CN107474155A - The method for preparing algin oligosaccharide using ultrasound and light wave auxiliary - Google Patents

The method for preparing algin oligosaccharide using ultrasound and light wave auxiliary Download PDF

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Publication number
CN107474155A
CN107474155A CN201710821566.4A CN201710821566A CN107474155A CN 107474155 A CN107474155 A CN 107474155A CN 201710821566 A CN201710821566 A CN 201710821566A CN 107474155 A CN107474155 A CN 107474155A
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China
Prior art keywords
light wave
algin
steps
concretely comprises
glue
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CN201710821566.4A
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CN107474155B (en
Inventor
吴仕鹏
程跃谟
封凯
于云霞
张璇
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QINGDAO JUDAYANG ALGAE INDUSTRY GROUP Co Ltd
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QINGDAO JUDAYANG ALGAE INDUSTRY GROUP Co Ltd
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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
    • C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02—Monosaccharides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/04—Disaccharides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/06—Oligosaccharides, i.e. having three to five saccharide radicals attached to each other by glycosidic linkages

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • Genetics & Genomics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Saccharide Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The method that the present invention prepares algin oligosaccharide using ultrasound and light wave auxiliary.Using sodium alginate raw material, by modes such as dissolving, refined filtration, acidifying, degraded, neutralization, alcohol precipitation, drying, algin oligosaccharide is prepared.Requirement of the client for ultra-low viscosity algin is reached.Chemical substance is not added and interrupts strand, and technique is advanced, realizes clean manufacturing.Product property is stable, and molecular weight is low.Step is simple and convenient to operate, is practical.

