CN105777381B - Vitamin B-containing medium-trace element compound fertilizer and preparation method thereof - Google Patents
Vitamin B-containing medium-trace element compound fertilizer and preparation method thereof Download PDFInfo
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- CN105777381B CN105777381B CN201610223724.1A CN201610223724A CN105777381B CN 105777381 B CN105777381 B CN 105777381B CN 201610223724 A CN201610223724 A CN 201610223724A CN 105777381 B CN105777381 B CN 105777381B
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
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- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
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- C05D9/02—Other inorganic fertilisers containing trace elements
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Abstract
The invention provides a microelement compound fertilizer containing vitamin B, which is characterized by at least comprising the following components in parts by weight: 0.1-2 parts by weight of EDTA chelated copper, 3-10 parts by weight of EDTA chelated zinc, 1-7 parts by weight of EDTA chelated iron, 1-6 parts by weight of EDTA chelated manganese, 1-5 parts by weight of EDTA chelated magnesium, 2-8 parts by weight of sodium borate, 2-10 parts by weight of vitamin B, 1-20 parts by weight of diethyl aminoethyl hexanoate DA-6 and 3-12 parts by weight of modified oligochitosan; the vitamin B-containing medium and trace element compound fertilizer provided by the invention has good cold resistance and disease resistance, has an obvious effect on yellowing caused by lack of medium and trace elements in plants, can improve the nutrient content and yield of crops, and has the advantages of simple operation and safe operation environment.
Description
Technical Field
The invention belongs to the field of agricultural planting, and particularly relates to a vitamin B-containing medium-trace element compound fertilizer and a preparation method thereof.
Background
The medium trace element has an extremely important effect on the growth of plants, the trace element is a chemical element with very low content in the nature, part of the trace element has biological significance and is necessary for the normal growth and life of plants and animals, the effect of the trace element in the bodies of the plants and the animals has very strong specificity and is irreplaceable and irreplaceable, when the supply is insufficient, the plants often show specific deficiency symptoms, for example, the lack of the medium trace element in the growth process of the plants can cause the yellowing of the plants, the yield of crops is reduced, the quality is reduced, and the crop is possibly produced absolutely in serious cases, and the application of the medium trace element fertilizer is favorable for improving the yield and the quality of the crops. At present, a certain research is carried out on a compound trace element fertilizer containing medium trace elements required by plant growth, and a chelating agent is adopted to carry out a chelating reaction with a plurality of trace elements, so that the obtained chelated trace element fertilizer can improve the yield of crops, but the actual requirements on vegetables and fruits cannot be met along with the improvement of the yield of the crops.
In order to solve the problems, a fertilizer which is environment-friendly, can obviously improve the yellowing phenomenon of plants and can improve the yield, the nutrient content, the cold resistance and the disease resistance of crops is needed.
Disclosure of Invention
In order to solve the above problems, one aspect of the present invention provides a vitamin B-containing medium trace element compound fertilizer, which is characterized by comprising, in parts by weight:
0.1-2 parts of EDTA chelated copper
3-10 parts of EDTA chelated zinc
EDTA chelated iron 1-7
EDTA chelated manganese 1-6
EDTA chelated magnesium 1-5
2-8% of boric acid sodium salt
2-10% of vitamin B
Diethyl aminoethyl hexanoate 1-20
3-12 parts of modified chitosan oligosaccharide,
wherein, the modified chitosan oligosaccharide is obtained by grafting at least piperazine diketonic acid, abscisic acid and salicylic acid on chitosan oligosaccharide.
In one embodiment, the vitamin B-containing medium trace element compound fertilizer further contains EDTA chelated calcium, wherein the EDTA chelated calcium is 1-10 parts by weight.
In one embodiment, the vitamin B is vitamin B1, B2, and B16.
In one embodiment, the mass ratio of the vitamins B1, B2 and B16 is (0.5-5): (0.005-0.8): 1.
in one embodiment, the mass ratio of the vitamins B1, B2 and B16 is (1-4.5): (0.01-0.7): 1.
in one embodiment, the modified oligochitosan has a weight average molecular weight of 3000 to 50000.
In one embodiment, the grafting ratio of the modified oligochitosan to the abscisic acid is 1-3%.
In one embodiment, the grafting ratio of the modified oligochitosan to piperazine diketonic acid is 1-2%.
In one embodiment, the grafting ratio of the modified oligochitosan to salicylic acid is 1-3%.
In another aspect of the present invention, there is provided a method for preparing a vitamin B-containing medium trace element compound fertilizer, comprising the steps of:
(1) immersing chitosan oligomer with the weight average molecular weight of 3000-50000 into 2V 2vt percent acetic acid solution and 2V5wt percent hydrogen peroxide solution according to the parts by weight;
(2) dissolving piperazinedioic acid in 10V methanol according to parts by weight, and adding the solution into the chitosan oligomer solution obtained in the step (1) to obtain a reaction solution;
(3) adjusting the pH of the reaction solution obtained in the step (2) to be neutral by using a 10wt% NaOH aqueous solution, filtering, soaking, washing, filtering and drying intercepted substances;
(4) dispersing the oligochitosan piperazinedioic acid amide synthesized in the step (3) in acetone, adding 20wt% of NaOH aqueous solution for alkalization, then adding abscisic acid and salicylic acid in batches according to parts by weight for grafting reaction, and finally discharging slurry;
(5) adjusting the slurry prepared in the step (4) to be neutral, then distilling under reduced pressure to remove the solvent to obtain a reaction crude product, dissolving the crude product in dimethyl sulfoxide (6V), then carrying out suction filtration, and distilling the filtrate under reduced pressure again to remove the dimethyl sulfoxide to obtain modified chitosan oligosaccharide;
(6) adding EDTA chelated copper, EDTA chelated zinc, EDTA chelated iron, EDTA chelated manganese, EDTA chelated magnesium, sodium borate, vitamin B, diethyl aminoethyl hexanoate, modified chitosan oligomer and EDTA chelated calcium into a reaction container according to the parts by weight for mixing;
(7) adding edible pigment into the materials in the step (6) for color matching;
(8) and (5) stirring the materials in the step (7), uniformly mixing, and drying to obtain the vitamin B-containing medium and trace element compound fertilizer.
