CN1330611C - Nano selenium nutrition conditioning agent for fruit and vegetable and its preparing process - Google Patents

Abstract

The fruit and vegetable nano-selenium nutrition regulator and its preparation method are composed of red nano-selenium with high biological activity, a wetting agent with strong wetting ability and other nutritional components. The preparation method is to dissolve the selenium compound in water, add a reducing agent and natural polysaccharide nano-microspheres as templates at the same time, stir and react at room temperature for 1 to 5 hours, and the solution is dark red, that is, red nano-selenium is obtained, and then adding a wetting agent , and with nutritional ingredients, that is. It has high biological activity and low toxicity, improves the speed and utilization rate of plant absorption, and reduces the damage to plants. The invention has the characteristics of high efficiency, low toxicity, simple preparation and convenient operation and use, is beneficial to the absorption and utilization of selenium by plants, effectively improves the yield and quality of fruits and vegetables, and is low in cost and easy for large-scale production.

Description

Fruit and vegetable nano-selenium nutrition regulator and preparation method thereof

technical field

The invention relates to the research and development of biological nanomaterials in the fields of plant nutrition, agricultural chemistry, agricultural biotechnology, etc., in particular to a selenium supplement nutritional regulator made by nanotechnology and a preparation method thereof.

Background technique

Selenium is one of the essential elements for human life. Numerous scientific studies have shown that selenium has the functions of anti-cancer, enhancing immune function, lowering blood sugar, protecting cardiovascular and cerebrovascular, preventing cataract and delaying aging, so there is a wave of selenium supplementation in the whole society. Human body selenium supplementation can be summarized into three forms: inorganic selenium supplementation, synthetic selenium supplementation and natural organic selenium supplementation. More and more attention has been paid to it because of its advantages such as high selenium supplementation effect, low toxicity and side effects, and wide sources. Natural organic selenium supplementation mainly lies in food supplementation, that is, eating some selenium-rich foods reasonably, such as selenium-rich meat, vegetables, fruits, rice, etc.

Since most areas of our country are selenium-deficient areas, the selenium absorbed by plants from the soil is extremely limited, so selenium-enriched fertilizers have emerged as the times require. At present, there are many kinds of selenium-rich fertilizers on the market, some are used as base fertilizers, and some are used as foliar fertilizers. In these existing selenium-enriched fertilizers, the added selenium is mainly inorganic selenium and selenium ore powder, and there are many problems in practical application, such as low plant utilization rate, relatively high concentration, and damage to leaves and fruits. phenomenon; as a base fertilizer, it is prone to soil compaction.

Contents of the invention

The object of the present invention is to provide a kind of fruit and vegetable nano-selenium nutritional regulator with high efficiency, low toxicity, and beneficial to the absorption and utilization of selenium by organisms.

Another object of the present invention is to provide a method for preparing a fruit and vegetable nano-selenium nutritional regulator that has a simple preparation process and is easy to produce on a large scale.

The purpose of the present invention is achieved in the following manner:

The components of the present invention include conventional nutritional ingredients, and it is also composed of red nano-selenium with high biological activity and a wetting agent with strong wetting ability. The red nano-selenium with biological activity is composed of starch nano-microsphere template or chitosan Nano-microsphere template and nano-selenium enriched thereon; the concentration range of the red nano-selenium in the nutrient regulator is 5-500ppm, and the concentration range of the wetting agent in the nutrient regulator is 0.01 -1% by weight. "

The wetting agent is one or more of the following substances: Tween series, AEO (fatty alcohol polyoxyethylene ether) series, OP (fatty phenol polyoxyethylene ether) series are easily soluble in water and have strong Adhesive nonionic and anionic surfactants.

The wetting agent is preferably Tween-80, Tween-20, AEO-10, Triton-100.

The conventional nutritional ingredients can be K ₂ SO ₄ , KH ₂ PO ₄ , KNO ₃ .

The preferred concentration of the red nano-selenium in the nutritional regulator is 30-100ppm.

The preferred concentration of the wetting agent in the nutrient regulator is 0.05-0.20%, by weight.

The concentration range of the conventional nutritional ingredients in the nutrition regulator is 0.1-10g/l, and the preferred concentration is 0.5-5g/l.

