CN102417548A - Method for extracting active polysaccharides from brown algae - Google Patents
Method for extracting active polysaccharides from brown algae Download PDFInfo
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- CN102417548A CN102417548A CN2011103435800A CN201110343580A CN102417548A CN 102417548 A CN102417548 A CN 102417548A CN 2011103435800 A CN2011103435800 A CN 2011103435800A CN 201110343580 A CN201110343580 A CN 201110343580A CN 102417548 A CN102417548 A CN 102417548A
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Abstract
The invention relates to a method for extracting active polysaccharides from brown algae. The method comprises the following specific steps of: putting a cleaned, dried and smashed alga raw material into an extraction container, and adding an organic acid solution or organic-inorganic mixed acid solution; heating a stirred and wetted material to 50-150 DEG C to realize partial degradation of high polymer polysaccharide substances of brown algae; fully washing with an organic solvent till the acid solution in the material is discharged completely; adding 5-8 times of volume of water for extracting, concentrating an extracting solution, regulating the pH value to neutral, and gradually depositing in alcohol to obtain align, fucoidin and laminaran which are rich in mannuronic acid fragments (rich in M) respectively; and pretreating brown alga raw material residues with water-extracted organic acid according to an alkali digestion process to obtain align which is rich in guluronic acid fragments (rich in G). By adopting the method, the defects of high water consumption, severe pollution and the like existing in the conventional align production process are overcome; and the method has the advantages of saving in energy, reduction in emission, high product yield, small extraction solvent dosage, and the like.
Description
Technical field
The present invention relates to active ingredient of natural product and extract the field, be specially a kind of method of from brown alga, extracting active polysaccharide.
Background technology
Marine alga is the general designation of marine products algae, and usually solid work is the individual plant that is made up of basic cell or a lot of simple plant on seabed or certain solid structure.Nutritive ingredient in the marine alga comprises polyose, protein, lipid, pigment and lower-molecular substance.Prove that through traditional Chinese medicine and present scientific research the material staple that has strengthening immunity and antitumour activity in the marine alga is a polyose.
Marine alga comprises red algae, green alga, brown alga etc., and research and use the more deep phaeophyta polysaccharide that is mainly in the Sargassum polysaccharides at present.Brown alga is one type of higher algae, has 250 to belong to kind more than 1500 approximately.The frond of phaeophyta is tawny or Vandyke brown, contains materials such as polyose, protein, lipid and N.F,USP MANNITOL.Kind that has such as sea-tangle, cell contain a large amount of iodine.
Algal polysaccharide is the important moity of brown alga, comprising algin, fucoidin, laminaran etc.Algin typically refers to sodium alginate, is that content is very high in brown alga by beta-D-mannuronic acid (being called for short M) and two kinds of linear polysaccharide segmented copolymers that the uronic acid monomer relies on the 1-4 glycosidic link to connect into of α-L-guluronic acid (being called for short G).Its section chain structure has three types: the M block of being made up of the continuous N unit, G block that is formed by continuous G unit and the MG block that is connected to form by G unit and M units alternately.Algin also is one type of seaweed chemical product the most representative, has according to data presentation, at present high the occupying first place in the world of China's algin YO.For ease of preserving and using, generally algin is converted into sodium alginate as the finished product.As the sodium salt of a kind of polyanionic polysaccharide (Lalgine), sodium alginate has purposes very widely with its inherent physico-chemical property in industry.In foodstuffs industry, the sodium alginate low-heat is nontoxic, it is expanded to be prone to, suppleness is high, add to can play in the food solidify, thickening, emulsification, suspension, stable and prevent many functions such as food drying, be a kind of good edible additive.In textile industry, characteristics such as sodium alginate has that easy coloring, dye yield are high, lovely luster and PRINTED FABRIC are soft are thickeners the most frequently used in the cotton fabric by utilizing reactive dye stamp.Simultaneously it also can be used as the water soluble fiber that warp size, waterproof processing, manufacturing lace such as use at technological process.Sodium alginate is as toothpaste base-material, shampoo, hair mousse etc. in cosmetic industry.On paper industry, can be used as applying glue, in rubber industry, be used as the latex enriching agent, can also process water-borne coatings and water tolerance coating.Sodium alginate still is a kind of important bio-medical material; Be widely used as medicinal slow release agent, polymeric film, cell encapsulation, wound dressings, operation sponge and suppository etc., receiving increasing concern in fields such as bio-medical material, clinical medicine, organizational engineering and pharmacology.