The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" embraces the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer".
"interpolymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally used to refer to polymers prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to polymers prepared from three different monomers). It also includes polymers made by polymerizing more monomers. "blend" means a polymer formed by two or more polymers being mixed together by physical or chemical means.
One aspect of the invention provides a vitamin B-containing medium trace element compound fertilizer, which at least comprises the following components in parts by weight:
0.1-2 parts of EDTA chelated copper
3-10 parts of EDTA chelated zinc
EDTA chelated iron 1-7
EDTA chelated manganese 1-6
EDTA chelated magnesium 1-5
2-8% of boric acid sodium salt
2-10% of vitamin B
Diethyl aminoethyl hexanoate 1-20
3-12 parts of modified chitosan oligosaccharide,
wherein, the modified chitosan oligosaccharide is obtained by grafting at least piperazine diketonic acid, abscisic acid and salicylic acid on chitosan oligosaccharide.
In one embodiment, the vitamin B-containing medium trace element compound fertilizer at least comprises the following components in parts by weight:
0.5-1.5 parts of EDTA chelated copper
EDTA chelated zinc 2-8
EDTA chelated iron 1-6
EDTA chelated manganese 1-4
EDTA chelated magnesium 1-4
2-6 parts of sodium borate salt
2 to 8 parts of vitamin B
Diethyl aminoethyl hexanoate 1-16
3-10 parts of modified chitosan oligosaccharide,
the chelate is a complex having a cyclic structure formed by binding a central ion and a polydentate ligand. The chelate is one of complexes, and one or more polydentate ligands are required to provide a plurality of pairs of electrons to form coordination bonds with a center body in the structure of the chelate. Chelates are generally more stable than the common complexes, and the structures often have five or six membered ring structures that enhance stability. The chelating agent can selectively capture certain metal ions in plant cells and release the metal ions in a proper amount when necessary, so that the crops can absorb nutrition more easily, fully and reasonably. In order to achieve the purpose of balanced fertilization, one or more medium trace elements are additionally applied according to the condition of nutrient deficiency of some plants, so that the fertilizer plays a certain role in balancing elements required by crops and preventing and treating physiological diseases caused by nutrient deficiency. However, most of the medium and trace elements used in China are simple inorganic salts, and the utilization rate is limited to a certain extent. Once the inorganic active medium and trace elements enter the fertilizer and are applied to soil, most of the inorganic active medium and trace elements lose activity and can be absorbed by plants very little, so even if balanced fertilization and balanced fertilizer distribution are carried out, balanced absorption by crops is not equal, and the reason why the soil balanced fertilization is tested is that the crops still have nutrient deficiency symptoms. In order to solve the contradiction, EDTA and EDTA disodium are used as chelating agents to generate chelate from trace elements, so that the stability of the trace elements is effectively improved, and the utilization rate of the fertilizer is improved.
The preparation method of the EDTA chelated trace elements comprises the following steps:
(1) adding 0.5mol of EDTA,200ml of purified water and 0.2mol of sodium hydroxide into a 500ml reaction bottle, stirring, adding 0.1mol of calcium sulfate after complete dissolution, heating to 80 ℃, carrying out chelation reaction, keeping the temperature for 1h, and adding 0.1mol/L hydrochloric acid to adjust the pH value to 9.0-10.0 after the reaction is finished;
(2) adding 0.1mol of ferrous sulfate, 0.1mol of manganese sulfate, 0.1mol of zinc sulfate and 0.1mol of copper sulfate into a reaction bottle, heating to 80 ℃, carrying out chelation reaction, keeping the temperature for 1 hour, and adding 0.1mol/L hydrochloric acid to adjust the pH value to 5.5-6.5 after the reaction is finished;
(3) and (3) adding 60g of bentonite into the reaction solution obtained in the step (2), and adjusting the pH value to 7.0-7.5 by using 0.1mol/L sodium hydroxide solution or 0.1mol/L hydrochloric acid solution to obtain the chelated trace elements.
The zinc can enhance the photosynthesis of crops and catalyze the synthesis of carbon dioxide, thereby improving the intensity of the photosynthesis, increasing the sugar content and increasing the content of protein in the granules. Zinc is rather closely related to the formation of ribonucleic acids which have a major influence on the genetic properties of plants. After zinc is applied, the ribonucleic acid content in the body can be increased, and the growth and development of plants are promoted. Plants are highly sensitive to zinc deficiency: corn, rice, buckwheat, soybean, cotton, tobacco, sunflower, cabbage, celery, spinach, apple, citrus, grape, coffee, etc. Moderately sensitive to zinc deficiency are: sorghum, potato, tomato, beet, onion, and the like.
