulfuric acid ester, is characterized in that, comprises the following steps:
(1) fucoidan of high molecular is dissolved in the water, fully stirs, make fucoidan solution, be heated to temperature of reaction stand-by;
(2) compound concentration is 10-1000mM Sodium Persulfate solution;
(3) added by Sodium Persulfate solution prepared by step (2) in the obtained fucoidan solution of step (1), mechanical stirring, constant temperature of reaction is 50-100 DEG C, reaction 10-120min.
(4) gained solution in (3) will be reacted, after dialysis method or ultrafiltration process desalination, concentrated, after spray-dried or lyophilize or alcohol precipitation, obtained low-molecular-weight fucoidan.
2. method according to claim 1, is characterized in that, in the fucoidan reaction soln in step (1), the weight percent of fucoidan is 0.1-5.0%.
3. method according to claim 2, is characterized in that, in the fucoidan reaction soln in step (1), the weight percent of fucoidan is 1.0-2.0%.
4. method according to claim 1, is characterized in that, the weight-average molecular weight of obtained low-molecular-weight algal polysaccharide sulfuric acid ester is 22-210kDa.
5. method according to claim 1, is characterized in that, the fucoidan of described high molecular refers to that weight-average molecular weight is 240-2400kDa fucoidan.
6. method according to claim 1, is characterized in that, the alcohol described in step (4) is methyl alcohol or ethanol.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6632446B1 (en) * | 1992-04-20 | 2003-10-14 | The Board Of Regents, University Of Texas System | Coating substrates by polymerizing macromers having free radical-polymerizable substituents |
| CN104710539A (en) * | 2013-12-17 | 2015-06-17 | 深圳海王药业有限公司 | Sulfate fucosan and preparation method thereof |
-
2016
- 2016-01-25 CN CN201610050718.0A patent/CN105418790A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6632446B1 (en) * | 1992-04-20 | 2003-10-14 | The Board Of Regents, University Of Texas System | Coating substrates by polymerizing macromers having free radical-polymerizable substituents |
| CN104710539A (en) * | 2013-12-17 | 2015-06-17 | 深圳海王药业有限公司 | Sulfate fucosan and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 刘桂芳等: "活化过硫酸盐技术的研究进展", 《工业水处理》 * |
| 杨世迎等: "过硫酸盐高级氧化技术的活化方法研究进展", 《现代化工》 * |
| 王兵等: "基于硫酸自由基的高级氧化技术研究及应用进展", 《环境工程》 * |
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