CN107216404A - A kind of alga oligosaccharides phosphate and preparation method thereof - Google Patents

A kind of alga oligosaccharides phosphate and preparation method thereof Download PDF

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Publication number
CN107216404A
CN107216404A CN201710418424.3A CN201710418424A CN107216404A CN 107216404 A CN107216404 A CN 107216404A CN 201710418424 A CN201710418424 A CN 201710418424A CN 107216404 A CN107216404 A CN 107216404A
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China
Prior art keywords
alga
phosphate
oligosaccharides
alga oligosaccharides
preparation
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CN201710418424.3A
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Inventor
单俊伟
台文静
王海华
郝晓晨
但丽霞
修玉飞
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Weihai Wenxi Biological Technology Co Ltd
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Weihai Wenxi Biological Technology Co Ltd
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Priority to CN201710418424.3A priority Critical patent/CN107216404A/en
Publication of CN107216404A publication Critical patent/CN107216404A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0003General processes for their isolation or fractionation, e.g. purification or extraction from biomass
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • Organic Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Sustainable Development (AREA)
  • Fertilizers (AREA)

Abstract

The invention provides a kind of preparation method for preparing alga oligosaccharides phosphate as raw material using marine alga and phosphate, belong to macromolecular compound modification field, raw material is provided to produce the bio-feritlizer with Plant-stimulating activity.The alga oligosaccharides that the present invention is provided, are that alga oligosaccharides are extracted from marine alga with oxidation degradation method, in alkaline environment, occurs esterification with phosphate, alga oligosaccharides phosphate is prepared, the compound has the effect of plant biological stimulin sample, can be applied to new bio-fertilizer etc..

