CN1330611C - Nano selenium nutrition conditioning agent for fruit and vegetable and its preparing process - Google Patents
Nano selenium nutrition conditioning agent for fruit and vegetable and its preparing process Download PDFInfo
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- CN1330611C CN1330611C CNB2004100233898A CN200410023389A CN1330611C CN 1330611 C CN1330611 C CN 1330611C CN B2004100233898 A CNB2004100233898 A CN B2004100233898A CN 200410023389 A CN200410023389 A CN 200410023389A CN 1330611 C CN1330611 C CN 1330611C
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Abstract
The present invention relates to a nanometer selenium nutrition conditioning agent for fruits and vegetables and a preparing method thereof. The nanometer selenium nutrition conditioning agent is composed of highly bioactive red nanometer selenium, a strongly infiltrating wetting agent and other nutrient components. The preparing method comprises the steps that a selenium compound dissolves in water, and a reducing agent and natural polysaccharide nanometer microspheres are added and used as mould plates; a solution is stirred for one to five hours at normal temperature; when the solution is dark red, red nanometer selenium is prepared; subsequently, the wetting agent and the nutrient components are added, and thus, the nanometer selenium nutrition conditioning agent is prepared. The nanometer selenium nutrition conditioning agent has high biological activity and low toxicity, raises the speed of plant absorption and utilization ratio and reduces harm to the vegetables. The nanometer selenium nutrition conditioning agent has the characteristics of high efficiency, low toxicity, simple preparation, convenient operation and use, low cost and easy large-scale production; besides, the nanometer selenium nutrition conditioning agent is favorable for the plants to absorb and utilize the selenium, and effectively raises the production capacity and quality of the fruits and the vegetables.
Description
Technical field
The present invention relates to the biological nano material in area research and exploitations such as Plant Nutrition, agrochemistry, Agricultural biotechnologies, refer in particular to a kind of benefit selemium nutrition conditioning agent of making by nanotechnology and preparation method thereof.
Background technology
Selenium is one of essential element of human life.Numerous scientific researches show, that selenium has is anticancer, raise immunity, hypoglycemic, protection cardiovascular and cerebrovascular, prevention cataract and effect such as delay senility, so the whole society has started one and mends the selenium upsurge.Human body is mended selenium and be can be summarized as inorganic benefit selenium, synthetic benefit selenium and three kinds of forms of natural organic benefit selenium, but preceding two kinds are mended the selenium modes and have unsurmountable shortcomings such as the big and cost height of toxic side effect, and natural organic benefit selenium owing to the bioavailability height, se complementary effect is good, toxic side effect is little and advantage such as wide material sources receives increasing concern.Natural organic benefit selenium mainly is tonic, is exactly reasonably to eat of selenium-enriched food, as the meat of rich selenium, vegetables, fruit, rice etc.
Lack the selenium area because the most of area of China belongs to, it is extremely limited only absorbing the selenium that obtains by plant in the soil, thereby selenium-enriched fertilizer just arises at the historic moment.Multiple selenium-enriched fertilizer is arranged at present on the market, have as base manure, have as foliage fertilizer.In existing these selenium-enriched fertilizers, the selenium of interpolation mainly is inorganic selenium and selenium mineral powder, has a lot of problems in actual applications, and for example the plant utilization rate is lower, and working concentration is higher relatively, thereby the phenomenon that leaf is hindered fruit occurs hindering; Then be prone to the phenomenon of soil compaction as base manure.
Summary of the invention
Purpose of the present invention aims to provide a kind of high-effect, hypotoxicity, helps the biological fruits and vegetables class nanometer selenium nutrition regulating agent that absorbs to selenium.
It is simple that another object of the present invention aims to provide preparation technology, is easy to the fruits and vegetables class nanometer selenium nutrition regulating agent preparation method of scale operation.
The objective of the invention is to realize by following manner:
Component of the present invention comprises conventional nutrition, it also is made of the wetting agent of red nano selenium with high biological activity and strong wetting capacity, and the red nano selenium of described biologically active is made of starch nano-microsphere template or chitosan nano microsphere template and enrichment nanometer selenium thereon; The concentration range of described red nano selenium in nutrition regulating agent is 5-500ppm, and the concentration range of described wetting agent in nutrition regulating agent is 0.01-1%, by weight.”
Described wetting agent is one or more cooperations in the following material: tween series, AEO (fatty alcohol-polyoxyethylene ether)) series, OP (fatty phenol polyethenoxy ether) series is soluble in water and have powerful adhesive nonionic and anion surfactant.
The preferred tween-80 of described wetting agent, tween 20, AEO-10, Triton-100.
Described conventional nutrition can be K
2SO
4, KH
2PO
4, KNO
3
The preferable concentration of described red nano selenium concentration in nutrition regulating agent is 30-100ppm.
