CN106478837B - A kind of green algae polysaccharide iron complexes and preparation method thereof that can be used for animals and plants and mend iron - Google Patents
A kind of green algae polysaccharide iron complexes and preparation method thereof that can be used for animals and plants and mend iron Download PDFInfo
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- CN106478837B CN106478837B CN201611056612.8A CN201611056612A CN106478837B CN 106478837 B CN106478837 B CN 106478837B CN 201611056612 A CN201611056612 A CN 201611056612A CN 106478837 B CN106478837 B CN 106478837B
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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
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
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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
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
Abstract
The present invention provides a kind of preparation methods that green algae polysaccharide iron is prepared using green alga and high price iron as raw material, belong to metal complex technical field.To produce, polyferose is compound to provide new raw material.Green algae polysaccharide provided by the invention, it is that the method extracted with thermokalite water extracts sea grass polysaccharide from green alga, in pH 6.5-9.0 aqueous solution, ferric sulfate is added dropwise into green algae polysaccharide extracting solution or ferric chloride solution prepares green algae polysaccharide iron complexes, and purified using nanofiltration technique, which can be applied to feed addictive, bio-feritlizer etc..
Description
Technical field
The present invention relates to a kind of green algae polysaccharide iron complexes and preparation method thereof that can be used for animals and plants and mend iron, and in particular to
It is a kind of using green algae polysaccharide and high price iron as the Nu-Iron preparation method of raw material, belong to metal complex field.
Background technique
Iron is plant, animal and the essential trace elements of the human body.Synthesis and promotion many enzymes of the iron to plant chlorophyll
Activity be essential, thus iron is for promoting the metabolism of photosynthesis, respiration, matter and energy of plant to play
Important role.In animal and human body, iron is the constituent of hemoglobin, and hemoglobin participates in the transport and storage of oxygen.
Since the anaemia that the storage of internal iron is not able to satisfy the needs of normocyte generation and occurs is known as hypoferric anemia.Iron simultaneously
Necessary for enzymes various in body and purine biosynthesis necessary substance, directly participation human energy metabolism, influence body and exempt from
Epidemic disease.
Inorganic iron preparation is easily oxidized or is formed precipitating, especially in oxidation state and neutrality into 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 generate thorn to body gastrointestinal tract simultaneously
Swash, the side effects such as Yi Yinqi constipation, nausea, diarrhea are also unfavorable for the absorption of animal and human body.On the other hand, it is inhaled about plant
Although there are many sayings for the mechanism of receipts iron, its absorption process is the first some complexings with plant secretion of iron ion as a whole
Agent (such as citric acid) forms complex compound, reaches root table with complex pattern, is absorbed into the cell, therefore chelated iron specific ionization iron is more
Be conducive to the absorption of plant.And iron in animal body absorption be also by way of complex compound, ferrous ion first have to
Vitamin C, certain sugar and amino acid in intestinal contents form complex compound, then absorb in duodenum and jejunum.Therefore, iron is mended
It is Organic Iron, Complexing Iron that preparation, which is also gradually developed by original inorganic iron, and wherein polyferose is a kind of ideal iron supplementary, property
Stablize, be not easily decomposed, will not polymerize at physiological ph, and exist with soluble form, absorptivity is high.
In Nu-Iron, the polysaccharide as ligand can be glucose oligosaccharide, Radix Angelicae Sinensis polysaccharide, red jujube polysaccharide etc.,
And polyoses content green alga abundant is also a kind of ideal, cheap polysaccharide ligand origins.In algae, Chlorophyta is type
Most one, widely distributed Yu Haiyang, in lake and rivers, rich in polysaccharide, protein, fat, vitamin and mineral etc.,
Wherein water-soluble sulfated polysaccharide content highest, it is common to have two classes: xylose-arabinose-galactan and glucuronic acid-wood
Sugar-rhamnosan.These polysaccharide generally have reducing blood lipid, anti-oxidant, antiviral and strengthen immunity bioactivity.Green alga
Polysaccharide can also be absorbed by plants, and can enhance drought resisting, the cold-resistant, saline-alkaline tolerance of plant.Green alga is widely distributed, cheap,
In contain a large amount of water-soluble polysaccharides, possess unique bioactivity, it is non-toxic, be that a kind of polyferose of rationality prepares ligand original
Material.