Description

The method for preparing algin oligosaccharide using ultrasound and light wave auxiliary
Technical field
The present invention relates to marine alga comprehensive processing and utilization, in particular with the ultrasonic skill that algin oligosaccharide is prepared with light wave auxiliary Art.
Background technology
Algin oligosaccharide is the oligomer of algin, is a kind of functional oligosaccharide.Brown alga oligose is by β-D mannuronic acids (ManA) it is formed by connecting with its C-5 epimer α-L guluronic acid (GulA) by 1-4 glycosidic bonds.Brown alga oligose molecule Low, not only water-soluble strong, stability height is measured, and there are many bioactivity, such as antitumor, anti-oxidant, antibacterial, growth promotion Deng having wide DEVELOPMENT PROSPECT in fields such as drug development, development of functional food, green agricultures.
Preparing algin oligosaccharide uses traditional handicraft at present, such as Pressurized-heated digestion process, addition hydrogen peroxide, addition time chlorine Sour sodium oxidative degradation, high pressure acidolysis, the mode of irradiation, enzymolysis process etc..It has production technology backwardness, yields poorly, production Algin oligosaccharide is unstable, high energy consumption, easily causes the algin oligosaccharide that chemical residue, production cycle are long, cost is high, produce Molecular weight is big, and viscosity is high, the shortcomings of not reaching customer requirement.
Chinese patent CN200610069060.4 discloses a kind of brown alga prepared using algin as raw material as bacteriostatic agent The method of glue oligosaccharides, feature are the alginate solution to 1-5% with ultrasonic wave, are degraded under being 2-5 in 40-80 DEG C of temperature, pH value After 7-10 hours, degradation solution adds absolute ethyl alcohol and carries out alcohol analysis, filters, and drying, grinds and produces algin oligosaccharide, its average polymerization Degree less than 10.But its degradation time is longer, high energy consumption.
Tai is extensive《Progress prepared by algin oligosaccharide》One text is pointed out：Ultraviolet irradiation method is that a kind of new degraded is brown Phycocolloid method.Under the conditions of existing for photochemical catalyst titanium dioxide, more than ultraviolet irradiation sodium alginate aqueous solution 3h can part water Solve sodium alginate.The relative molecular mass of catabolite is relatively low, and G/M ratios are similar to acid degradation method product.This method it is excellent Gesture is not needing special equipment, it is not necessary to the strict control of temperature and titanium dioxide are easily removed, can be obtained purer Product.But the degradation efficiency of ultraviolet irradiation method is too low, reaction mechanism is indefinite, still needs to make further research improvement, to adapt to The requirement of large-scale production.
The content of the invention
In order to overcome above-mentioned deficiency, the present invention is degraded using light wave, thoroughly interrupts strand, be preferably minimized viscosity, point The sub- degree of polymerization reaches minimum.The solution of ultra-low viscosity algin product viscosity 1% of Laboratory Production at present<10mpas, 10% is molten Liquid 100-800mpas, requirement of the client for ultra-low viscosity algin is reached.Chemical substance is not added interrupts strand, work Skill is advanced, realizes clean manufacturing.Product property is stable, and molecular weight is low.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of method for preparing algin oligosaccharide using ultrasound and light wave auxiliary, including：
Sodium alginate is dissolved in the aqueous solution, filtering, acidifying, dehydration, degraded, alkali neutralization, alcohol precipitation, drying, crushing, produced；
The degraded includes：Ultrasonic degradation and light degradation.
In order to overcome existing ultrasonotomography, the problem of ultraviolet irradiation method degradation efficiency is low, the present invention is to algin in difference The mechanism of action under degraded mode has carried out system research, attempts to improve the drop of algin by way of multifactor collaboration processing Speed is solved, is chanced in large scale experiment：Alginic acid after ul-trasonic irradiation, can make two kinds of uronic acids of connection Isosorbide-5-Nitrae-glycosidic bond becomes active, then Isosorbide-5-Nitrae-glycosidic bond is accelerated fracture by optical wavelength radiation, and degradation efficiency is substantially improved, and entirely Process is not required to add catalyst, and the algin product viscosity of final obtained high-purity is up to 1% solution<10mpas, 10% solution 100-800mpas。
Preferably, the acidifying concretely comprises the following steps：Alginic glue after filtering is added into hydrochloric acid, stirring, aging.
The algin that prior art typically uses makees raw material, causes preparation process just to lose a part of yield, then molten Solution is lower to the utilization rate of raw material.Therefore, the present invention is handled the intermediate product alginic acid for producing algin, brown alga is prepared Oligosaccharides yield is higher, and is more suitable for grafting and is produced on current algin production line.
Preferably, the dehydration concretely comprises the following steps：By the glue centrifugal dehydration after acidifying.
Preferably, the degraded concretely comprises the following steps：Alginic acid block is put into ultrasound reactor, set power as 500-1500W, time 0.5-1h, then alginic acid block is transferred in light wave reactor, set light wave power 300-350W, light wave Radiate 30min.
Preferably, the light source that the optical wavelength radiation uses is halide torch (i.e. optical wave tube).
Preferably, the neutralization concretely comprises the following steps：Alginic acid block is added into NaOH solution, regulation pH value is 7-8, is formed Glue.
Preferably, the alcohol precipitation concretely comprises the following steps：The absolute ethyl alcohol of 6-10 times of its volume is added in glue, is stirred, Precipitation is separated out, is precipitated using 200 mesh filter screen filtrations.
Directly with alcohol, alcohol analyses brown alga oligose to prior art from glue, because glue gel content is low, there is substantial amounts of water, ethanol Consumption is high；Glue gel content is high before alcohol analysis of the present invention, separates out equal quality brown alga oligose, glue volume is only before alcohol analysis of the present invention The 1/25-1/5 of existing glue total amount, only a small amount of alcohol need to be added to separate out, alcohol consumption is low.
Preferably, the condition of the drying is that moisture 12%-15% is dried at 60-80 DEG C.
Preferably, the grinding and sieving.
Present invention also offers brown alga oligose prepared by any above-mentioned method.
Present invention also offers above-mentioned brown alga oligose in antitumor, anti-oxidant, antibacterial or growth promotion medicine is prepared Using.Beneficial effects of the present invention
(1) present invention prepares algin oligosaccharides using ultrasound, light wave auxiliary first, in 1-2 hours, institute the time required to degraded Take time short, the strand degree of polymerization of formation can reach less than 10.The degree of polymerization is low.
(2) present invention prepares algin oligosaccharides using ultrasound, light wave auxiliary, and controllability is strong, and the algin oligosaccharides of preparation contains Amount can reach more than 95%.Purity is high.
(3) saboteur's chain of the present invention is not added with any other chemical substance, improves the quality of product.
(4) preparation method of the present invention is simple, preparation efficiency is high, practical, easy to spread.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.
Fig. 1 is the Technology Roadmap of the present invention.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
Embodiment 1
1. dissolving
50g sodium alginate is weighed, adds the distilled water of 50-100 times of its quality, it is quick at normal temperatures with electric mixer Stir 30-40min dissolvings.
2. filtering
Glue is filtered using stainless steel bag filter.
3. acidifying
Glue volume 1/10-1/5 mass concentration 15%-25% hydrochloric acid solution is added, stirs 10-15min, is stood old Change 1h.
4. dehydration
Glue after acidifying is centrifuged into 20min, abandoning supernatant, by Centrifuge Cup bottom solid with 8500r/min rotating speed Sour block is transferred in glass beaker.
5. degraded
Sour block is put into ultrasound reactor, sets power as 500-1500W, time 0.5-1h, then sour block is shifted To light wave reactor, light wave power 300-350W, optical wavelength radiation 30min are set.
6. neutralize
Sour block adds mass concentration 25%-35% NaOH solution while stirring, and regulation pH is 7-8, forms glue.
7. alcohol precipitation
The absolute ethyl alcohol of 6-10 times of its volume is added in above-mentioned glue, is stirred, precipitation is separated out, using 200 mesh screen packs Filtering precipitation.
8. drying
It will precipitate to be placed in baking oven and moisture 12%-15% be dried to using 60-80 DEG C of temperature.
9. crush
Algin oligosaccharide is pulverized and sieved to certain mesh number.
Testing result shows：Obtained algin oligosaccharide content can reach more than 95%, and the strand degree of polymerization can reach 10 Below.
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.