So far, alkali digestion technology is still continued to use in the production of algin basically, and ultimate principle is to utilize soda ash (Na
2CO
3) change into sodium alginate to various water-fast alginates, and be dissolved in the water, the exsiccant sodium alginate powder obtained again after filtering.
Fucoidin is a kind of mixed polysaccharide, forms except containing Fucose and sulfate radical, also contains monose such as semi-lactosi, wood sugar, seminose and uronic acid.Owing to have particular structure and excellent physiologically active; Like regulating blood fat, hypoglycemic, hypotensive, anticoagulation, antitumor, mutation and radioprotective, antiviral, raise immunity etc., fucoidin has become one of focus of marine drug research in this century.Laminaran has another name called laminarin, is a kind of polysaccharide with multiple physiologically active equally.The waste of producing main utilization production algin, iodine and N.F,USP MANNITOL of fucoidin and laminaran is main raw material, classification alcohol precipitation after flooding.
The main drawback of existing algin producing and manufacturing technique:
1) the water consumption power consumption is serious, pollutes big.This also is a restriction seaweed industry development key factor.The alkali digestion technological principle is simple, but often needs tens of roads process in the practical commercial manufacture, and some step is very difficult.For example sea-tangle is handled compositions such as many water-fast Mierocrystalline celluloses are arranged in the sodium alginate underflow that forms through SPC-D needs filtering; Because underflow viscosity is too high; Except flocculating aidss such as needs adding zeyssatite, also need consume a large amount of water dilutes, and requires very high to quality of water.According to statistics, produce 1 ton of finished product sodium-alginate and need use 700-1000 ton water approximately.In addition; The chemical process of existing alkali digestion technology mainly contains and adds acid and add two kinds of methods of calcium salt: at first convert water-fast alginate in the brown alga to water-soluble sodium alginate; Adding acid or calcium ion makes sodium alginate form alginic acid or calcium alginate deposition; Clean the back then and change back sodium alginate, further be processed into various product to sodium alginate more at last.No matter adopt which kind of method, a large amount of trade effluents that all will produce have constituted serious threat to ecotope.
2) range of product is single, and it is excellent that quality is owed, and added value is low.The classification of sodium alginate on structure, can be divided into high G/M than, G/M than, low G/M than three kinds; On viscosity, can be divided into ultra-low viscosity, LV, medium-viscosity, HV and hyperviscosity sodium alginate; Can be divided on the purity industrial, edible and medical three ranks.Probably there is Er Shijia in China Lalgine manufacturing enterprise.Through the development of decades, China has become Lalgine big producing country.But China is particularly also existing very big gap aspect the exploitation of developing high-grade Lalgine raw material and high added value derived product compared with developed countries on the degree of depth and range of Application and Development Lalgine.The field, particularly Chinese Enterprise that it is very fierce that Lalgine industry is a competition adopts the strategy of low price to make most of Lalgine industry be in low profit state, only in high-end applications fields such as medical and health bigger profit margin arranged.The restriction of characteristics such as the sodium alginate that China domestic enterprise produces is the medium-viscosity product mostly, and it is stronger to receive its gelling as the pharmaceutical product application that keeps healthy, and solubleness is low, activity can not get demonstrating fully.Above-mentioned many reasons all make the present a lot of seaweed gel manufacturing enterprise of China manage very difficulty.
For breaking through above-mentioned predicament, the researchist is not enough to above each item both at home and abroad, has done long-term and unremitting effort in a plurality of links, and many researchs are fruitful, obtained some important progress.These researchs comprise the improvement of old technology and the exploitation of novel process; Extrude novel process such as the algin reaction of foreign scholar's report recently; Just possess water saving simultaneously, save time, the alkali consumption is few; And the viscosity of product and yield all have raising in various degree, but from problems such as costs, this equipment does not also obtain promoting at present.The modification of traditional Sargassum polysaccharides product comprised utilize biological, chemistry or physical method, sodium alginate and fucoidin are degraded to algin oligosaccharide, oligosaccharides and lower molecular weight Fucose, the sulphur content of fucoidin such as is adjusted at measure.Result of study also confirms; The sodium alginate after the degraded and the activity of fucoidin have obtained improving effectively; Some low-molecular-weight algal acid sodium has had the antitumor and antiviral physiologically active of similar heparin, can be used for the medicinal research of cardiovascular and cerebrovascular diseases and viral aspect.Some has effects such as whole intestines and detoxifcation, hypoglycemic blood fat, anticoagulation, anti-inflammatory, immunomodulatory, can be used as mellitus, obesity, carcinoma of the colon and rectum, habitual constipation patient's dietetic food.Especially in recent years, the physiological action of the low-molecular-weight algal glue after process is modified or the uniqueness of fucoidin constantly comes to light out, and the research of its activity and pharmaceutical use has become one of new research focus.In addition, POLYMANNURONATE is peculiar in the algin molecule with gathering guluronic acid, does not find to have this compounds of exist singly as yet at occurring in nature.And in the algin ratio (M/G), the block of two kinds of uronic acid glycan structure and arrangement etc. not simultaneously, its performance can show remarkable difference.Therefore, also have many researchers to obtain this class formation unique polysaccharide fragment and oligosaccharides thereof through different degradeds, separation method, it is active to study its unique biological, becomes the medicine with special efficacy in the hope of exploitation.Serial oligose or oligosaccharides that all these structures are different have greatly enriched the variety of Sargassum polysaccharides product.But above-mentioned these researchs are raw material with the medium-viscosity algin all, fundamentally do not solve problems such as existing water consumption consumes energy in the sodium alginate traditional processing technology, seriously polluted.Therefore, be necessary to carry on the research and development of ocean science and seaweed industry novel process, new technology, product innovation.