Magnesium is the main component of chlorophyll, and can activate a plurality of enzymes in the metabolism of phosphoric acid, the metabolism of nitrogen and the metabolism of carbon, thus playing the role of an activator. Magnesium is indispensable for maintaining the structure of ribose and nucleoprotein and determining the physicochemical properties of protoplasm, and has indirect influence on respiration. Generally, the soil is easy to lack magnesium when acid sandy soil, soil with high leaching and low cation exchange amount, calcareous soil with low magnesium content of matrix or acid soil is too much and lime or potash fertilizer is applied. The young trees lack magnesium and are easy to cause early leaf fall, which mostly occurs in mid-summer, and sometimes leaves are basically fallen clean in one night. The grown trees lack magnesium, mostly begin from the base leaves of the new tips, the pulse is dark green when the trees are light, the fruits cannot be normally ripe when the trees are heavy, the fruits are small, the color is different, and the fruits have no fragrance. When the amount of magnesium is too large, imbalance between elements in the tree body is caused, such as insufficient calcium absorption, potassium deficiency, zinc deficiency, and the like. The magnesium deficiency of crops appears on the leaves with obvious characteristics, namely, the magnesium deficiency appears on the middle and lower leaves firstly, and then gradually develops upwards. Since magnesium is a constituent of chlorophyll, in the absence of magnesium, leaves usually lose green, begin with a diminished color between the tip and the limbus, turn yellow from pale green, and then expand toward the base and center of the leaf. But the veins are still green, and clear reticular veins are formed on the leaves. In severe cases, the leaves wither and fall off.
Boron can promote the normal development of reproductive organs, and one important symptom of boron deficiency is that seeds cannot normally develop or even cannot form, thereby influencing the harvest of crops. Boron has a promoting effect on the synthesis and transportation of sugar in crops, and chloroplast is degenerated in the absence of boron to influence photosynthesis. The boron can improve the nitrogen fixation activity of the legume rhizobium and increase the nitrogen fixation amount. In the absence of boron, nodules develop and affect the nitrogen fixation. Boron can also enhance crop stress resistance. Boron is indispensable and irreplaceable for normal growth and development of crops, has good effects on growth and reproduction of the crops, can improve the supply condition of organic matters in each organ of plants and increase the maturing rate of the crops. The lack of boron in crops can cause the unevenness of leaves, the thickening, the brittleness and the deep color of old leaves, the atrophy, the curling, the green loss and the longitudinal fissure of leaf veins, the thickening, the shortening and the cracking of leaf stalks, less and small flowers, less pollen grains, deformity and weak vitality, the normal fertilization process is not easy to complete, and the seed setting rate is low. Fruit dysplasia, which is often misshapen, small and hard, affects yield. Is mainly applied to rape, cotton, beet, orange and solanaceous vegetables.
Manganese plays a catalytic role in chlorophyll synthesis, plant chloroplasts contain manganese which can promote seed germination and seedling growth, and the photosynthesis of crops is influenced in the absence of manganese, and the photosynthesis is shown as the green and yellow between leaf veins with brown spots which are gradually increased and scattered on whole leaves, so that the leaves are changed into red and gray, and the leaves are shrunken. Plants are highly sensitive to manganese deficiency: peanut, soybean, pea, mung bean, wheat, tobacco, beet, potato, sweet potato, cucumber, onion, radish, spinach, strawberry, cherry, lemon, apple, peach, hickory, orange, etc. Moderately sensitive to manganese deficiency are: sesbania, vetch, clover, barley, corn, sorghum, flax, broccoli, cabbage, celery, tomato, turnip, carrot, cotton, etc.
Diethyl aminoethyl hexanoate DA-6 was a high-energy plant growth regulator newly discovered by American scientists in the 90 s and has a broad-spectrum and breakthrough effect. It can increase the activity of plant peroxidase and nitrate reductase, increase the content of chlorophyll to accelerate photosynthesis speed, promote division and elongation of plant cells, promote root development, regulate the balance of nutrients in vivo, and has obvious effect on yellowing caused by trace elements lacking in plants.
DA-6 is more efficient than other plant growth regulators, and is mainly reflected in the aspect of improving the growth vigor, so that farmers can know the DA-6 as a good regulator at a glance, and the DA-6 is capable of promoting the stout and lodging resistance of plants, which is not possessed by other growth regulators such as plant growth regulators.
In one embodiment, the vitamin B-containing trace element compound fertilizer further contains EDTA chelated calcium, wherein the EDTA chelated calcium is 1-10 parts by weight; preferably, the microelement compound fertilizer containing vitamin B also contains EDTA chelated calcium, wherein the weight portion of the EDTA chelated calcium is 3-8.
Ca element, not only is a structural substance of cells, but also is a second messenger that mediates almost all responses of plant growth and development and environmental changes such as low temperature stress. Low temperature or hormonal causes not onlyCytoplasmic Ca2+Increased levels of and cause intracellular Ca2+The concentration increases rapidly. Cytoplasmic Ca2+Low concentration (less than or equal to 0.10 mu mol/L) and Ca in cell wall, endoplasmic reticulum and vacuole2+The concentration is higher than cytoplasm by more than 2 orders of magnitude. These sites or organelles are called the "calcium stores" of the cell, the cell wall is the "extracellular calcium store", and the "intracellular calcium stores" include vacuoles, endoplasmic reticulum, and mitochondria, among others. Fine Ca is present in plant cells2+The mechanism of concentration regulation, mainly Ca2+Channel, Ca2+/H+Exchanger and Ca2+-ATPase and Ca2+-a binding protein. Intracellular Ca2+Strictly regionalized distribution and maintenance of cytoplasmic Ca2+Homeostasis is a prerequisite for normal growth of cells. Ca in the cytoplasm after cells are stimulated2+The concentration rose briefly and significantly. Ca in cytoplasm2+The concentration is increased, originating from the extracellular and intracellular calcium stores. Extracellular Ca2+Can pass Ca on the plasma membrane along the chemical potential gradient2+Passage into the cytoplasm, intracellular Ca2+By Ca on the inner membrane2+The channel enters the cytoplasm.