Summary of the invention
In order to overcome the technical deficiency of inorganic iron preparation in the prior art, the present invention, which provides one kind, can be used for animals and plants benefit iron
Green algae polysaccharide iron complexes and preparation method thereof,.
To achieve the above object, technical solution of the present invention is as follows: main process include green algae polysaccharide extraction and polysaccharide
With the complex reaction of high price iron, wherein
1) green algae polysaccharide is extracted: after green alga drying and crushing, the water of 10-20 times of volume is added, tune pH is 9.0-12.0,60-
Stirring is extracted 2-4 hours at 80 DEG C, and extracting solution merges after continuous extraction 2-3 times, obtains green algae polysaccharide using 750 mesh filter-cloth filterings
Extracting solution；
2) preparation of green algae polysaccharide iron complexes: the pH of addition citric acid adjusting green algae polysaccharide extracting solution is thereto
Solution is warming up to 70-90 DEG C by 6.5-9.0, and the iron chloride or ferrum sulfuricum oxydatum solutum of 2mol/L are slowly added dropwise thereto, until generating
Reddish brown precipitation continues to be stirred to react 2-6 hours at 70-90 DEG C, and reaction solution is centrifuged 10-20 minutes under 3500rpm revolving speed,
Supernatant crosses nanofiltration membrane and obtains nanofiltration concentrate, and nanofiltration concentrate is spray-dried to get green algae polysaccharide iron complexes.
The preparation method of green algae polysaccharide iron complexes as described above, the molecular cut off of the nanofiltration membrane are 300-
500Da.Wherein the supernatant multiple can cross nanofiltration membrane, until concentrate conductivity < 30us/cm.
Green algae polysaccharide iron complexes described above can be used for preparing feed addictive or bio-feritlizer.It can be used for
Animals and plants mend iron.Influence experiment of 3 green algae polysaccharide of the embodiment of the present invention to spinach growth shows foliar spray green algae polysaccharide iron, EDTA
Ferrisodium can increase the leaf of spinach the piece number, leaf color value, vane thickness and spinach dry weight in various degree, and wherein foliar spray iron fertilizer is increasing
Also there is preferable performance in vane thickness and increase spinach dry weight, the advantage of green algae polysaccharide iron becomes apparent.
Compared with prior art, the present invention it is a technical advantage that:
1) preparation-obtained green algae polysaccharide iron complexes overcome inorganic iron preparation and are easily oxidized or are formed precipitating
Technical deficiency, and stimulation, the side effects such as Yi Yinqi constipation, nausea, diarrhea are generated to body gastrointestinal tract, animals and plants preferably are mended
Iron uses.
2) the green algae polysaccharide iron complexes preparation process described in is simple, and raw material is easy to get, and is suitble to industrially apply on a large scale.
3) the green algae polysaccharide iron complexes described in can enhance the drought resisting of plant, cold-resistant, saline-alkaline tolerance, and have reducing blood lipid, resist
Oxidation, antiviral and strengthen immunity bioactivity.
Detailed description of the invention
Fig. 1 sea grass polysaccharide iron is applied to the influence in the experiment of iron deficiency mouse to content of hemoglobin
Specific embodiment:
Embodiment 1: the preparation method of sea grass polysaccharide iron complexes
The Enteromorpha dry powder 1kg of 60 meshes was taken, 10L water is added, adjusts pH 9.5, is warming up to 80 DEG C, stirring is extracted 3 hours,
It extracts 2 times repeatedly, combined extract, using being neutralized to neutrality after 750 mesh filter cloth plate-frame filterings.Citric acid is added into filtrate,
Stirring and dissolving is warming up to 70 DEG C, keeps pH between 6.5-8.0, and 2 mol/L liquor ferri trichloridis are added dropwise, until generating reddish brown
Until color precipitates, continuation is stirred to react 2 hours at 70 DEG C.Reaction solution is centrifuged 10 minutes under 3500rpm revolving speed, and supernatant is used
Nanofiltration equipment desalination, the molecular cut off of the nanofiltration membrane are 300 Da, spraying when nanofiltration concentrate conductivity is 18us/cm
It is dry, obtain sea grass polysaccharide iron complexes.