Summary of the invention
To water consumption power consumption, seriously polluted in the course of processing that exists in the prior art; Weak points such as the product activity can not get demonstrating fully; The technical problem that the present invention will solve is to provide a kind of and directly in the brown alga raw material, algal polysaccharide (sodium alginate, fucoidin etc.) is degraded to oligose and oligosaccharides; Improve its biological activity, reduce and extract solvent load, water saving, the reduction of discharging that realizes technological process is the method for from brown alga, extracting active polysaccharide of purpose.
In order to solve above-mentioned technical problem, the technical scheme that the present invention adopts is described below:
A kind of method of from brown alga, extracting active polysaccharide is characterized in that: comprise following step:
1) will place extraction vessel through the phaeophyta raw material after clean, drying, the pulverizing, and add organic acid soln or organic and inorganic mixed acid solution, fully stirring makes evenly wetting;
2) heat treated: the material heating to step 1) after wetting, temperature is 50-150 ℃, soaking time is 10-180min, utilizes the organic acid molecule appropriateness to cut off the glycosidic link of brown alga macromolecule polysaccharide, realizes its part degraded;
3) utilize organic solvent to carry out thorough washing, accomplish the organic acid pre-treatment of brown alga to getting rid of acid solution in the most material;
4) through pretreated brown alga, add 5-8 times of water by volume and extract, extracting solution concentrates, and regulates pH value to neutral back classification alcohol precipitation and obtains the water-soluble good algin, fucoidin and the laminaran that are rich in mannuronic acid fragment (rich M) respectively;
5) the organic acid pre-treatment brown alga raw material residue after process water is carried is handled by alkali digestion technology again, can obtain to be rich in the algin of guluronic acid fragment (rich G).
The weight ratio of brown alga powder and organic acid soln or organic and inorganic mixed acid solution is 5/1-1/5 in the step 1).Phaeophyta is selected from Laminaria (Laminaria) sea-tangle; Sargassum (Sargassum) Sargassum, sargassum kjellmanianum Yendo, Sargassum fusiforme, mouse tail algae, a sargassun of crawling; Fucus (Fucus) rock algae, black wrack; Killeen (Pelvetia) siliquosa Pelvetia, undaria (Undaria) wakame, Macrocystis (Maerocystis) bulk kelp.
Said organic acid soln is selected from a kind of in the propionic acid aqueous solution of acetate and 10%-99% of formic acid, mass percent concentration 10%-99% of oxalic acid that mass percent concentration is 5%-50%, mass percent concentration 10%-99%.
Mineral acid is selected from hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid in the organic and inorganic nitration mixture, and the mass percent concentration of mineral acid is 0.1%-15%. in the organic-inorganic nitration mixture
The organic solvent that is used for washing acid residues is selected from alcohol or acetone a kind of of C1-C3.
When the organic acid in said organic acid soln or the organic and inorganic mixed acid solution is selected oxalic acid solution for use, handle the back and adopt organic solvent washing to remove residual oxalic acid; When the organic acid in said organic acid soln or the organic and inorganic mixed acid solution is selected from formic acid, acetate, propionic acid solution, adopt distillation, the centrifugal or most of residual acid of filtration removal after the processing earlier, adopt organic solvent washing to remove the acid of small amount of residual again.