The preferred concentration of described wetting agent in nutrition regulating agent is 0.05-0.20%, by weight.
The concentration range of described conventional nutrition in nutrition regulating agent is 0.1-10g/l, and wherein preferred concentration is 0.5-5g/l.
Another object of the present invention realizes by following manner:
Selenium compound is soluble in water, add reductive agent simultaneously, reach starch nano-microsphere or chitosan nano microballoon as template, stirring reaction is 1～5 hour at normal temperatures, and solution is scarlet, promptly makes red nano selenium, add wetting agent again, and be equipped with conventional nutrition, promptly; Described template: selenium compound: reductive agent=4～6: 1: 2～3.3;
Described starch nano-microsphere template is prepared as Zulkovsky starch is dissolved in the water fully by heating, adds linking agent POCL when waiting to be chilled to 30-50 ℃
3, dispersed with stirring makes;
Described chitosan nano microsphere template is prepared as chitosan is dissolved in the acetum of 0.5-5% fully, the chitosan positively charged, and dripping concentration is the electronegative tripoly phosphate sodium STPP of 0.1-5%, and solution is by the static combination, and stirring makes.
Conventional nutrition concentration is 60～260 times of selenium compound.
Described selenium compound is molten to be water miscible inorganic selenium, comprises sodium selenate, Sodium Selenite etc.; Described reductive agent is natural organic matter xitix with reductibility, trisodium citrate, mercaptoethanol etc.Described natural polysaccharide Nano microsphere template comprises that starch or chitosan nano microballoon are as template.Described wetting agent comprise add tween series, AEO (fatty alcohol-polyoxyethylene ether)) series, OP (fatty phenol polyethenoxy ether) series is soluble in water and have powerful adhesive nonionic and anion surfactant; The preferred tween-80 of described wetting agent, tween 20, AEO-10, Triton-100; Conventional nutrition is K
2SO
4, KNO
3, KH
2PO
4Deng.
The present invention mainly adopts the nanometer technology of preparing, inorganic selenium is prepared into has highly active red elemental selenium, and make it to be enriched in the surface of the nano particle of biopolymer such as polyose, thereby obtain the nm-class core-and-shell particles of sugar/selenium, again according to the growth and development characteristics and the nutritional-physiological characteristics of fruits and vegetables, be equipped with suitable conventional nutritive element and wetting agent, just obtain nanometer selenium nutrition regulating agent efficiently.The present invention has filled up nanometer selenium is mended the selemium nutrition conditioning agent as fruits and vegetables class plant blank.
The present invention utilizes this red nano selemium nutrition conditioning agent to spray in the surface of the cauline leaf fruit of fruits and vegetables class in the fruits and vegetables class suitable growth phase, can effectively improve the selenium content of fruits and vegetables on the one hand, and can improve other qualities of fruits and vegetables greatly, on the other hand in the growth that effectively promotes the fruits and vegetables plant, delay to have remarkable advantages on the plant senesecence.In addition, because use is simple to operate, using dosage is very little, and it is very low to use cost, therefore helps the popularization and the application of this invention product.
Described nanometer selenium is that the Nano microsphere with natural polysaccharide is a template, makes with selenium compound and reductive agent generation redox reaction.Natural polysaccharide comprises starch and chitosan; Selenium compound is water miscible inorganic selenium, comprises sodium selenate, Sodium Selenite etc.; Reductive agent is natural organic matter xitix, trisodium citrate, the mercaptoethanol with reductibility.Described wetting agent and stablizer comprise tween-80, tween 20, AEO-10 etc. for soluble in water and have powerful adhesive tensio-active agent on fruits and vegetables class plant stem-leaf.
The present invention is reduced to zeroth order selenium to high price selenium by redox system, add suitable template, make selenium attached to template surface, obtain nanometer selenium by the nanometer technology of preparing, and with the nonionic surface active agent tween-80, tween 20, AEO-10 etc. are wetting agent and stablizer, and be equipped with other nutritive elements, obtain the nanometer selenium nutrition regulating agent.
Characteristics of the present invention are:
One. the nanometer selenium of the present invention's preparation, compare inorganic selenium, have very high biological activity and lower toxicity, improved the speed and the utilization ratio of plant absorbing, reduced injury to plant.
Two. it is template that the present invention adopts the polysaccharide Nano microsphere, selects for use tensio-active agents such as tween-80 as stablizer and wetting agent, has strengthened the infiltration of nanometer selenium nutrition regulating agent and has sticked ability, helps plant absorbing nanometer selenium.
Three. fruits and vegetables class nanometer selenium nutrition regulating agent of the present invention can effectively promote the fruits and vegetables plant growth, delay senility, effectively improve fruits and vegetables output, particularly improve the selenium content of fruits and vegetables and significantly improve the quality of fruits and vegetables.