Claims (10)

  1. A kind of 1. method for preparing algin oligosaccharide using ultrasound and light wave auxiliary, it is characterised in that including：
    Sodium alginate is dissolved in the aqueous solution, filtering, acidifying, dehydration, degraded, alkali neutralization, alcohol precipitation, drying, crushing, produced；
    The degraded includes：Ultrasonic degradation and light degradation.
  2. 2. the method as described in claim 1, it is characterised in that the acidifying concretely comprises the following steps：By the algin after filtering Liquid adds hydrochloric acid, stirring, aging.
  3. 3. the method as described in claim 1, it is characterised in that the dehydration concretely comprises the following steps：By the glue after acidifying from The heart is dehydrated.
  4. 4. the method as described in claim 1, it is characterised in that the degraded concretely comprises the following steps：Alginic acid block is put into super In sound wave reactor, power is set as 500-1500W, time 0.5-1h, then alginic acid block is transferred in light wave reactor, if Determine light wave power 300-350W, optical wavelength radiation 30min.
  5. 5. the method as described in claim 1, it is characterised in that the neutralization concretely comprises the following steps：Alginic acid block is added NaOH solution, regulation pH value are 7-8, form glue.
  6. 6. the method as described in claim 1, it is characterised in that the alcohol precipitation concretely comprises the following steps：Its body is added in glue The absolute ethyl alcohol of 6-10 times of product, stirring, precipitation is separated out, precipitated using 200 mesh filter screen filtrations.
  7. 7. method as claimed in claim 7, it is characterised in that the condition of the drying is to be dried to moisture at 60-80 DEG C 12%-15%.
  8. 8. the method as described in claim 1, it is characterised in that the grinding and sieving.
  9. 9. brown alga oligose prepared by the method described in claim any one of 1-8.
  10. 10. application of the brown alga oligose in antitumor, anti-oxidant, antibacterial or growth promotion medicine is prepared described in claim 9.
CN201710821566.4A 2017-09-13 2017-09-13 The method for preparing algin oligosaccharide using ultrasound and light wave auxiliary Active CN107474155B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108285474A (en) * 2018-04-19 2018-07-17 成都欧甘拓展有限公司 The preparation method of sodium alginate or potassium alginate oligosaccharides
CN111410670A (en) * 2020-04-24 2020-07-14 湖南省核农学与航天育种研究所 Method for preparing oligosaccharide by using lignocellulose

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101074246A (en) * 2006-09-21 2007-11-21 寻山集团有限公司 Production and use for algin oligose
CN103565817A (en) * 2013-11-11 2014-02-12 深圳大学 Application of alginate oligosaccharide
CN105315384A (en) * 2014-06-18 2016-02-10 山东大学（威海） Method of producing alginate-derived oligosaccharide through gradient dilution and oxidization

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101074246A (en) * 2006-09-21 2007-11-21 寻山集团有限公司 Production and use for algin oligose
CN103565817A (en) * 2013-11-11 2014-02-12 深圳大学 Application of alginate oligosaccharide
CN105315384A (en) * 2014-06-18 2016-02-10 山东大学（威海） Method of producing alginate-derived oligosaccharide through gradient dilution and oxidization

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
祝玲等: "褐藻胶寡糖潜在药用价值的研究进展", 《中药材》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108285474A (en) * 2018-04-19 2018-07-17 成都欧甘拓展有限公司 The preparation method of sodium alginate or potassium alginate oligosaccharides
CN111410670A (en) * 2020-04-24 2020-07-14 湖南省核农学与航天育种研究所 Method for preparing oligosaccharide by using lignocellulose
CN111410670B (en) * 2020-04-24 2022-03-18 湖南省核农学与航天育种研究所 Method for preparing oligosaccharide by using lignocellulose

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