Another object of the present invention is achieved in the following manner:

Dissolving the selenium compound in water, adding a reducing agent, and starch nanospheres or chitosan nanospheres as a template, stirring and reacting at room temperature for 1 to 5 hours, the solution is dark red, that is, red nano-selenium is obtained, and then Add a wetting agent and mix with conventional nutritional ingredients to get ready; said template: selenium compound: reducing agent = 4～6:1:2～3.3;

The starch nano-microsphere template is prepared by dissolving soluble starch in water completely by heating, adding cross-linking agent POCL ₃ when it is cooled to 30-50°C, stirring and dispersing;

The chitosan nano microsphere template is prepared by dissolving chitosan completely in 0.5-5% acetic acid solution, chitosan is positively charged, and the negatively charged tripolyphosphoric acid with a concentration of 0.1-5% is added dropwise Sodium, the solution is obtained by electrostatic combination and stirring.

The concentration of conventional nutrients is 60 to 260 times that of selenium compounds.

The selenium compound is dissolved as a water-soluble inorganic selenium compound, including sodium selenate, sodium selenite, etc.; the reducing agent is natural organic ascorbic acid with reducing properties, trisodium citrate, mercaptoethanol, etc. The natural polysaccharide nano-microsphere template includes starch or chitosan nano-microsphere as a template. The wetting agent includes adding Tween series, AEO (fatty alcohol polyoxyethylene ether) series, OP (fatty phenol polyoxyethylene ether) series of nonionic and anionic surfactants that are easily soluble in water and have strong adhesion ; The wetting agent is preferably Tween-80, Tween-20, AEO-10, Triton-100; conventional nutritional ingredients are K ₂ SO ₄ , KNO ₃ , KH ₂ PO ₄ and the like.

The present invention mainly adopts nano-preparation technology to prepare inorganic selenium into red elemental selenium with high activity, and enrich it on the surface of biopolymers such as polysaccharide nanoparticles, thereby obtaining sugar/selenium core-shell nano Granules, according to the growth and development characteristics and nutritional physiological characteristics of fruits and vegetables, with appropriate conventional nutritional elements and wetting agents, you can get a highly efficient nano-selenium nutritional regulator. The invention fills up the blank of nano-selenium used as a selenium-supplementing nutritional regulator for fruit and vegetable plants.

The present invention utilizes the red nano-selenium nutrition regulator to spray on the surface of the stems, leaves and fruits of fruits and vegetables during the suitable growth period of fruits and vegetables. On the one hand, the selenium content of fruits and vegetables can be effectively improved, and other qualities of fruits and vegetables can be greatly improved. On the other hand, It has obvious advantages in effectively promoting the growth of fruit and vegetable plants and delaying plant aging. In addition, because the use and operation are simple, the dosage is small, and the application cost is very low, it is beneficial to the popularization and application of the inventive product.

The nano-selenium is prepared by taking the nano-microspheres of natural polysaccharides as a template and redox reaction of a selenium compound and a reducing agent. Natural polysaccharides include starch and chitosan; selenium compounds are water-soluble inorganic selenium compounds, including sodium selenate, sodium selenite, etc.; reducing agents are reducing natural organic substances ascorbic acid, trisodium citrate, and mercaptoethanol. The wetting agent and stabilizer are surfactants that are easily soluble in water and have strong adhesion on the stems and leaves of fruit and vegetable plants, including Tween-80, Tween-20, AEO-10 and the like.

The present invention reduces high-valent selenium to zero-valent selenium through a redox system, adds a suitable template to make selenium adhere to the surface of the template, and obtains nano-selenium through nano-preparation technology, and uses non-ionic surfactant Tween-80, Tween -20, AEO-10, etc. are wetting agents and stabilizers, and are combined with other nutritional elements to obtain nano-selenium nutritional regulators.

The features of the present invention are:

One. Compared with inorganic selenium, the nano-selenium prepared by the present invention has high biological activity and lower toxicity, improves the speed and utilization rate of plant absorption, and reduces the damage to plants.

Two. the present invention adopts polysaccharide nano-microspheres as a template, and selects surfactants such as Tween-80 as stabilizers and wetting agents, which enhances the penetration and adhesion of nano-selenium nutrition regulators, and is conducive to the absorption of nano-selenium by plants use.

3. The nano-selenium nutritional regulator for fruits and vegetables of the present invention can effectively promote the growth of fruit and vegetable plants, delay aging, effectively increase the yield of fruits and vegetables, especially increase the selenium content of fruits and vegetables and significantly improve the quality of fruits and vegetables.

4. The nano-selenium nutrient regulator prepared by the present invention is an aqueous preparation, which can be directly mixed with water for foliar spraying. It is very convenient to operate, easy for users to accept and popularize the product.

