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CN106478837A - A kind of can be used for green algae polysaccharide iron complexes of animals and plants iron supplement and preparation method thereof - Google Patents

A kind of can be used for green algae polysaccharide iron complexes of animals and plants iron supplement and preparation method thereof Download PDF

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Publication number
CN106478837A
CN106478837A CN201611056612.8A CN201611056612A CN106478837A CN 106478837 A CN106478837 A CN 106478837A CN 201611056612 A CN201611056612 A CN 201611056612A CN 106478837 A CN106478837 A CN 106478837A
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green algae
algae polysaccharide
iron complexes
iron
preparation
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CN106478837B (en
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单俊伟
台文静
王海华
郝晓晨
宿露译
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Qingdao Haida biological Group Co.,Ltd.
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QINGDAO SEAWIN BIOTECH GROUP Co Ltd
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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
    • C08B37/006Heteroglycans, 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
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00Other inorganic fertilisers
    • C05D9/02Other inorganic fertilisers containing trace elements
    • 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Sustainable Development (AREA)
  • Medicines Containing Plant Substances (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention provides a kind of prepare the preparation method of green algae polysaccharide ferrum with chlorella and high price ferrum for raw material, belong to metal complex technical field.It is combined offer new raw material for producing polyferose.The green algae polysaccharide that the present invention provides, it is that sea grass polysaccharide is extracted from chlorella with the method for thermokalite water extraction, in pH 6.5 9.0 aqueous solution, Deca iron sulfate or ferric chloride solution preparation green algae polysaccharide iron complexes in green algae polysaccharide extracting solution, and purification is carried out using nanofiltration technique, this complex can be applicable to feed additive, bio-feritlizer etc..