Step 4) classification alcohol precipitation is for adding ethanol to containing alcohol amount 20wt%-40wt%; Filtering perhaps, spinning goes out deposition; It is the segmental oligomeric algin deposition of rich M that the mannuronic acid fragment is rich in acquisition, adds ethanol when containing alcohol amount 60wt%-70wt%, filters or spinning can obtain the fucoidin deposition; Add ethanol when containing alcohol amount 80wt%-85wt%, filter or spinning can obtain the laminaran deposition.
The segmental oligomeric algin deposition adding yellow soda ash of rich M transforms and obtains rich M fragment sodium alginate.
The algal polysaccharide of different structures such as said rich M fragment algin, fucoidin, laminaran and rich G fragment algin is to be raw material with the pretreated brown alga of organic acid, obtains through steps such as flooding, classification alcohol precipitation, alkali digestions respectively.
The principle of the invention is: when brown alga raw material and the heating of organic acid mixed system; Organic acid carries out the degraded of gentle appropriateness to organic macromolecule polysaccharide such as algins in the brown alga; Polysaccharide material with different molecular structures is different to the susceptibility of organic acid effect; Thereby selectively fracture glycosidic link wherein obtains structure and unique algal polysaccharide product.For example: have M-M, G-G, three kinds of glycosidic links of M-G in the algin; Wherein M-M, G-G glycosidic link are more insensitive to organic acid; And the M-G glycosidic link is comparatively responsive to organic acid, the organic acid M-G glycosidic link that optionally ruptures, so algin is degraded to rich M fragment and rich G fragment.Rich M fragment is water-soluble good, need not pass through digestion and just can propose smoothly, and because molecular weight reduces, extract water loss and significantly reduce.Water-soluble relatively poor rich G fragment then remains in the brown alga residue, can propose through alkali digestion technology.Like this, not only the algal polysaccharide of different molecular structures obtains separating, and has reduced water of productive use significantly and used alkali, has simplified the treating processes of technological process and sewage.Simultaneously, the reduction of product algal polysaccharide molecular weight, water-soluble enhancing, favourable its bioactive expression, thus improved value-added content of product.
The advantage of organic acid pre-treatment algal polysaccharide technology:
Special ocean living environment makes the brown alga cell have firm Mierocrystalline cellulose cell walls, and cellularstructure is tight, and is strong but pliable in texture, and wherein contained effective constituent is difficult for being extracted.And; Natural algal polysaccharide has generally that molecular weight is big, poorly water-soluble, in human body, be difficult for problem such as absorption; Therefore; How algal polysaccharide (sodium alginate, fucoidin etc.) is degraded to oligose and oligosaccharides, has become one of research focus of present marine drug thereby improve its biological activity.
Under certain condition, organic acid makes plant cell wall glucide (Mierocrystalline cellulose and semicellulose) partly hydrolysed take place and stripping.If in the extraction of brown alga active polysaccharide, use this organic acid system; Just might pass through the CONTROL PROCESS condition; Make brown alga cell walls cellulosic and phycocolloid class material that the part degraded take place; Thereby change the structural sheet of brown alga cell walls, when making in the born of the same parents the rapid stripping of effective constituent, cell wall polysaccharide also is able to discharge as early as possible.Adopt the moderate organic acid system of acid intensity, also possibly in the process of extracting, under mild conditions, the molecular structure of algal polysaccharide suitably degraded, improve its inherent structure and physico-chemical property, improve its biological activity.Therefore the invention provides a kind of from brown alga the method for high efficiency extraction active polysaccharide, promptly utilize the organic acid soln appropriateness to cut off the glycosidic link in the algal polysaccharide molecule, thereby obtain the polysaccharide product of high added value.Simultaneously, because the change of raw material cell wall structural sheet makes that extracting solvent load significantly reduces, therefore realized water saving, the reduction of discharging purpose of technological process.
Therefore compared with prior art, the present invention has more following advantage:
1. after adopting the organic acid pre-treatment, water saving and emission reduction effect are remarkable, and water consumption is the 1/4-1/5 of traditional method; The alkali charge of this technology digestive process is about the 1/2-1/3 of old digestion process;
2. be compared to traditional technology, novel process polysaccharide product yield is improved, and particularly fucoidin is the highest improves about 1 times;
3. leaching process had both directly been realized the polysaccharide molecule structure regulating; The acquisition molecular-weight average is low, range of molecular weight distributions is narrow, water-soluble good high added value polysaccharide product; The rich M algin of also direct realization separates with rich G algin; And the sulfate radical content of fucoidin gets and also obtained adjustment, is expected to keeping its active its toxic side effect that reduces simultaneously.The novel process polysaccharide product has special advantages as exploitations such as medicine, protective foodss.