The signal receptors of calcium ion channels, Calcium Dependent Protein Kinases (CDPKs) and the like on cell membranes induce cells to release Ca after receiving low-temperature stress signals2+Or inducing the cells to produce secondary signal molecules such as inositol polyphosphate, cADP ribose and NADP salt, thereby stimulating the cells to release Ca2+Activating protein kinase to participate in protein phosphorylation metabolic process and inducing the expression of stress target gene. With Ca2+Chelating agent, Ca2+Channel blockers and trans-Ca2+The research result of the channel protein gene technology shows that Ca2+Is involved in the response of plants to low-temperature stress and is related to the expression regulation of some low-temperature induced genes of plants. Influencing Ca by altering the biochemical metabolic pathways of secondary signal molecules2+The level of the released fluid can adjust the expression of low-temperature stress genes and influence the cold resistance of plants. When the inositol phospholipid system (IP3) in the cell is activated, Ca in the intima system can also be promoted2+Because IP3 has an opening Ca2+The function of the channel. IP3 is water soluble and diffuses from the plasma membrane to the cytosolGlue, then with IP3-Ca on the endoplasmic reticulum or vacuolar membrane2+The channels join to open the channels. The physiological functions of IP3 are all through Ca2+Increased concentration of Ca2+Is mediated as a second messenger.
In one embodiment, the trace element compound fertilizer contains vitamin B, wherein the vitamin B is vitamin B1, B2 and B16.
The vitamin B group can enhance the transformation of crop protease to improve the yield, prolong the functional period of leaves, improve the vitamin content of melons and fruits, enhance the disease resistance and cold resistance of crops, promote the development of crop roots, thick and green leaves, thick and strong stems and plump seeds, improve the quality of crops, fruits and vegetables and improve the standard of the vitamin content.
In one embodiment, the microelement compound fertilizer contains vitamin B, and the mass ratio of the vitamin B1, the vitamin B2 and the vitamin B16 is (0.5-5): (0.005-0.8): 1.
in one embodiment, the microelement compound fertilizer contains vitamin B, and the mass ratio of the vitamin B1, the vitamin B2 and the vitamin B16 is (1-4.5): (0.01-0.7): 1.
in one embodiment, the trace element compound fertilizer containing vitamin B, the modified chitosan oligosaccharide is chitosan oligosaccharide grafted with at least abscisic acid, piperazinone acid and salicylic acid.
Low-temperature exercise (4 ℃/2 ℃) or exogenous abscisic acid treatment can induce low-temperature induced gene expression and enhance the cold resistance of plants, and the freezing resistance of the plants is reduced due to the fact that synthesis of abscisic acid of the abscisic acid deletion mutant abscisic acid-1 or the insensitive mutant abi-1 is blocked or insensitive to the action of abscisic acid, but cor gene expression of abscisic acid-1 mutant plants is normal, abi-1 can influence the abscisic acid induced cor gene expression without influencing the low-temperature induced cor gene expression, and ABRE deletion can not influence the low-temperature stress factor induced expression of CRT/DRE. The gene induced by abscisic acid signal transmission at low temperature can be divided into three categories according to whether the gene expression depends on abscisic acid, (1) abscisic acid-dependent transmission (such as seed storage protein gene and adversity inducing gene) for gene expression, (2) abscisic acid-independent transmission path for cold-induced gene expression, and (3) abscisic acid and low temperature combined action control gene expression.
Both low temperature exercise and abscisic acid treatment have the effect of enhancing the cold resistance of plants. It has now been found that the expression of a number of genes can be induced by exogenous abscisic acid, most of which are expressed during the post-maturation phase of seeds or in the response of plant organs to stress. Spraying exogenous abscisic acid to enhance the SOD activity of the rice seedlings under low-temperature stress and in temperature return recovery, but the increase of the SOD activity of the rice seedlings does not activate the enzyme but promotes the resynthesis of the enzyme.
The basic structure of the diketopiperazine compound is cyclodipeptide formed by condensing two amino acids, and the skeleton of the diketopiperazine compound has a stable six-membered ring structure and two hydrogen bond donors and two hydrogen bond receptors, so that the DKPs have stronger biological activity and pharmacological activity and become an important pharmacophore in medicinal chemistry. In recent years, a series of cyclic dipeptide compounds are discovered from marine microorganisms, and researches show that the functions of the cyclic dipeptide compounds are not limited in the aspects of antibiosis, cytotoxic activity and the like, and the cyclic dipeptide compounds also play an important role in a quorum sensing regulation mechanism.
The piperazine ring is a commonly used nitrogen heterocycle in medicinal chemistry research, the physicochemical property of a compound can be effectively adjusted by introducing the piperazine ring into a medicament molecule, the pharmacokinetic property of a medicament is improved, a plurality of compounds containing the piperazine ring have strong antifungal activity, a series of derivatives of which the catenin is modified by the piperazine ring have good antifungal effect, show wide antifungal spectrum and have good inhibition effect on bacteria such as bacillus subtilis and the like.
Hormones are considered to be promoters of cold-resistant gene expression. The plant growth regulator can effectively influence and control the growth and development of plants and the adaptability to low-temperature stress. Chemical induction of plant cold resistance is based on the intensive research of the plant cold resistance mechanism, especially the thorough understanding of the species, properties and actions of chemical signal substances of plant cold resistance. Although the chemical induction effect can not take effect instantly, the application technology is mature under certain conditions,
The effect is remarkable. At present, the most cold-resistant chemical inducers used in practice are molecules and derivatives thereof, such as Salicylic Acid (SA) and derivatives thereof, abscisic acid (ABA) and derivatives thereof, which act as low-temperature stress signal transducers during the formation of cold resistance of plant systems.