Description

A kind of alga oligosaccharides phosphate and preparation method thereof
Technical field
The present invention relates to a kind of alga oligosaccharides phosphate compound acted on plant biological stimulin sample, belong to big point The compound-modified field of son.
Background technology
Plant biological stimulin is a kind of when being applied to plant or rhizosphere, and the natural growth course to plant plays thorn Swash effect, strengthen or be beneficial to nutrient absorption, the non-nutritive composition of nutritive effect, abiotic stress drag and crop quality.It is raw Thing stimulin can be done directly on plant, and plant bulk damage will not be caused during use, possess balance plant growth system Maintain plant auxin balance and induction plant to strengthen adverse circumstance the function of defensive ability/resistance ability, plant new old generation can be influenceed Thank, help to excavate crop yield and quality potential, positive acting can be played to plant healthy growth, while also having improves The effect of soil ecology.Biostimulant is neither conventional fertilizers, are less agricultural chemicals, and it is different from common fertilizer, passes through difference Machining function in crop, and whether need not contain nutrient in fastidious product;Different from plant protection product, crop is acted only on Growth vigor, and systemic disease resistance is obtained, there is no any direct killing action to pest and disease damage;It is biological in crop-planting Stimulin is that, as crop nutrition and protectant collaboration role, three cooperates with to maintain the healthy growth of crop.
Phosphorus is the necessary element of plant growth, is the plasmic component of plant cell, growth and propagation lifting to cell Act on.Phosphorus also participates in the photosynthesis of plant life process, the utilization of sugar and starch and the transmittance process of energy.Meanwhile, Phosphate fertilizer can also promote the growth of plant seedling stage root system, plant is done sth. in advance maturation.Plant is in result, and phosphorus is largely transferred to seed In so that full seed.
Alga fertilizer is a kind of bio-organic fertilizer newly risen in recent years, cheap because of its aboundresources, and growth promotion is made With obvious, and the good characteristics such as the vicious circle that poisonous and harmful substance is remained and the soil organism is lost in will not be caused to turn into The practicality fertilizer that country widelys popularize, and the main active of alga oligosaccharides exactly alga fertilizer.The activity of oligosaccharides is by its point The influence of minor structure, is specifically modified oligosaccharide molecular, can improve or assign oligosaccharides more bioactivity.It is few by marine alga The process that sugar prepares alga oligosaccharides phosphate is exactly the hydroxyl on the process that phosphorylation modification is carried out to oligosaccharide molecular, oligosaccharide molecular Replaced by phosphate, form oligosaccharides phosphate.
Current Phosphation modification is concentrated mainly on the Phosphation of polysaccharide, and the Phosphation of alga oligosaccharides is rarely reported. And the activity research of existing polysaccharide phosphate ester focuses mostly in terms of antiviral, antitumor and strengthen immunity, on The polysaccharide or oligosaccharides phosphate of plant biological stimulin effect have no report.
The content of the invention
The invention provides a kind of preparation method of the algal polysaccharides phosphate acted on biostimulant sample, specific skill Art scheme is as follows:Preparation and polysaccharide and phosphatic esterification of the main process including alga oligosaccharides, wherein alga oligosaccharides Prepare:New fresh seaweed is dried or directly crushed using after marine alga dry product, crosses 20-60 mesh sieves.Algae powder after sieving adds 5-10 times The water of quality, adjusts pH 4.0-6.0, adds H2O2, its final concentration in reaction system is reached 0.5-2%, add it is ferrous from Son, makes its final concentration reach that stirring is extracted 4-8 hours at 10-30mg/L, 40-50 DEG C.Extract solution is neutralized to pH 6.5-7.5, 750 mesh filter-cloth filterings, filtrate is alga oligosaccharides extract solution.
The preparation of alga oligosaccharides phosphate:5-10 times of water is added into above-mentioned alga oligosaccharides extract solution, phosphate is added (Sodium tripolyphosphate presses 6 with sodium trimetaphosphate:1-5:2 ratio mixing), make its final concentration of 30-50g/ in reaction system L, pH is to 8.0-9.5 for regulation, is warming up to 70-90 DEG C, stirring reaction 4-8 hours.Reaction solution passes through molecular cut off 300-500Da NF membrane, filter repeatedly, until concentrate in solid content > 10%, spraying or be freeze-dried, obtain alga oligosaccharides phosphoric acid Ester.
The alga oligosaccharides phosphate that above-mentioned preparation method is obtained has the effect of plant biological stimulin sample, plant can be promoted to give birth to It is long, it can be applied to novel bio-organic fertilizer.
The present invention compared with prior art, it is a technical advantage that:
1)Described alga oligosaccharides phosphate is different from polysaccharide phosphate ester class material, and its molecular weight is smaller, and Phosphation degree is more It is high.
2)Described alga oligosaccharides phosphate is directly prepared since marine alga raw material, and technique is simple, and raw material is easy to get, and is adapted to big Scale is industrially applied.
3)Described alga oligosaccharides phosphate has the effect of plant biological stimulin sample, can promote plant growth, and can increase The drought resisting of strong plant, cold-resistant, saline-alkaline tolerance, can be applied to new bio-fertilizer.
Embodiment
Embodiment 1:The preparation of enteromorpha oligosaccharide phosphate
Fresh Enteromorpha dehydration is crushed, and crosses 40 mesh sieves.The algae powder 100g after sieving is taken, 600mL running water is added, stirs, is used Dilute sulfuric acid adjusts pH to 5.0, adds 16mL 30% H2O2, and 60mg FeSO4·7H2O, is extracted 6 hours in stirring at 50 DEG C. Extract solution is filtered after neutralizing, and obtains enteromorpha oligosaccharide extract solution.2.4L water is added into above-mentioned extract solution, and adds tripolyphosphate Sodium 180g, sodium trimetaphosphate 36g, KOH regulation pH are warming up to 80 DEG C, stirring reaction 4 hours to 9.0.Reaction solution passes through retention point Son amount 300-500Da NF membrane, is filtered repeatedly, until solid content > 10% in concentrate, freeze-drying, obtain Enteromorpha Oligosaccharides phosphate 82.8g, phosphate content 10.6%, total sugar content 37.8%, molecular weight 600-3000Da or so.
Embodiment 2:The preparation of sargassum oligosaccharides phosphate
Dry sargassum about 1kg is taken, is put into after crushing in 15L reactors, 10L running water is added, stirring is opened, uses dilute sulfuric acid PH to 4.0 is adjusted, 300mL 30% H is added2O2, and 800mg FeSO4·7H2O, is extracted 4 hours in stirring at 45 DEG C.Extract Plate-frame filtering after liquid is neutralized, filtrate is squeezed into 100L retort, adds 50L water, and sodium tripolyphosphate 1.8kg, three inclined phosphorus Sour sodium 0.7kg, KOH adjust pH to 8.5, are warming up to 70 DEG C, stirring reaction 6 hours.Reaction solution passes through molecular cut off 300- 500Da NF membrane, is filtered repeatedly, until solid content > 10% in concentrate, spray drying, obtain sargassum oligosaccharides phosphorus Acid esters 307.8g, phosphate content 9.53%, total sugar content 45.1%, molecular weight 1000-5000Da or so
Embodiment 3:Influence of the enteromorpha oligosaccharide phosphate to Growth of Cabbage
It is enteromorpha oligosaccharide phosphate, enteromorpha oligosaccharide for examination fertilizer.3 processing of experiment point(Oligosaccharides phosphate group(Made by embodiment 1 Standby technique is made), enteromorpha oligosaccharide group, clear water control group), each processing 2 is repeated, each to repeat kind of 10 plants of pakchois, using fertilizer Material is diluted with water 2000 times, was sprayed every 7 days, each index determining is carried out after 1 week, as a result as shown in the table.
Influence of the enteromorpha oligosaccharide phosphate of table 1 to Growth of Cabbage
Under this experimental condition, the pakchoi of foliar spray enteromorpha oligosaccharide phosphate increases bright on the number of blade, leaf thickness and single-strain fresh weight It is aobvious, while leaf length and leaf width are also increased slightly, but effect is not notable.These data are all higher than the little Bai of foliar spray enteromorpha oligosaccharide Dish, illustrates that the enteromorpha oligosaccharide after phosphorylated modification is acted on Growth of Cabbage is promoted and becomes apparent, spray enteromorpha oligosaccharide phosphorus Acid esters solution can be effectively increased the cell production of pakchoi.