Embodiment 2: the preparation method of Codiumfragile(sur.) Hariot. Nu-Iron
Fresh Codiumfragile(sur.) Hariot., dries 2 days after cleaning, and 60 DEG C of drying take 500g to crush and cross 40 meshes, 10L water is added, adjust
PH is 12.0, is warming up to 70 DEG C, and stirring is extracted 2 hours, is repeated 3 times, is obtained Juniperus formosana polysaccharides using 750 mesh filter cloth plate-frame filterings
Extracting solution.Citric acid is added into filtrate, is warming up to 70 DEG C, adjusts and keeps pH 7.5-8.5,2mol/L is added dropwise while stirring
Liquor ferri trichloridi, until generating reddish brown precipitation, maintaining reaction temperature is 70 DEG C and continues to be stirred to react 3 hours.Reaction solution exists
It is centrifuged 10 minutes under 3500rpm revolving speed, supernatant passes through the nanofiltration membrane of molecular cut off 500Da, is filtered repeatedly to concentrate electricity
Conductance is 12us/cm, and spray drying obtains Codiumfragile(sur.) Hariot. Nu-Iron.
Embodiment 3: influence of the green algae polysaccharide iron to spinach growth
It is green algae polysaccharide iron, NaFeEDTA sodium for examination fertilizer.(polyferose group (prepares work by embodiment 1 to 3 processing of test point
Skill is made), NaFeEDTA sodium group, clear water control group), each processing 2 repeats, each to repeat kind of 10 plants of spinach, applies fertilizer water
After 1000 times of dilution, every progress foliar spray processing in 7 days, each index determining is carried out after spraying 1 week, it, will 1 week after spraying for the last time
Whole spinach harvests, measure dry weight, as a result as shown in the table.
Influence of 1 green algae polysaccharide of table to spinach growth
Under this experiment condition, foliar spray green algae polysaccharide iron, NaFeEDTA sodium can increase the leaf of spinach the piece number, leaf color in various degree
Value, vane thickness and spinach dry weight, wherein foliar spray iron fertilizer also has preferable table on increasing vane thickness and increase spinach dry weight
Existing, the advantage of green algae polysaccharide iron becomes apparent.
Embodiment 4: sea grass polysaccharide iron is applied to the experimental study of iron deficiency mouse
Experimental subjects: iron deficiency mouse
Use drug: sea grass polysaccharide iron (preparation of embodiment 1), red source reach (positive control drug), ferrous sulfate
6 groups of experiment mice point, normal mouse control group, iron deficiency control mice group, positive controls (red source reaches), sulfuric acid are sub-
Iron group, sea grass polysaccharide iron group, carrying out corresponding drug stomach-filling to mouse daily, (normal mouse combines iron deficiency mouse group with equivalent clear water
Stomach-filling), after stomach-filling 2 weeks, detect hemoglobin situation of change in mouse blood.
Fig. 1 is sea grass polysaccharide iron applied to the influence in the experiment of iron deficiency mouse to content of hemoglobin.By experimental result
As can be seen that sea grass polysaccharide iron to iron deficiency intragastric administration on mice after two weeks, content of hemoglobin is already close to normal water in mouse blood
It is flat, and effect is suitable with positive controls.The mouse of inorganic molysite (ferrous sulfate) stomach-filling, content of hemoglobin be not apparent
(by detecting in stool in mice) directly is discharged by excrement after being oxidized, precipitating in variation, most of ferrous ion, and with bright
Aobvious constipation phenomenon.It can be seen that the utilization rate of inorganic molysite in animal body is extremely low, and will appear the side effects such as constipation, it is green
Polysaccharides iron can effectively improve the content of hemoglobin of iron deficiency mouse as a kind of organic complex iron, with treatment iron-deficient
Drug (red source reaches) function and effect of anaemia are suitable.
Embodiment 5: green algae polysaccharide iron is applied to sow and its piglet
Experimental subjects: pregnant sow 24 similar in term are randomly divided into 3 groups
Use drug: Codiumfragile(sur.) Hariot. polyferose (preparation of 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, and green alga is more
Sugared iron group feeds basal diet+Codiumfragile(sur.) Hariot. polyferose 1kg/t.