In one embodiment, the microelement complex fertilizer containing vitamin B, the modified oligochitosan has the weight-average molecular weight of 3000-50000; optimally, the weight average molecular weight of the modified chitosan oligosaccharide is 5000-30000.
The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (abbreviated as "GPC"). The measurement conditions of GPC are measured by conditions conventional in the art, and can be measured, for example, in the following manner.
Column: the following columns were connected in series and used.
"TSKgelG 5000" (7.8 mmI.D.. times.30 cm). times.1 roots
"TSKgelG 4000" (7.8 mmI.D.. times.30 cm). times.1 roots
"TSKgelG 3000" (7.8 mmI.D.. times.30 cm). times.1 roots
"TSKgelG 2000" (7.8 mmI.D.. times.30 cm). times.1 roots
A detector: RI (differential refractometer); column temperature: 40 ℃; eluent: tetrahydrofuran (THF); flow rate: 1.0 mL/min; injection amount: 100. mu.L (sample concentration 4mg/mL tetrahydrofuran solution); standard sample: the following monodisperse polystyrene was used to prepare a calibration curve.
The term "oligomeric chitosan" as used herein refers to a polymer comprising chitosan monomer units. In one embodiment, the chitosan monomer may be represented by the following formula
In one embodiment, the oligochitosan may be represented by the formula
Wherein n is about 16 to 310, and in a preferred embodiment, n is about 16 to 124.
The chitosan is a natural plant nutrient growth promoter-leaf fertilizer raw material, and the leaf fertilizer compounded by the chitosan can not only kill insects and resist diseases for plants, play a role of fertilizer, but also decompose animal and plant residues and trace metal elements in soil, thereby converting the animal and plant residues into nutrients for plants, enhancing the immunity of the plants and promoting the health of the plants.
Chitosan has broad-spectrum antibacterial activity, and the antibacterial action mechanism of the chitosan is mainly divided into two types: for macromolecular chitosan, a layer of macromolecular membrane is formed on the surface of bacteria mainly through the dense macromolecular chains, which influences the transportation of in vitro nutrient substances into cells, prevents the excretion of metabolites, and makes the metabolism of bacteria body disordered, thereby achieving the effects of sterilization and bacteriostasis; the small molecular chitosan can reach the inside of bacteria through osmosis, adsorb cytoplasm with anions in cells, flocculate and denature the cytoplasm, disturb normal physiological activities of the bacteria, and play a role in antibiosis and sterilization.
The low-molecular chitosan with the weight-average molecular weight of 5000-10000, which is prepared by degrading chitosan, has a certain inhibition effect on bacteria and microorganisms, and the inhibition effect is enhanced along with the increase of mass concentration. The inhibition effect of chitosan on different bacteria changes with the change of molecular weight, and the antibacterial effect of chitosan on staphylococcus aureus gradually weakens with the reduction of molecular weight. The research shows that the chitosan has the effect of inhibiting the growth of the streptomyces variabilis, the chitosan molecules with positive charges act with the cell membranes with negative charges of bacteria to damage the cell walls, and the chitosan is easy to penetrate through the damaged cell walls to enter the cell cores and is combined with molecules to damage DNA synthesis, so that the chitosan has antibacterial activity.
The term "modified chitosan oligosaccharide" used herein refers to modified chitosan oligosaccharide with piperazine dione acid, and then modified with abscisic acid and salicylic acid.
The invention aims to modify chitosan molecules by taking chitosan as a lead compound. In order to enhance the bactericidal and bacteriostatic activity of chitosan, the invention adopts the following two approaches:
firstly, modifying chitosan molecules, and inoculating piperazine diketonic acid which is an active group with bactericidal and bacteriostatic activity into the chitosan molecules, so that the activities of the inoculated active group and the chitosan are mutually enhanced, and the aim of enhancing the bactericidal and bacteriostatic activity is fulfilled.
Secondly, the bactericidal and bacteriostatic activity of the chitosan is enhanced. The biological activity of chitosan is derived from its C2Position-active amino groups, C3And C6The active hydroxyl group, wherein the bactericidal and bacteriostatic activity is mainly related to the amino group, and the polycation of the amino, namely the electropositivity of the amino plays a key role. The electropositive property of amino can be changed by modifying chitosan, and the bactericidal and bacteriostatic activity of the chitosan is enhanced, namely the cold resistance of crops is enhanced by grafting abscisic acid and salicylic acid on the modified oligomeric chitosan, so that the novel bacteriostatic agent with the functions of enhancing the cold resistance and the antibacterial active center of the crops is prepared.
In one embodiment, the grafting ratio of the modified oligochitosan to the abscisic acid is 1-3%; optimally, the grafting rate of the modified chitosan oligosaccharide and the abscisic acid is 1-2.4%.
In one embodiment, the microelement complex fertilizer containing vitamin B has a grafting ratio of the modified oligochitosan to piperazine diketonic acid of 1-2%; optimally, the grafting rate of the modified chitosan oligosaccharide and piperazine diketonic acid is 1-1.8%.
In one embodiment, the grafting ratio of the modified oligochitosan to salicylic acid is 1-3%; optimally, the grafting rate of the modified chitosan oligosaccharide and salicylic acid is 1-2.5%.