Description

A kind of can be used for green algae polysaccharide iron complexes of animals and plants iron supplement and preparation method thereof
Technical field
The present invention relates to a kind of can be used for green algae polysaccharide iron complexes of animals and plants iron supplement and preparation method thereof and in particular to A kind of with green algae polysaccharide and the Nu-Iron preparation method as raw material for the high price ferrum, belong to metal complex field.
Background technology
Ferrum is plant, animal and trace element needed by human.Ferrum to the synthesis of plant chlorophyll and promotes many enzymes Activity be requisite, thus ferrum plays for the metabolism promoting the photosynthesis of plant, Repiration, matter and energy Important effect.In animal and human body, ferrum is the constituent of hemoglobin, and hemoglobin participates in transport and the storage of oxygen. Because the storage of internal ferrum can not meet the needs of normocyte generation, the anemia that occurs is referred to as iron deficiency anemia.Ferrum simultaneously Necessary for enzymes various in body, it is also the necessary material of purine biosynthesis, directly participates in human energy metabolism, impact body is exempted from Epidemic disease.
Inorganic iron preparation is easily oxidized or forms precipitation, especially in oxidation state and neutrality in basic soil, ion The concentration of iron of state is very low, and the inorganic iron of supply is far below the needs of plant.Inorganic iron can produce thorn to body gastrointestinal tract simultaneously Swash, easily cause the side effect such as constipation, nausea, diarrhoea, be also unfavorable for the absorption of animal and human body.On the other hand, inhale with regard to plant Although the mechanism receiving ferrum has multiple sayings, its absorption process is as a whole, iron ion first some complexations with plant secretion Agent(As citric acid)Form complex, root table is reached with complex pattern, is absorbed into intracellular, therefore chelated iron specific ionization ferrum is more Be conducive to the absorption of plant.And absorption in animal body for the ferrum is also the form by complex, ferrous ion first have to Vitamin C in intestinal contentses, some sugar and aminoacid form complex, then absorb in duodenum and jejunum.Therefore, iron supplement Preparation also progressively develops into Organic Iron, Complexing Iron by original inorganic iron, and wherein polyferose is a kind of preferable iron supplementary, property Stable, it is not easily decomposed at physiological ph, also will not be polymerized, and existed with soluble form, absorbance is high.
In Nu-Iron, the polysaccharide as part can be oligomeric glucose, Radix Angelicae Sinensis polysaccharide, red jujube polysaccharide etc., And the chlorella that polyoses content enriches is also a kind of preferable, cheap polysaccharide ligand origins.In algae, Chlorophyta is species Most one, widely distributed Yu Haiyang, in lake and rivers, rich in polysaccharide, protein, fat, vitamin and mineral etc., Wherein water solublity sulfated polysaccharide content highest, common have two classes:Xylose-arabinose-galactan and glucuronic acid-wood Sugar-rhamnosan.These polysaccharide generally have the biological activity of blood fat reducing, antioxidation, antiviral and enhancing immunity.Chlorella Polysaccharide can also be absorbed by plants, and can strengthen the drought resisting of plant, cold-resistant, saline-alkaline tolerance.Chlorella is widely distributed, cheap, its In contain a large amount of water soluble polysaccharide, have the biological activity of uniqueness, avirulence, it is former to be that part prepared by a kind of polyferose of rationality Material.
Content of the invention
In order to overcome the technical deficiency of inorganic iron preparation in prior art, the present invention provides one kind to can be used for animals and plants iron supplement Green algae polysaccharide iron complexes and preparation method thereof,.
For achieving the above object, technical solution of the present invention is as follows:Main process include extraction and the polysaccharide of green algae polysaccharide With the complex reaction of high price ferrum, wherein
1)Green algae polysaccharide is extracted:After chlorella drying and crushing, add the water of 10-20 times of volume, tune pH is 9.0-12.0,60-80 DEG C 2-4 hour is extracted in lower stirring, and continuous 2-3 rear extracting solution of extraction merges, and obtains green algae polysaccharide using 750 mesh filter-cloth filterings and extracts Liquid;
2)The preparation of green algae polysaccharide iron complexes:The pH being added thereto to citric acid regulation green algae polysaccharide extracting solution is 6.5- 9.0, solution is warming up to 70-90 DEG C, is slowly added dropwise iron chloride or the ferrum sulfuricum oxydatum solutum of 2mol/L thereto, until producing reddish brown Color precipitates, and continues stirring reaction 2-6 hour at 70-90 DEG C, and reactant liquor is centrifuged 10-20 minute, supernatant under 3500rpm rotating speed Liquid is crossed NF membrane and is obtained nanofiltration concentrate, and nanofiltration concentrate is spray-dried, and obtains final product green algae polysaccharide iron complexes.
The preparation method of green algae polysaccharide iron complexes as above, the molecular cut off of described NF membrane is 300- 500Da.Wherein said supernatant multiple can cross NF membrane, until concentrated solution electrical conductivity < 30us/cm.
Green algae polysaccharide iron complexes described above can be used for preparing feed additive or bio-feritlizer.It can be used for Animals and plants iron supplement.The impact experiment to spinach growth for the embodiment of the present invention 3 green algae polysaccharide shows, foliar spray green algae polysaccharide ferrum, EDTA Ferrum sodium all can increase Spinach Leaf number, leaf color value, vane thickness and Herba Spinaciae dry weight in various degree, and wherein foliar spray iron fertilizer is increasing Also there is preferable performance, the advantage of green algae polysaccharide ferrum becomes apparent from vane thickness and increase Herba Spinaciae dry weight.
The present invention compared with prior art, it is a technical advantage that:
1)Preparation-obtained green algae polysaccharide iron complexes overcome inorganic iron preparation technology that is easily oxidized or forming precipitation Deficiency, and stimulation is produced to body gastrointestinal tract, easily cause the side effect such as constipation, nausea, diarrhoea, animals and plants iron supplement preferably makes With.
2)Described green algae polysaccharide iron complexes preparation process is simple, raw material is easy to get, and is suitable for industrially applying on a large scale.