Influence of the 2 green algae polysaccharide iron of table to number born of sow and piglet survival ratio, weight
| Group | Nest litter size | Survival rate | Nest produces young counterpoise living |
| Control group | 10±1.22 | 85.92 | 1.21±0.05 |
| Positive controls | 11±0.78 | 95.75 | 1.27±0.07 |
| Green algae polysaccharide iron group | 11±0.41 | 95.43 | 1.39±0.06 |
Table 2 is influence of the green algae polysaccharide iron to number born of sow and piglet survival ratio, weight.It can be seen that green algae polysaccharide
The absorptivity of iron is high, after feeding pregnant sow, so that more Organic Irons is passed to fetus by placental barrier, thus piglet is born
When body in iron promoter it is more, improve immunoglobulin concentrations, so as to improve the connatae vitality of piglet and health
Situation.The nest litter size of green algae polysaccharide iron group increased, and survival rate is substantially improved, and effect is suitable with injection domestic animal sanguinin；Together
When green algae polysaccharide iron prop counterpoise living young promoted obvious, higher than control group by 14.9%, the positive controls than injecting domestic animal sanguinin are high
9.45%。
Claims (1)
1. molecular cut off is that the green algae polysaccharide iron complexes of 300-500Da are preparing the application in bio-feritlizer, described is green
Polysaccharides iron complexes are prepared using green algae polysaccharide and high price iron as synthesis material, and preparation method includes the following steps:
1) green algae polysaccharide extract: after green alga drying and crushing, be added 10-20 times of volume water, tunes pH be 9.0-12.0,60-80 DEG C
Lower stirring is extracted 2-4 hours, continuous to extract 2-3 rear extracting solution merging, is obtained green algae polysaccharide using 750 mesh filter-cloth filterings and is extracted
Liquid；
2) preparation of green algae polysaccharide iron complexes: it is 6.5-9.0 that citric acid is added thereto and adjusts the pH of green algae polysaccharide extracting solution,
Solution is warming up to 70-90 DEG C, the iron chloride or ferrum sulfuricum oxydatum solutum of 2mol/L are slowly added dropwise thereto, until it is heavy to generate brownish red
It forms sediment, continues to be stirred to react 2-6 hours at 70-90 DEG C, reaction solution is centrifuged 10-20 minutes under 3500rpm revolving speed, supernatant mistake
Nanofiltration membrane obtains nanofiltration concentrate, and nanofiltration concentrate is spray-dried to get green algae polysaccharide iron complexes；
The molecular cut off of the nanofiltration membrane is 300-500Da, and the supernatant multiple can cross nanofiltration membrane, until concentrate electricity
Conductance < 30us/cm.
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| CN1148600A (en) * | 1996-03-05 | 1997-04-30 | 中国科学院南海海洋研究所 | Seaweed polysaccharide trace-element complex and its preparation method and usage |
| CN102351958A (en) * | 2011-08-22 | 2012-02-15 | 河南中医学院 | Preparation method and application of astragalus polysaccharide-calcium complex |
| CN103864950A (en) * | 2014-03-21 | 2014-06-18 | 张忠山 | Preparation method and application of low-molecular porphyra haitanensis polyferose compound |
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2016
- 2016-11-26 CN CN201611056612.8A patent/CN106478837B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148600A (en) * | 1996-03-05 | 1997-04-30 | 中国科学院南海海洋研究所 | Seaweed polysaccharide trace-element complex and its preparation method and usage |
| CN102351958A (en) * | 2011-08-22 | 2012-02-15 | 河南中医学院 | Preparation method and application of astragalus polysaccharide-calcium complex |
| CN103864950A (en) * | 2014-03-21 | 2014-06-18 | 张忠山 | Preparation method and application of low-molecular porphyra haitanensis polyferose compound |
Non-Patent Citations (1)
| Title |
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| 褐藻多糖铁（III）的制备及其性质测定;唐冬临等;《中国药学杂志》;20160930;第51卷(第17期);1513-1518 |
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