In another aspect of the present invention, there is provided a method for preparing a trace element complex fertilizer containing vitamin B, the method comprising the steps of:
(1) immersing chitosan oligomer with the weight average molecular weight of 3000-50000 into 2V 2vt percent acetic acid solution and 2V5wt percent hydrogen peroxide solution according to the parts by weight;
(2) dissolving piperazinedioic acid in 10V methanol according to parts by weight, and adding the solution into the chitosan oligomer solution obtained in the step (1) to obtain a reaction solution;
(3) adjusting the pH of the reaction solution obtained in the step (2) to be neutral by using a 10wt% NaOH aqueous solution, filtering, soaking, washing, filtering and drying intercepted substances;
(4) dispersing the oligochitosan piperazinedioic acid amide synthesized in the step (3) in acetone, adding 20wt% of NaOH aqueous solution for alkalization, then adding abscisic acid and salicylic acid in batches according to parts by weight for grafting reaction, and finally discharging slurry;
(5) adjusting the slurry prepared in the step (4) to be neutral, then distilling under reduced pressure to remove the solvent to obtain a reaction crude product, dissolving the crude product in dimethyl sulfoxide (6V), then carrying out suction filtration, and distilling the filtrate under reduced pressure again to remove the dimethyl sulfoxide to obtain modified chitosan oligosaccharide;
(6) adding EDTA chelated copper, EDTA chelated zinc, EDTA chelated iron, EDTA chelated manganese, EDTA chelated magnesium, sodium borate, vitamin B, diethyl aminoethyl hexanoate, modified chitosan oligomer and EDTA chelated calcium into a reaction container according to the parts by weight for mixing;
(7) adding edible pigment into the materials in the step (6) for color matching;
(8) and (5) stirring the materials in the step (7), uniformly mixing, and drying to obtain the vitamin B-containing medium and trace element compound fertilizer.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the raw materials used are commercially available from national chemical reagents, unless otherwise specified.
The raw material chitosan is purchased from Shanghai province shellfish Marine bioengineering limited company.
Example 1
(1) Grafting piperazine diketonic acid on chitosan oligomer
Adding 50g of chitosan oligomer with weight average molecular weight of 20000, 100ml of 2vt% acetic acid solution and 100ml of 5wt% hydrogen peroxide solution into a 1000ml three-necked bottle, stirring, completely dissolving, and keeping the temperature at 55 ℃ for 5 h; after the reaction is finished, adding piperazinedioic acid (1g) dissolved in 10ml of methanol, and stirring and reacting for 12 hours at room temperature to obtain a reaction solution; adjusting pH of the reaction solution to neutral with 10wt% NaOH aqueous solution, filtering, soaking in 200ml acetone for 10 hr, washing with 50ml acetone, filtering, and drying at 40 deg.C under reduced pressure for 12 hr.
(2) Grafting abscisic acid and salicylic acid on piperazinone diacid modified oligochitosan
Adding synthesized oligomeric chitosan piperazine dione amide, 300ml acetone and 100ml20wt% NaOH aqueous solution into a 1000ml three-necked bottle, alkalizing for 3h at 50 ℃, then adding 1.5g abscisic acid in batches, reacting for 10h at 55 ℃, then adding 1.5g salicylic acid, reacting for 10h at 55 ℃, cooling to room temperature after the reaction is finished, and finally discharging slurry; then 10wt% acetic acid solution is used for adjusting to be neutral, and then the solvent is removed by reduced pressure distillation to obtain a reaction crude product; and dissolving the crude product in dimethyl sulfoxide (300 ml), then carrying out suction filtration, and distilling the filtrate under reduced pressure again to remove the dimethyl sulfoxide to obtain the modified oligochitosan grafted with piperazine diketonic acid, abscisic acid and salicylic acid simultaneously.
(3) Adding 1.3 parts by weight of EDTA chelated copper, 6 parts by weight of EDTA chelated zinc, 4 parts by weight of EDTA chelated iron, 3 parts by weight of EDTA chelated manganese, 4 parts by weight of EDTA chelated magnesium, 5 parts by weight of sodium borate, 6 parts by weight of vitamin B1, 12 parts by weight of diethyl aminoethyl hexanoate DA-6, 8 parts by weight of modified oligochitosan and 6 parts by weight of EDTA chelated calcium into a reaction container for mixing;
(4) adding edible 5g of pigment into the materials in the step (3) for color matching;
(5) and (5) stirring the materials in the step (4), uniformly mixing, and drying to obtain the vitamin B-containing medium and trace element compound fertilizer.
Examples 2 to 6
The preparation was the same as in example 1, except that the vitamin B species was different;
the vitamin B in example 2 is vitamin B2, the vitamin B in example 3 is vitamin B16, and the vitamin B in example 4 is vitamin B1, B2 and B16 (the mass ratio of B1, B2 and B16 is 3: 0.6: 1); in example 5, vitamin B is vitamin B1, B2, and B16 (the mass ratio of B1, B2, and B16 is 0.5: 0.005: 1); in example 6, vitamin B is vitamin B1, B2, and B16 (mass ratio of B1, B2, and B16 is 5: 0.8: 1).
Example 7
(1) Grafting piperazine diketonic acid on chitosan oligomer
Adding 50g of chitosan oligomer with weight-average molecular weight of 3000, 100ml of 2vt% acetic acid solution and 100ml of 5wt% hydrogen peroxide solution into a 1000ml three-necked bottle, stirring, completely dissolving, and keeping the temperature at 55 ℃ for 5 h; after the reaction is finished, adding piperazinedioic acid (1g) dissolved in 10ml of methanol, and stirring and reacting for 12 hours at room temperature to obtain a reaction solution; adjusting pH of the reaction solution to neutral with 10wt% NaOH aqueous solution, filtering, soaking in 200ml acetone for 10 hr, washing with 50ml acetone, filtering, and drying at 40 deg.C under reduced pressure for 12 hr.