Description of drawings
Fig. 1 is a process schematic representation of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is done further explain.
Comparative example 1
Take by weighing the sea-tangle powder raw material of 100 grams after clean, drying, pulverizing and put into the beaker of 2L; Add 1L water and 20g yellow soda ash and in 70 ℃ hot water bath, stirred 1 hour, the water with 80-100L carries out fully stirring after-filtration towards rare then; Filtrating adds hydrochloric acid and regulates pH value to 2.0; Spinning adds yellow soda ash and transforms in the deposition, obtain sodium alginate.Centrifugal gained supernatant is used ethanol precipitation, adds ethanol and can obtain fucoidin to containing when alcohol is measured 65wt%, adds ethanol and can obtain laminaran to containing when alcohol is measured 85wt%.Each calculates extraction yield respectively after going on foot the product drying, and extraction yield is the percentage ratio of the mass ratio of each step product and raw material sea-tangle powder.And with the extraction yield of polysaccharide component in this three main laminaria of sodium alginate, fucoidin and laminaran, and the data such as viscosity of the total water consumption in the technological process, sodium alginate product compare.Sodium alginate product utilization traditional method carries out must forming behind the purifying monomer polysaccharide of homogeneous, adopts H
1-NMR method is measured its POLYMANNURONATE fragment (M) and guluronic acid fragment (G) ratio M/G.Adopt Ubbelohde viscometer to measure sodium alginate viscosity 25 ℃ of water-baths.Adopt sulfate radical content in the turbidimetry for Determination fucoidin.All analytical resultss are seen table 1.
Embodiment 1
Process schematic representation as shown in Figure 1, carry out according to following technology:
1) the dried sea-tangle powder of 1.5kg places the extraction vessel of 10L;
2) get anhydrous formic acid 1L, add water 0.5L and be made into formic acid solution 1.5L;
3) with step 2) in formic acid solution 1.5L, be added in the extraction vessel in the step 1), fully stir and make the sea-tangle powder evenly wetting;
4) the wetting material that obtains of step 3) is heated to 100 ℃, behind the insulation 20min, and underpressure distillation, no obvious liquid to the extraction vessel.
5) advanced in the step 4) in the extraction vessel after the underpressure distillation to add absolute ethyl alcohol 5L, and fully stirred, and filtered, ethanol is reclaimed in the filtrating distillation, is after the filter residue and drying through the pretreated sea-tangle powder of organic acid.
6) get organic acid pre-treatment sea-tangle powder 100 grams in the step 5), put into the beaker of 1L, add 500ml zero(ppm) water; In 70 ℃ hot water bath, extract 40min, filter, repeat said process 1 time; Merge filtrating and extremely neutral with sodium carbonate solution accent PH twice, filter residue is subsequent use.
7) filtrating concentrates back classification alcohol precipitation in the step 6), adds ethanol to containing alcohol amount 30wt%, and deposition obtains the segmental sodium alginate of rich M; Add ethanol and obtain fucoidin to containing alcohol amount 65wt% deposition; Add ethanol and obtain laminaran for the 85wt% deposition to containing the alcohol amount.
8) adding 6g yellow soda ash and 500ml water in the step 6) gained filter residue stir 40min in 70 ℃ hot water bath, filter, and filtrating adjusting pH value extremely concentrates the neutrality back, and alcohol precipitation (adding ethanol extremely precipitates till the no longer appearance) obtains the segmental alginic acid of rich G and receives.
The test POLYMANNURONATE fragment (M) with guluronic acid fragment (G) ratio M/G, sodium alginate viscosity and fucoidin in sulfate radical content method all with comparative example 1 in condition identical; Each goes on foot the product extraction yield, and data results such as sulfate radical content is seen table 1 in the viscosity of the total water consumption in the technological process, sodium alginate product, fucoidin.Wherein the extraction yield of polysaccharide all is weight ratios of gained title product and total raw material.The fucoidin sulfate radical content is meant the mass percent of sulfate radical in the fucoidin molecule.