Four. the nanometer selenium nutrition regulating agent of the present invention's preparation is an aqua, can directly convert water and do foliage-spray, and operation is very easy, is easy to the popularization of user's acceptance and product.
Five. the used starting material of the present invention are natural polysaccharide, Sodium Selenite and xitix and the fruits and vegetables required K that grows
2SO
4, KH
2PO
4, KNO
3Deng raw material, all be cheap and product that be easy to get, raw materials cost is cheap relatively.And nanometer selenium preparation technology is simple, and equipment requirements is not high, and the reaction times is short, and mild condition all is to carry out at normal temperatures and pressures, is easy to scale operation.
Description of drawings
Accompanying drawing be embodiments of the invention 1 prepared be the nano granules of selenium of template with starch, detect with transmission electron microscope that to obtain the particulate mean diameter be 45nm, prepared particle diameter scope is between 1～200nm.
Embodiment:
Embodiment 1:
With the starch nano-microsphere is the preparation of the nanometer selenium of template
(1) preparation of starch nano-microsphere
1, take by weighing the 1.5g Zulkovsky starch, heating hydrolysis is in 150ml distilled water.
Slowly add the linking agent POCL that accounts for starch quality 1% when 2, hydrolyzed solution is cooled to 40 ℃
3, 500r/min stirring reaction 30 minutes.
(2) preparation of nanometer selenium
1, takes by weighing the 300mg Sodium Selenite, be dissolved in the 150ml water;
2, take by weighing the 900mg xitix and add in the aqueous solution of Sodium Selenite, simultaneously the amidin that makes in () is added in the reaction soln, 500r/min stirring reaction 3h forms red transparent solution, obtains red nano selenium.
In the above-mentioned red nano selenium solution that makes, add wetting agent tween-80 and conventional nutritive ingredient K
2SO
4, KNO
3, KH
2PO
4, stirring and evenly mixing can make nanometer selenium 50ppm, K
2SO
41g/l, KNO
32g/l, KH
2PO
41g/l, the fruits and vegetables class nanometer selenium nutrition regulating agent of tween-80 0.05% (weight meter).
Embodiment 2:
With the chitosan is the preparation of the nanometer selenium of template
(1) preparation of chitosan nano microballoon
1. take by weighing 1.5g chitosan powder, under agitation condition, be dissolved in fully in the acetum of 150ml 1%.
2. slowly add 1% TPP solution to oyster white occurring, the amount that drips TPP is 1/10 of a chitosan, and 500r/min stirs and formed emulsion in 30 minutes.
(2) preparation of nanometer selenium
1. take by weighing Sodium Selenite 300mg, be dissolved in the 150ml water;
2. the chitosan nano microballoon that () is made adds in the aqueous solution of Sodium Selenite, and 500r/min stirs 10min;
3. take by weighing xitix 900mg, be added in the mixing solutions of above-mentioned chitosan nano microballoon and Sodium Selenite, continue stirring reaction 3h, form the transparent solution of scarlet, obtain red nano selenium.
In the above-mentioned red nano selenium solution that makes, add wetting agent tween 20 and conventional nutritive ingredient K
2SO
4, KNO
3, KH
2PO
4, stirring and evenly mixing can make nanometer selenium 80ppm, K
2SO
42g/l, KNO
33g/l, KH
2PO
42g/l, the fruits and vegetables class nanometer selenium nutrition regulating agent of tween 20 0.1% (weight meter).
Embodiment 3:
With the chitosan is the preparation of the nanometer selenium of template
(1) preparation of chitosan nano microballoon
1. take by weighing 1.8g chitosan powder, under agitation condition, be dissolved in fully in the acetum of 150ml 1%.
2. slowly add 1% TPP solution to oyster white occurring, the amount that drips TPP is 1/10 of a chitosan, and 500r/min stirs and formed emulsion in 30 minutes.
(2) preparation of nanometer selenium
1. take by weighing sodium selenate 300mg, be dissolved in the 150ml water;
2. the chitosan nano microballoon that () is made adds in the aqueous solution of sodium selenate, and 500r/min stirs 10min;
4. take by weighing lemon acid trisodium 1000mg, be added in the mixing solutions of above-mentioned chitosan nano microballoon and sodium selenate, continue stirring reaction 3h, form the transparent solution of scarlet, obtain red nano selenium.
In the above-mentioned red nano selenium solution that makes, add wetting agent tween 20 and conventional nutritive ingredient K2SO4, KNO
3, KH2PO4, stirring and evenly mixing can be prepared red nano selenium 30ppm; K2SO4 1g/l, KNO
32g/l, KH2PO4 1g/l, tween-80 0.1, the fruits and vegetables class nanometer selenium nutrition regulating agent of (weight meter).
Embodiment 4
(1) preparation of starch nano-microsphere
1, take by weighing the 1.2g Zulkovsky starch, heating hydrolysis is in 150ml distilled water.