(2) Grafting abscisic acid and salicylic acid on piperazinone diacid modified oligochitosan
Adding synthesized oligomeric chitosan piperazine dione amide, 300ml acetone and 100ml20wt% NaOH aqueous solution into a 1000ml three-necked bottle, alkalizing for 3h at 50 ℃, then adding 1.5g abscisic acid in batches, reacting for 10h at 55 ℃, then adding 1.5g salicylic acid, reacting for 10h at 55 ℃, cooling to room temperature after the reaction is finished, and finally discharging slurry; then 10wt% acetic acid solution is used for adjusting to be neutral, and then the solvent is removed by reduced pressure distillation to obtain a reaction crude product; and dissolving the crude product in dimethyl sulfoxide (300 ml), then carrying out suction filtration, and distilling the filtrate under reduced pressure again to remove the dimethyl sulfoxide to obtain the modified oligochitosan grafted with piperazine diketonic acid, abscisic acid and salicylic acid simultaneously.
(3) Adding 1.3 parts by weight of EDTA chelated copper, 6 parts by weight of EDTA chelated zinc, 4 parts by weight of EDTA chelated iron, 3 parts by weight of EDTA chelated manganese, 4 parts by weight of EDTA chelated magnesium, 5 parts by weight of sodium borate, 6 parts by weight of vitamin B (the mass ratio of B1, B2 and B16 is 3: 0.6: 1), 12 parts by weight of diethyl aminoethyl hexanoate DA-6, 8 parts by weight of modified oligochitosan and 6 parts by weight of EDTA chelated calcium into a reaction vessel for mixing;
(4) adding edible 5g of pigment into the materials in the step (3) for color matching;
(5) and (5) stirring the materials in the step (4), uniformly mixing, and drying to obtain the vitamin B-containing medium and trace element compound fertilizer.
Example 8
The preparation method is the same as that of example 7 except that the weight average molecular weight of the modified chitosan is different; example 8 the weight average molecular weight of the modified chitosan was 50000.
Example 9
(1) Grafting piperazine diketonic acid on chitosan oligomer
Adding 50g of chitosan oligosaccharide with weight average molecular weight of 20000, 100ml of 2vt% acetic acid solution and 100ml of 5% hydrogen peroxide solution into a 1000ml three-necked bottle, stirring, completely dissolving, and keeping the temperature at 55 deg.C for 5 h; after the reaction, piperazine diketonic acid (0.1g) dissolved in 20ml of methanol was added and the mixture was stirred at room temperature for 12 hours to obtain a reaction solution; and (2) adjusting the pH of the reaction solution to be neutral by using 10wt% of NaOH aqueous solution, filtering, soaking for 10h by using 20ml of acetone, washing for 50ml of acetone, filtering, and drying for 12h under reduced pressure at 40 ℃ to obtain the modified oligochitosan grafted with piperazine diketonic acid.
(2) Adding 1.3 parts by weight of EDTA chelated copper, 6 parts by weight of EDTA chelated zinc, 4 parts by weight of EDTA chelated iron, 3 parts by weight of EDTA chelated manganese, 4 parts by weight of EDTA chelated magnesium, 5 parts by weight of sodium borate, 6 parts by weight of vitamin B (the mass ratio of B1, B2 and B16 is 3: 0.6: 1), 12 parts by weight of diethyl aminoethyl hexanoate DA-6, 8 parts by weight of modified oligochitosan and 6 parts by weight of EDTA chelated calcium into a reaction vessel for mixing;
(3) adding edible 5g of pigment into the materials in the step (2) for color matching;
(4) and (4) stirring the materials in the step (3), uniformly mixing, and drying to obtain the vitamin B-containing medium and trace element compound fertilizer.
Example 10
(1) Grafting abscisic acid on oligochitosan
Adding 50g of chitosan oligosaccharide with weight average molecular weight of 20000, 100ml of 2vt% acetic acid solution and 100ml of 5% hydrogen peroxide solution into a 1000ml three-necked bottle, stirring, completely dissolving, and keeping the temperature at 55 deg.C for 5 h; after the reaction is finished, adding 0.15g of abscisic acid, reacting for 10 hours at 55 ℃, cooling to room temperature after the reaction is finished, and finally discharging slurry; then 10wt% acetic acid solution is used for adjusting to be neutral, and then the solvent is removed by reduced pressure distillation to obtain a reaction crude product; and dissolving the crude product in dimethyl sulfoxide, carrying out suction filtration, and distilling the filtrate under reduced pressure again to remove the dimethyl sulfoxide to obtain the modified oligochitosan grafted with piperazine diketonic acid, abscisic acid and salicylic acid simultaneously.
(2) Adding 1.3 parts by weight of EDTA chelated copper, 6 parts by weight of EDTA chelated zinc, 4 parts by weight of EDTA chelated iron, 3 parts by weight of EDTA chelated manganese, 4 parts by weight of EDTA chelated magnesium, 5 parts by weight of sodium borate, 6 parts by weight of vitamin B (the mass ratio of B1, B2 and B16 is 3: 0.6: 1), 12 parts by weight of diethyl aminoethyl hexanoate DA-6, 8 parts by weight of modified oligochitosan and 6 parts by weight of EDTA chelated calcium into a reaction vessel for mixing;
(3) adding edible 5g of pigment into the materials in the step (3) for color matching;
(4) and (5) stirring the materials in the step (4), uniformly mixing, and drying to obtain the vitamin B-containing medium and trace element compound fertilizer.