Five. raw materials used in the present invention are raw materials such as natural polysaccharide, sodium selenite and ascorbic acid and the required K ₂ SO ₄ , KH ₂ PO ₄ , KNO ₃ for growth and development of fruits and vegetables, all are cheap and easy-to-get products, and the cost of raw materials is relatively low. Moreover, the preparation process of nano-selenium is simple, the requirements for equipment are not high, the reaction time is short, and the conditions are mild, all of which are carried out at normal temperature and pressure, and are easy to produce on a large scale.

Description of drawings

The accompanying drawing shows the nano-selenium particles prepared in Example 1 of the present invention using starch as a template. The average diameter of the particles detected by transmission electron microscopy is 45nm, and the diameter of the prepared particles ranges from 1 to 200nm.

Detailed ways:

Example 1:

Preparation of Nano Selenium Using Starch Nanospheres as Template

(1) Preparation of starch nanospheres

1. Weigh 1.5g soluble starch, heat and hydrolyze it in 150ml distilled water.

2. When the hydrolyzate is cooled to 40° C., slowly add cross-linking agent POCL ₃ accounting for 1% of the starch mass, and stir at 500 r/min for 30 minutes.

(2) Preparation of nano-selenium

1. Weigh 300mg sodium selenite and dissolve it in 150ml water;

2. Take by weighing 900 mg of ascorbic acid and add it to the aqueous solution of sodium selenite, and add the starch aqueous solution prepared in (1) to the reaction solution simultaneously, stir and react at 500 r/min for 3 hours, form a red transparent solution, and obtain red nano-selenium.

Add wetting agent Tween-80 and conventional nutrients K ₂ SO ₄ , KNO ₃ , KH ₂ PO ₄ to the red nano-selenium solution prepared above, stir and mix well to prepare nano-selenium 50ppm, K ₂ SO ₄ 1g/l, KNO ₃ 2g/l, KH ₂ PO ₄ 1g/l, Tween-80 0.05% (by weight) a fruit and vegetable nano-selenium nutritional regulator.

Example 2:

Preparation of Nano Selenium Using Chitosan as Template

(1) Preparation of Chitosan Nanospheres

1. Weigh 1.5g chitosan powder and dissolve it completely in 150ml 1% acetic acid solution under stirring condition.

2. Slowly add 1% TPP solution until milky white appears, the amount of TPP added dropwise is 1/10 of chitosan, and stirred at 500r/min for 30 minutes to form an emulsion.

(2) Preparation of nano-selenium

1. Weigh 300mg of sodium selenite and dissolve it in 150ml of water;

2. The chitosan nano-microspheres prepared by (1) are added in the aqueous solution of sodium selenite, and stirred at 500r/min for 10min;

3. Weigh 900 mg of ascorbic acid, add it to the mixed solution of chitosan nanospheres and sodium selenite, continue to stir and react for 3 hours to form a deep red transparent solution, and obtain red nano selenium.

Add wetting agent Tween-20 and conventional nutrients K ₂ SO ₄ , KNO ₃ , KH ₂ PO ₄ to the red nano-selenium solution prepared above, stir and mix well to prepare nano-selenium 80ppm, K ₂ SO ₄ 2g/l, KNO ₃ 3g/l, KH ₂ PO ₄ 2g/l, Tween-20 0.1% (by weight) is a fruit and vegetable nano-selenium nutrition regulator.

Example 3:

Preparation of Nano Selenium Using Chitosan as Template

(1) Preparation of Chitosan Nanospheres

1. Take by weighing 1.8g chitosan powder, dissolve completely in 150ml 1% acetic acid solution under stirring condition.

2. Slowly add 1% TPP solution until milky white appears, the amount of TPP added dropwise is 1/10 of chitosan, and stirred at 500r/min for 30 minutes to form an emulsion.

(2) Preparation of nano-selenium

1. Weigh 300mg of sodium selenate and dissolve it in 150ml of water;

2. The chitosan nano-microspheres prepared by (1) are added in the aqueous solution of sodium selenate, and stirred at 500r/min for 10min;

4. Weigh 1000 mg of trisodium citrate, add it to the mixed solution of chitosan nano-microspheres and sodium selenate, continue to stir and react for 3 hours to form a dark red transparent solution, and obtain red nano-selenium.

Add wetting agent Tween-20 and conventional nutritional components K2SO4, _KNO3 , KH2PO4 to the red nano-selenium solution prepared above, stir and mix well, and then red nano-selenium 30ppm can be prepared; K2SO4 1g/l, KNO3 _2g / 1, KH2PO4 1g/l, Tween-80 0.1, (by weight) the fruit and vegetable nano-selenium nutritional regulator.