Slowly add the linking agent POCL that accounts for starch quality 1% when 2, hydrolyzed solution is cooled to 40 ℃
3, 500r/min stirring reaction 30 minutes.
(2) preparation of nanometer selenium
3, take by weighing the 300mg Sodium Selenite, be dissolved in the 150ml water;
4, take by weighing the 600mg mercaptoethanol and add in the aqueous solution of Sodium Selenite, simultaneously the amidin that makes in () is added in the reaction soln, 500r/min stirring reaction 3h forms red transparent solution, obtains red nano selenium.
In the above-mentioned red nano selenium solution that makes, add wetting agent tween-80 and conventional nutritive ingredient K
2SO
4, KNO
3, KH
2PO
4, stirring and evenly mixing can make red nano selenium 50ppm; K
25O
44g/, KNO
35g/l, KH
2PO
44g/l, the fruits and vegetables class nanometer selenium nutrition regulating agent of AEO-10 0.2% (weight meter).
Embodiment 5
Step is with embodiment 2, red nano selenium 5ppm; K
2SO
40.1g/l KNO
30.1g/l KH
2PO
40.1g/l Triton-100 0.1%
Embodiment 6
Step is with embodiment 2, red nano selenium 500ppm; K
2SO
410g/l KNO
310g/l KH
2PO
410g/l Triton-100 1%
Embodiment 7:
Implement in the field of nanometer selenium nutrition regulating agent
One. the fruits grape field test in Yuelu District zenith township, Changsha: spray the product that embodiment 1 is provided three times in grape flowering period, shedding phase and ripening stage, working concentration is and contains selenium element 50ppm.The grape selenium content reaches (85 ± 5) μ g/kg, has improved nearly 15 times than control group; Sugar content reaches (19 ± 1.4) %, has improved more than 11% than control group; Acidity is (6.1 ± 0.4) g/l, has reduced more than 7% than control group.Grape quality significantly improves.
Two. the greengrocery sponge gourd field test in Meishan village, town, Lengshuijiang City tongued bell mountain, Hunan Province: sponge gourd bloom the early stage and the knot melon phase secondary spray the product that embodiment 1 is provided, working concentration is and contains selenium element 50ppm.The selenium content that detection obtains sponge gourd reaches (73 ± 4) μ g/kg, has improved nearly 8 times than control group, and mouthfeel is obviously improved.
Claims (5)
1, fruits and vegetables class nanometer selenium nutrition regulating agent, component comprises conventional nutrition, it is characterized in that: it also is made of the wetting agent of red nano selenium with high biological activity and strong wetting capacity, and the red nano selenium of described biologically active is made of starch nano-microsphere template or chitosan nano microsphere template and enrichment nanometer selenium thereon; The concentration range of described red nano selenium in nutrition regulating agent is 5-500ppm, and the concentration range of described wetting agent in nutrition regulating agent is 0.01-1%, by weight.
2, fruits and vegetables class nanometer selenium nutrition regulating agent according to claim 1, it is characterized in that: described wetting agent is one or more cooperations in the following material: tween series, fatty alcohol-polyoxyethylene ether series, fatty phenol polyethenoxy ether series is soluble in water and have powerful adhesive nonionic and anion surfactant; Described conventional nutrition is K
2SO
4, KH
2PO
4, KNO
3
3, fruits and vegetables class nanometer selenium nutrition regulating agent according to claim 2, it is characterized in that: described wetting agent is tween-80, tween 20, AEO-10, Triton-100.
4, fruits and vegetables class nanometer selenium nutrition regulating agent according to claim 1, it is characterized in that: the concentration range of described conventional nutrition in nutrition regulating agent is 0.1-10g/l.
5, fruits and vegetables class nanometer selenium nutrition regulating agent according to claim 1, it is characterized in that: the concentration range of red nano selenium in nutrition regulating agent is 30-100ppm, the concentration range of described wetting agent in nutrition regulating agent is 0.05-0.2%, by weight, the concentration range of described conventional nutrition in nutrition regulating agent is 0.5-5g/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100233898A CN1330611C (en) | 2004-07-06 | 2004-07-06 | Nano selenium nutrition conditioning agent for fruit and vegetable and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100233898A CN1330611C (en) | 2004-07-06 | 2004-07-06 | Nano selenium nutrition conditioning agent for fruit and vegetable and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1594236A CN1594236A (en) | 2005-03-16 |
| CN1330611C true CN1330611C (en) | 2007-08-08 |
Family
ID=34663424
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| CNB2004100233898A Expired - Fee Related CN1330611C (en) | 2004-07-06 | 2004-07-06 | Nano selenium nutrition conditioning agent for fruit and vegetable and its preparing process |
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| CN1594236A (en) | 2005-03-16 |
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