Claims (4)

1. a kind of alga oligosaccharides phosphate, it is characterised in that it is the oligosaccharides and phosphate obtained with extracting and degrading in marine alga Prepared for synthesis material.
2. a kind of method for preparing alga oligosaccharides phosphate described in claim 1, it is characterised in that it comprises the following steps:
1)The preparation of alga oligosaccharides:New fresh seaweed is dried or directly crushed using after marine alga dry product, crosses 20-60 mesh sieves,
Algae powder after sieving adds the water of 5-10 times of quality, adjusts pH 4.0-6.0, adds H2O2, make its end in reaction system Concentration reaches 0.5-2%, adds ferrous ion, its final concentration is reached that stirring extraction 4-8 is small at 10-30mg/L, 40-50 DEG C When, extract solution is neutralized to pH 6.5-7.5, and 750 mesh filter-cloth filterings, filtrate is alga oligosaccharides extract solution;
2)The phosphating reaction of alga oligosaccharides:5-10 times of water is added into above-mentioned alga oligosaccharides extract solution, phosphate is added (Sodium tripolyphosphate presses 6 with sodium trimetaphosphate:1-5:2 ratio mixing), make its final concentration of 30-50g/ in reaction system L, pH is to 8.0-9.5 for regulation, is warming up to 70-90 DEG C, stirring reaction 4-8 hours, and reaction solution passes through molecular cut off 300-500Da NF membrane, filter repeatedly, until concentrate in solid content > 10%, spraying or be freeze-dried, obtain alga oligosaccharides phosphoric acid Ester.
3. the preparation method of alga oligosaccharides phosphate as claimed in claim 2, it is characterised in that the marine alga include red algae, One or more in brown alga, green alga and blue-green algae.
4. application of the alga oligosaccharides phosphate in bio-feritlizer is prepared described in claim 1.
CN201710418424.3A 2017-06-06 2017-06-06 A kind of alga oligosaccharides phosphate and preparation method thereof Pending CN107216404A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107285919A (en) * 2017-08-10 2017-10-24 糖化实业(上海)有限公司 A kind of multi-functional water-soluble fertilizer and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1467226A (en) * 2002-07-11 2004-01-14 中国科学院海洋研究所 Degradation method for agar polysaccharide
CN104592411A (en) * 2015-01-21 2015-05-06 合肥工业大学 Phosphoric acid esterification snakegourd peel polysaccharide and medical application thereof
CN104829341A (en) * 2015-05-04 2015-08-12 山东金利丰生物科技股份有限公司 Seaweed oligosaccharide micro-ecology drip irrigation fertilizer and preparation method thereof
CN105560352A (en) * 2016-02-01 2016-05-11 南京农业大学 Duck viral hepatitis resisting astraglus polysaccharide phosphorylated molecular modification method
CN105601760A (en) * 2016-03-14 2016-05-25 南京农业大学 Preparation method of phosphorylated epimedium polysaccharide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1467226A (en) * 2002-07-11 2004-01-14 中国科学院海洋研究所 Degradation method for agar polysaccharide
CN104592411A (en) * 2015-01-21 2015-05-06 合肥工业大学 Phosphoric acid esterification snakegourd peel polysaccharide and medical application thereof
CN104829341A (en) * 2015-05-04 2015-08-12 山东金利丰生物科技股份有限公司 Seaweed oligosaccharide micro-ecology drip irrigation fertilizer and preparation method thereof
CN105560352A (en) * 2016-02-01 2016-05-11 南京农业大学 Duck viral hepatitis resisting astraglus polysaccharide phosphorylated molecular modification method
CN105601760A (en) * 2016-03-14 2016-05-25 南京农业大学 Preparation method of phosphorylated epimedium polysaccharide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107285919A (en) * 2017-08-10 2017-10-24 糖化实业(上海)有限公司 A kind of multi-functional water-soluble fertilizer and application

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