Example 4

(1) Preparation of starch nanospheres

1. Weigh 1.2g soluble starch, heat and hydrolyze it in 150ml distilled water.

2. When the hydrolyzate is cooled to 40° C., slowly add cross-linking agent POCL ₃ accounting for 1% of the starch mass, and stir at 500 r/min for 30 minutes.

(2) Preparation of nano-selenium

3. Weigh 300mg of sodium selenite and dissolve it in 150ml of water;

4. Weigh 600mg of mercaptoethanol and add it to the aqueous solution of sodium selenite. At the same time, add the starch aqueous solution prepared in (1) to the reaction solution, stir and react at 500r/min for 3h, and form a red transparent solution to obtain red nano-selenium .

Add wetting agent Tween-80 and conventional nutrients K ₂ SO ₄ , KNO ₃ , KH ₂ PO ₄ to the red nano-selenium solution prepared above, stir and mix well, and then prepare red nano-selenium 50ppm; K ₂ 5O ₄ 4g/l, KNO ₃ 5g/l, KH ₂ PO ₄ 4g/l, AEO-10 0.2% (by weight) is a fruit and vegetable nano-selenium nutritional regulator.

Example 5

The steps are the same as in Example 2, red nano-selenium 5ppm; K ₂ SO ₄ 0.1g/l KNO ₃ 0.1g/l KH ₂ PO ₄ 0.1g/l Triton-100 0.1%

Example 6

The steps are the same as in Example 2, red nano-selenium 500ppm; K ₂ SO ₄ 10g/l KNO ₃ 10g/l KH ₂ PO ₄ 10g/l Triton-100 1%

Embodiment 7:

Field implementation of nano-selenium nutrient regulator

One. The field test of fruit grapes in Tianding Township, Yuelu District, Changsha, Hunan: spray the product provided by embodiment 1 three times in the grape flowering stage, fruit drop stage and ripe stage, and the use concentration is 50ppm of selenium element. The selenium content of grapes reached (85±5) μg/kg, which was nearly 15 times higher than that of the control group; the sugar content reached (19±1.4)%, which was more than 11% higher than that of the control group; the acidity was (6.1±0.4) g /l, which was more than 7% lower than that of the control group. Grape quality has improved significantly.

Two. The field test of vegetable loofah in Meishan Village, Duoshan Town, Lengshuijiang City, Hunan Province: the product provided by embodiment 1 is sprayed twice in the loofah flowering early stage and fruiting stage, and the use concentration is 50ppm containing selenium element. It was detected that the selenium content of the loofah reached (73±4) μg/kg, which was nearly 8 times higher than that of the control group, and the taste was significantly improved.

Claims (5)

1. Fruit and vegetable nano-selenium nutrition regulator, whose components include conventional nutritional ingredients, is characterized in that it is also composed of red nano-selenium with high biological activity and a wetting agent with strong wetting ability. Nano-selenium is composed of starch nano-microsphere template or chitosan nano-microsphere template and nano-selenium enriched thereon; the concentration range of the red nano-selenium in the nutrient regulator is 5-500ppm, and the moisturizing The concentration range of the wet agent in the nutrient conditioner is 0.01-1%, by weight. 2. The nano-selenium nutrition regulator for fruits and vegetables according to claim 1, characterized in that: the wetting agent is one or more of the following substances: Tween series, fatty alcohol polyoxyethylene ether series, Fatty phenol polyoxyethylene ether series are nonionic and anionic surfactants that are easily soluble in water and have strong adhesion; the conventional nutritional ingredients are K ₂ SO ₄ , KH ₂ PO ₄ , and KNO ₃ . 3. The fruit and vegetable nano-selenium nutrition regulator according to claim 2, characterized in that: the wetting agent is Tween-80, Tween-20, AEO-10, and Triton-100. 4. The fruit and vegetable nano-selenium nutrition regulator according to claim 1, characterized in that: the concentration range of the conventional nutritional ingredients in the nutrition regulator is 0.1-10g/l. 5. The fruit and vegetable nano-selenium nutrition regulator according to claim 1, characterized in that: the concentration range of red nano-selenium in the nutrition regulator is 30-100ppm, and the concentration of the wetting agent in the nutrition regulator The range is 0.05-0.2%, and the concentration range of the conventional nutritional ingredients in the nutrition regulator is 0.5-5g/l by weight.