Table 1 organic acid pre-treatment sea-tangle dry powder and unprocessed dried seaweed powder raw material respectively go on foot polysaccharide product extraction yield, total water amount and sodium alginate viscosity comparable situation:
Comparative example 2
Take by weighing the Sangassivm fuciforime (Harv) Setch powder raw material of 100 grams after clean, drying, pulverizing and put into the beaker of 2L; Add 1L water and 25g yellow soda ash and in 70 ℃ hot water bath, stirred 1 hour, the water with 80-100L carries out fully stirring after-filtration towards rare then; Filtrating adds hydrochloric acid and regulates pH value to 2.0; Spinning adds yellow soda ash and transforms in the deposition, obtain sodium alginate.Centrifugal gained supernatant is used ethanol precipitation, can obtain fucoidin (adding ethanol to containing alcohol amount 65wt%) and laminaran (adding ethanol to containing alcohol amount 85wt%).The product parametric measurement method is with embodiment 1.All analytical resultss are seen table 2.
Embodiment 2
1) the dried Sangassivm fuciforime (Harv) Setch powder of 1.5kg places extraction vessel;
2) get oxalic acid 180g, add water 2.0L and be made into oxalic acid solution;
3) get step 2) in oxalic acid solution 2L, be added in the extraction vessel in the step 1), fully stir and make dried Sangassivm fuciforime (Harv) Setch powder evenly wetting;
4) material of step 3) is heated to 80 ℃, behind the insulation 20min, and underpressure distillation (extraction vessel in WP be 100mmHg), no obvious liquid to the extraction vessel.
5) add absolute ethyl alcohol 5L in the step 4) in the extraction vessel after the underpressure distillation, fully stir, filter, ethanol and oxalic acid are reclaimed in the filtrating distillation, are organic acid pre-treatment Sangassivm fuciforime (Harv) Setch powder after the filter residue and drying.
6) get pretreated Sangassivm fuciforime (Harv) Setch powder 100 grams of organic acid in the step 5), put into the beaker of 1L, add 500ml zero(ppm) water; In 70 ℃ hot water bath, extract 40min, filter, repeat said process 1 time; Merge filtrating and extremely neutral with sodium carbonate solution accent PH twice, filter residue is subsequent use.
7) filtrating concentrates back classification alcohol precipitation in the step 6), adds ethanol to containing alcohol amount 30wt%, and deposition obtains the segmental sodium alginate of rich M; Add ethanol to containing alcohol amount 65wt%, deposition obtains fucoidin; Add ethanol to containing alcohol amount 85wt%, deposition obtains laminaran.
8) add 6g yellow soda ash and 500ml water in the step 6) gained filter residue, in 70 ℃ hot water bath, stir 40min, filter, filtrating is regulated the extremely neutral back of pH value and is concentrated, and alcohol precipitation (add ethanol, occur to precipitating no longer) obtains the segmental alginic acid of rich G and receives.
In test POLYMANNURONATE fragment (M) and the fucoidin equal with guluronic acid fragment (G) ratio M/G, sodium alginate viscosity the method for sulfate radical content all with comparative example 1 in identical; Each goes on foot the product extraction yield, and data results such as viscosity of the total water consumption in the technological process, sodium alginate product, fucoidin sulfate radical content is seen table 2.
The relatively situation such as polysaccharide product extraction yield, total water amount, sodium alginate viscosity and fucoidin sulfate radical content that respectively goes on foot of table 2 organic acid pre-treatment Sargassum fusiforme dry powder and unprocessed Sargassum fusiforme dry powder raw material:
Comparative example 3
Take by weighing the Algemin raw material of 100 grams after clean, drying, pulverizing and put into the beaker of 2L; Add 1L water and 25g yellow soda ash and in 70 ℃ hot water bath, stirred 1 hour, the water with 80-100L carries out fully stirring after-filtration towards rare then; Filtrating adds hydrochloric acid and regulates pH value to 2.0; Spinning adds yellow soda ash and transforms in the deposition, obtain sodium alginate.Centrifugal gained supernatant is used ethanol precipitation, can obtain fucoidin (adding ethanol to containing alcohol amount 65wt%) and laminaran (adding ethanol to containing alcohol amount 85wt%).The product parametric measurement method is with embodiment 1.All analytical resultss are seen table 3.
Embodiment 3
1) the dried Algemin of 1.5Kg places the extraction vessel of 10L;
2) get anhydrous acetic acid 0.8L, add water 0.2L and be made into acetic acid soln 1L;
3) get step 2) acetic acid soln 1L, be added in the extraction vessel in the step 1), fully stir make evenly wetting;
4) the wetting material of step 3) is heated to 60 ℃, and behind the insulation 60min, organic acid soln is got rid of in underpressure distillation, no obvious liquid to the extraction vessel.