3)Described green algae polysaccharide iron complexes can strengthen the drought resisting of plant, cold-resistant, saline-alkaline tolerance, and have blood fat reducing, resist The biological activity of oxidation, antiviral and enhancing immunity.
Brief description
Fig. 1 sea grass polysaccharide ferrum is applied to the impact to content of hemoglobin in the experiment of iron deficiency mice
Specific embodiment:
Embodiment 1:The preparation method of sea grass polysaccharide iron complexes
Took the Entermorpha dry powder 1kg of 60 mesh sieves, added 10L water, and adjusted pH 9.5, be warming up to 80 DEG C, stirring extraction 3 hours, repeatedly Extract 2 times, united extraction liquid, be neutralized to neutrality using after 750 mesh filter cloth plate-and-frame filtration.Citric acid, stirring is added in filtrate Dissolving, is warming up to 70 DEG C, keeps pH between 6.5-8.0, and Deca 2 mol/L liquor ferri trichloridi, sinks to producing brownish red Till shallow lake, continue stirring reaction 2 hours at 70 DEG C.Reactant liquor is centrifuged 10 minutes under 3500rpm rotating speed, supernatant nanofiltration Equipment desalination, the molecular cut off of described NF membrane is 300 Da, spray dried when nanofiltration concentrate electrical conductivity is 18us/cm Dry, obtain sea grass polysaccharide iron complexes.
Embodiment 2:The preparation method of Codiumfragile(sur.) Hariot. Nu-Iron
Fresh Codiumfragile(sur.) Hariot., dry in the sun 2 days after cleaning, 60 DEG C of drying, take 500g to pulverize and cross 40 mesh sieves, add 10L water, adjusting pH is 12.0, it is warming up to 70 DEG C, stirring is extracted 2 hours, is repeated 3 times, obtains Codiumfragile(sur.) Hariot. Polyose extraction using 750 mesh filter cloth plate-and-frame filtration Liquid.Add citric acid in filtrate, be warming up to 70 DEG C, adjust and keep pH 7.5-8.5, while stirring Deca 2mol/L trichlorine Change ferrous solution, to producing reddish brown precipitation, maintain reaction temperature to be 70 DEG C and continue stirring reaction 3 hours.Reactant liquor is in 3500rpm It is centrifuged 10 minutes under rotating speed, supernatant, by the NF membrane of molecular cut off 500Da, repeatedly filters and to concentrated solution electrical conductivity is 12us/cm, is spray-dried, obtains Codiumfragile(sur.) Hariot. Nu-Iron.
Embodiment 3:The impact to spinach growth for the green algae polysaccharide ferrum
It is green algae polysaccharide ferrum, NaFeEDTA sodium for examination fertilizer.3 process of test point(Polyferose group(By embodiment 1 preparation technology system ?), NaFeEDTA sodium group, clear water matched group), each processes 2 repetitions, and each repeats kind of 10 plants of Herba Spinaciaes, applying fertilizer dilute with water After 1000 times, carry out foliar spray process every 7 days, after spraying 1 week, carry out each index determining, 1 week after spraying for the last time, will all Herba Spinaciae harvests, and measures dry weight, and result is as shown in the table.
The impact to spinach growth for table 1 green algae polysaccharide
Under this experiment condition, foliar spray green algae polysaccharide ferrum, NaFeEDTA sodium all can increase in various degree Spinach Leaf number, leaf color value, Vane thickness and Herba Spinaciae dry weight, wherein foliar spray iron fertilizer also have preferable performance on increasing vane thickness and increase Herba Spinaciae dry weight, The advantage of green algae polysaccharide ferrum becomes apparent from.
Embodiment 4:Sea grass polysaccharide ferrum is applied to the experimentation of iron deficiency mice
Experimental subject:Iron deficiency mice
Using medicine:Sea grass polysaccharide ferrum(Prepared by embodiment 1), red source reaches(Positive control drug), ferrous sulfate
Experiment mice divides 6 groups, normal mouse matched group, iron deficiency control mice group, positive controls(Red source reaches), ferrous sulfate Group, sea grass polysaccharide ferrum group, carry out corresponding medicine gavage daily to mice(Normal mouse combination iron deficiency mice group is filled with equivalent clear water Stomach), gavage is after 2 weeks, hemoglobin situation of change in detection mouse blood.
Fig. 1 is applied to the impact to content of hemoglobin in the experiment of iron deficiency mice for sea grass polysaccharide ferrum.By experimental result As can be seen that after sea grass polysaccharide ferrum was to iron deficiency mouse stomach two weeks, in mouse blood, content of hemoglobin is already close to normal water Flat, and effect is suitable with positive controls.Inorganic molysite(Ferrous sulfate)The mice of gavage, content of hemoglobin is not significantly Change, most of ferrous ion is oxidized, directly discharged by feces after precipitation(Detected by stool in mice), and with bright Aobvious constipation phenomenon.As can be seen here, inorganic molysite utilization rate in animal body is extremely low, and the side effect such as constipation occurs, green Polysaccharides ferrum, as a kind of organic complex ferrum, can effectively improve the content of hemoglobin of iron deficiency mice, with treatment iron-deficient The medicine of anemia(Red source reaches)Action effect is suitable.
Embodiment 5:Green algae polysaccharide ferrum is applied to sow and its piglet
Experimental subject:Term close in-pig 24, is randomly divided into 3 groups
Using medicine:Codiumfragile(sur.) Hariot. polyferose(Prepared by embodiment 2), domestic animal sanguinin(Positive control drug)
3 groups of experiment point, control group fed basal diet, positive controls feed basal diet+injection domestic animal sanguinin, green algae polysaccharide ferrum Group feeding basal diet+Codiumfragile(sur.) Hariot. polyferose 1kg/t.
The impact to number born of sow and piglet survival ratio, body weight for the table 2 green algae polysaccharide ferrum
Group Nest litter size Survival rate Nest produces son's counterpoise of living
Matched group 10±1.22 85.92 1.21±0.05
Positive controls 11±0.78 95.75 1.27±0.07
Green algae polysaccharide ferrum group 11±0.41 95.43 1.39±0.06
Table 2 is the impact to number born of sow and piglet survival ratio, body weight for the green algae polysaccharide ferrum.As can be seen that green algae polysaccharide ferrum Absorbance is high, after feeding in-pig, makes more Organic Irons pass to fetus by placental barrier, thus body during piglet birth Interior iron promoter is more, so that immunoglobulin concentrations in blood is improved, thus improving the connatae vitality of piglet and health status. The nest litter size of green algae polysaccharide ferrum group increased, and survival rate is substantially improved, and effect is suitable with injection domestic animal sanguinin;Chlorella simultaneously Polysaccharide iron prop lives son's counterpoise lifting substantially, higher by 14.9% than matched group, higher by 9.45% than the positive controls of injection domestic animal sanguinin.

Claims (5)

1. a kind of green algae polysaccharide iron complexes are it is characterised in that it is to be prepared into green algae polysaccharide and high price ferrum for synthesis material Arrive.
2. a kind of method preparing green algae polysaccharide iron complexes described in claim 1 is it is characterised in that it comprises the following steps:
1)Green algae polysaccharide is extracted:After chlorella drying and crushing, add the water of 10-20 times of volume, tune pH is 9.0-12.0,60-80 DEG C 2-4 hour is extracted in lower stirring, and continuous 2-3 rear extracting solution of extraction merges, and obtains green algae polysaccharide using 750 mesh filter-cloth filterings and extracts Liquid;
2)The preparation of green algae polysaccharide iron complexes:The pH being added thereto to citric acid regulation green algae polysaccharide extracting solution is 6.5- 9.0, solution is warming up to 70-90 DEG C, is slowly added dropwise iron chloride or the ferrum sulfuricum oxydatum solutum of 2mol/L thereto, until producing reddish brown Color precipitates, and continues stirring reaction 2-6 hour at 70-90 DEG C, and reactant liquor is centrifuged 10-20 minute, supernatant under 3500rpm rotating speed Liquid is crossed NF membrane and is obtained nanofiltration concentrate, and nanofiltration concentrate is spray-dried, and obtains final product green algae polysaccharide iron complexes.
3. the preparation method of green algae polysaccharide iron complexes as claimed in claim 2 is it is characterised in that the retention of described NF membrane Molecular weight is 300-500Da.
4. the preparation method of green algae polysaccharide iron complexes as claimed in claim 2 is it is characterised in that described supernatant can be many Secondary NF membrane excessively, until concentrated solution electrical conductivity < 30us/cm.
5. application in preparing feed additive or bio-feritlizer for the green algae polysaccharide iron complexes described in claim 1.
CN201611056612.8A 2016-11-26 2016-11-26 A kind of green algae polysaccharide iron complexes and preparation method thereof that can be used for animals and plants and mend iron Active CN106478837B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110194809A (en) * 2019-06-18 2019-09-03 武汉轻工大学 The preparation method and application of Codonopsis pilosula polysaccharide iron complexes
CN118063643A (en) * 2024-04-18 2024-05-24 康源领鲜科技有限公司 Enteromorpha polysaccharide extraction process and application thereof in salmon feed

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110194809A (en) * 2019-06-18 2019-09-03 武汉轻工大学 The preparation method and application of Codonopsis pilosula polysaccharide iron complexes
CN110194809B (en) * 2019-06-18 2021-10-26 武汉轻工大学 Preparation method and application of codonopsis pilosula polysaccharide-iron compound
CN118063643A (en) * 2024-04-18 2024-05-24 康源领鲜科技有限公司 Enteromorpha polysaccharide extraction process and application thereof in salmon feed
CN118063643B (en) * 2024-04-18 2024-07-16 康源领鲜科技有限公司 Enteromorpha polysaccharide extraction process and application thereof in salmon feed

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