5) through adding methyl alcohol 5L in the extracting container of step 4), fully stir, filter, methyl alcohol is reclaimed in the filtrating distillation, is organic acid pre-treatment Algemin after the filter residue and drying;
6) get the dried organic acid pre-treatment of step 5) Algemin 100 grams, put into the beaker of 1L, add 500ml zero(ppm) water, in 70 ℃ hot water bath, extract 40min, filter, repeat 1 time, merge filtrating and extremely neutral with sodium carbonate solution accent PH twice, filter residue is subsequent use.
7) filtrating concentrates back classification alcohol precipitation in the step 6), adds ethanol to containing alcohol amount 30wt%, and deposition obtains the segmental sodium alginate of rich M; Add ethanol and contain alcohol amount 65wt%, deposition obtains fucoidin; Add ethanol to containing alcohol amount 85wt%, deposition obtains laminaran.
8) add 6g yellow soda ash and 500ml water in the step 6) gained filter residue, in 70 ℃ hot water bath, stir 40min, filter, filtrating is regulated the extremely neutral back of pH value and is concentrated, and alcohol precipitation (add ethanol, occur to precipitating no longer) obtains the segmental alginic acid of rich G and receives.
The test POLYMANNURONATE fragment (M) with guluronic acid fragment (G) ratio M/G, sodium alginate viscosity and fucoidin in sulfate radical content method all with comparative example 1 in condition identical; Each goes on foot the product extraction yield, and data results such as sulfate radical content is seen table 3 in the viscosity of the total water consumption in the technological process, sodium alginate product, fucoidin.
Table 3 organic acid pre-treatment bulk kelp dry powder and unprocessed bulk kelp dry powder raw material respectively go on foot polysaccharide product extraction yield, total water amount, sodium alginate viscosity and fucoidin sulfate radical content comparable situation:
Comparative example 4
Take by weighing the wakame raw material of 100 grams after clean, drying, pulverizing and put into the beaker of 2L; Add 1L water and 25g yellow soda ash and in 70 ℃ hot water bath, stirred 1 hour, the water with 80-100L carries out fully stirring after-filtration towards rare then; Filtrating adds hydrochloric acid and regulates pH value to 2.0; Spinning adds yellow soda ash and transforms in the deposition, obtain sodium alginate.Centrifugal gained supernatant is used ethanol precipitation, can obtain fucoidin (adding ethanol to containing alcohol amount 65wt%) and laminaran (adding ethanol to containing alcohol amount 85wt%).The product parametric measurement method is with embodiment 1.All analytical resultss are seen table 4.
Embodiment 4
Be with embodiment 1 difference:
1) wakame of 1.5kg after dry removal of impurities, pulverizing places extraction vessel;
2) get anhydrous formic acid 1L, add water 0.45L, add 10% sulphuric acid soln and be made into formic acid-sulfuric acid mixed acid solution 1.5L;
3) get above-mentioned solution 1.5L, be added in the said extracted container, fully stirring makes evenly wetting;
4) above-mentioned material is heated to 110 ℃, behind the insulation 20min, is cooled to room temperature, filters, and the filtrating part is distilled recyclable organic acid soln.
5) above-mentioned steps 4) in filter residue partly add absolute ethyl alcohol 5L, fully stir, filter.Ethanol is reclaimed in the filtrating distillation, is organic acid pre-treatment undaria powder after the filter residue and drying.
6) get above-mentioned steps 5) in organic acid pre-treatment undaria powder 100 gram, put into the beaker of 1L, add 500ml zero(ppm) water; In 70 ℃ hot water bath, extract 40min, filter, repeat said process 1 time; Merge filtrating twice, transfer PH to neutral with sodium carbonate solution, filter residue is subsequent use.
7) filtrating concentrates back classification alcohol precipitation in the step 6), adds ethanol to containing alcohol amount 30wt%, and deposition obtains the segmental sodium alginate of rich M; Add ethanol and obtain fucoidin to containing alcohol amount 65wt% deposition; Adding ethanol contains alcohol amount 85wt% deposition and obtains laminaran.
8) add 6g yellow soda ash and 500ml water in the step 6) gained filter residue; In 70 ℃ hot water bath, stir 40min; Filter, filtrating is regulated pH value and is concentrated to neutral back, and alcohol precipitation (adds ethanol; Making polysaccharide precipitation wherein come out, generally is to be added to till deposition no longer occurs) obtain the segmental alginic acid of rich G and receive.
The test POLYMANNURONATE fragment (M) with guluronic acid fragment (G) ratio M/G, sodium alginate viscosity and fucoidin in sulfate radical content method all with comparative example 1 in condition identical; Each goes on foot the product extraction yield, and data results such as sulfate radical content is seen table 4 in the viscosity of the total water consumption in the technological process, sodium alginate product, fucoidin.
Pre-treatment of table 4 organic acid and unprocessed raw material respectively go on foot polysaccharide product extraction yield, total water amount, sodium alginate viscosity and fucoidin sulfate radical content comparable situation:
Result and analysis:
From comparative example and embodiment, can find out, can reduce extraction water consumption and digestion alkali charge in the existing technology significantly, obtain having the segmental LV sodium alginate of different M/G product through method of the present invention.In addition, adopt present method when improving the fucoidin extraction yield, to make sulfate radical content wherein be in a moderate scope.
Claims (9)
1. method of from brown alga, extracting active polysaccharide is characterized in that: comprise following step:
1) will put in the extraction vessel through the phaeophyta raw material after clean, drying, the pulverizing, and add organic acid soln or organic and inorganic mixed acid solution, fully stirring makes evenly wetting;
2) heat treated: the material heating to step 1) after wetting; Temperature is 50-150 ℃, and soaking time is 10-180min, and the WP of extraction vessel is 20mmHg-760mmHg; Utilize the organic acid molecule appropriateness to cut off the glycosidic link of brown alga macromolecule polysaccharide, realize its part degraded;
3) utilize organic solvent to carry out thorough washing, get rid of acid solution in the material, accomplish the organic acid pre-treatment of brown alga;
4) through pretreated brown alga, add 5-8 times of water by volume and extract, extracting solution concentrates, and regulates pH value to neutral back classification alcohol precipitation, obtains water-soluble good mannuronic acid fragment (rich M) algin, fucoidin and the laminaran of being rich in respectively;
5) the organic acid pre-treatment brown alga raw material residue after process water is carried is handled by alkali digestion technology again, can obtain to be rich in the algin of guluronic acid fragment (rich G).
2. according to the described method of from brown alga, extracting active polysaccharide of claim 1, it is characterized in that: the weight ratio of brown alga powder and organic acid soln or organic and inorganic mixed acid solution is 5/1-1/5 in the step 1).
3. according to the described method of from brown alga, extracting active polysaccharide of claim 1; It is characterized in that: described phaeophyta is selected from the Laminaria sea-tangle; Sargassum Sargassum, sargassum kjellmanianum Yendo, Sargassum fusiforme, mouse tail algae, a sargassun of crawling, fucus rock algae, black wrack; Killeen siliquosa Pelvetia, undaria wakame and/or Macrocystis bulk kelp.
4. by the method for extracting active polysaccharide in the described brown alga of claim 1; It is characterized in that: concentration by mass percentage, said organic acid soln are selected from a kind of in the propionic acid aqueous solution of acetate or 10%-99% of formic acid, 10%-99% of oxalic acid, the 10%-99% of 5%-50%.
5. by the described method of from brown alga, extracting active polysaccharide of claim 1, it is characterized in that: the mineral acid mass percent concentration is 0.1%-15% in the organic and inorganic mixed acid solution, and mineral acid is selected from a kind of in hydrochloric acid, sulfuric acid, nitric acid or the phosphoric acid.
6. by the described method of from brown alga, extracting active polysaccharide of claim 1, it is characterized in that: the organic solvent that is used for washing acid residues is selected from alcohol or acetone a kind of of C1-C3.
7. by claim 1, the 4 or 6 described methods of from brown alga, extracting active polysaccharide; It is characterized in that: when organic acid soln is selected from formic acid, acetate, propionic acid solution; At first adopt distillation, centrifugal, filter method to remove most of acid solution in the step 3), select for use organic solvent washing to remove the acid of small amount of residual again.
8. by the described method of from brown alga, extracting active polysaccharide of claim 1; It is characterized in that: step 4) classification alcohol precipitation filters perhaps spinning and goes out to precipitate for adding ethanol to containing alcohol amount 20wt%-40wt%, and obtaining to be rich in the mannuronic acid fragment is the segmental oligomeric algin deposition of rich M; Add ethanol when containing alcohol amount 60wt%-70wt%; Filter or spinning can obtain the fucoidin deposition, add ethanol when containing alcohol amount 80wt%-85wt%, filter or spinning can obtain the laminaran deposition.
9. by claim 1 or the 8 described methods of from brown alga, extracting active polysaccharide, it is characterized in that: the segmental oligomeric algin deposition of rich M adds yellow soda ash and is converted into rich M fragment sodium alginate.
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