Example 11
(1) Grafting salicylic acid on oligochitosan
Adding 50g of chitosan oligosaccharide with weight average molecular weight of 20000, 100ml of 2vt% acetic acid solution and 100ml of 5% hydrogen peroxide solution into a 1000ml three-necked bottle, stirring, completely dissolving, and keeping the temperature at 55 deg.C for 5 h; after the reaction is finished, adding 0.15g of abscisic acid, reacting for 10 hours at 55 ℃, cooling to room temperature after the reaction is finished, and finally discharging slurry; then 10wt% acetic acid solution is used for adjusting to be neutral, and then the solvent is removed by reduced pressure distillation to obtain a reaction crude product; and dissolving the crude product in dimethyl sulfoxide, carrying out suction filtration, and distilling the filtrate under reduced pressure again to remove the dimethyl sulfoxide to obtain the modified oligochitosan grafted with piperazine diketonic acid, abscisic acid and salicylic acid simultaneously.
(2) Adding 1.3 parts by weight of EDTA chelated copper, 6 parts by weight of EDTA chelated zinc, 4 parts by weight of EDTA chelated iron, 3 parts by weight of EDTA chelated manganese, 4 parts by weight of EDTA chelated magnesium, 5 parts by weight of sodium borate, 6 parts by weight of vitamin B (the mass ratio of B1, B2 and B16 is 3: 0.6: 1), 12 parts by weight of diethyl aminoethyl hexanoate DA-6, 8 parts by weight of modified oligochitosan and 6 parts by weight of EDTA chelated calcium into a reaction vessel for mixing;
(3) adding edible 5g of pigment into the materials in the step (2) for color matching;
(4) and (4) stirring the materials in the step (3), uniformly mixing, and drying to obtain the vitamin B-containing medium and trace element compound fertilizer.
Comparative example 1
(1) Grafting piperazine diketonic acid on chitosan oligomer
Adding 50g of chitosan oligosaccharide with weight average molecular weight of 20000, 100ml of 2vt% acetic acid solution and 100ml of 5% hydrogen peroxide solution into a 1000ml three-necked bottle, stirring, completely dissolving, and keeping the temperature at 55 deg.C for 5 h; after the reaction, piperazine diketonic acid (0.1g) dissolved in 20ml of methanol was added and the mixture was stirred at room temperature for 12 hours to obtain a reaction solution; adjusting pH of the reaction solution to neutral with 10wt% NaOH aqueous solution, filtering, soaking in 20ml acetone for 10 hr, washing with 50ml acetone, filtering, and drying at 40 deg.C under reduced pressure for 12 hr.
(2) Grafting abscisic acid and salicylic acid on piperazinone diacid modified oligochitosan
Adding synthesized oligomeric chitosan piperazine dione amide, 300ml acetone and 20wt% NaOH aqueous solution into a 1000ml three-necked bottle, alkalizing for 3h at 50 ℃, then adding 0.15g abscisic acid in batches, reacting for 10h at 55 ℃, then adding 0.15g salicylic acid, reacting for 10h at 55 ℃, cooling to room temperature after the reaction is finished, and finally discharging slurry; then 10wt% acetic acid solution is used for adjusting to be neutral, and then the solvent is removed by reduced pressure distillation to obtain a reaction crude product; and dissolving the crude product in dimethyl sulfoxide, carrying out suction filtration, and distilling the filtrate under reduced pressure again to remove the dimethyl sulfoxide to obtain the modified oligochitosan grafted with piperazine diketonic acid, abscisic acid and salicylic acid simultaneously.
(3) Adding 1.3 parts by weight of EDTA chelated copper, 6 parts by weight of EDTA chelated zinc, 4 parts by weight of EDTA chelated iron, 3 parts by weight of EDTA chelated manganese, 4 parts by weight of EDTA chelated magnesium, 5 parts by weight of sodium borate salt, 12 parts by weight of diethyl aminoethyl hexanoate DA-6, 8 parts by weight of modified oligochitosan and 6 parts by weight of EDTA chelated calcium into a reaction container for mixing;
(4) adding edible 5g of pigment into the materials in the step (3) for color matching;
(5) and (5) stirring the materials in the step (4), uniformly mixing, and drying to obtain the vitamin B-containing medium and trace element compound fertilizer.
Comparative example 2
(1) Adding 1.3 parts by weight of EDTA chelated copper, 6 parts by weight of EDTA chelated zinc, 4 parts by weight of EDTA chelated iron, 3 parts by weight of EDTA chelated manganese, 4 parts by weight of EDTA chelated magnesium, 5 parts by weight of sodium borate, 6 parts by weight of vitamin B (the mass ratio of B1, B2 and B16 is 3: 0.6: 1), 12 parts by weight of diethyl aminoethyl hexanoate DA-6, 8 parts by weight of modified oligochitosan and 6 parts by weight of EDTA chelated calcium into a reaction vessel for mixing;
(2) adding 5g of pigment into the material in the step (1) for toning;
(3) and (3) stirring the materials in the step (2), uniformly mixing, and drying to obtain the vitamin B-containing medium and trace element compound fertilizer.
Comparative example 3
(1) Adding 1.3 parts by weight of EDTA chelated copper, 6 parts by weight of EDTA chelated zinc, 4 parts by weight of EDTA chelated iron, 3 parts by weight of EDTA chelated manganese, 4 parts by weight of EDTA chelated magnesium, 5 parts by weight of sodium borate salt, 12 parts by weight of diethyl aminoethyl hexanoate DA-6, 8 parts by weight of modified oligochitosan and 6 parts by weight of EDTA chelated calcium into a reaction container for mixing;
(2) adding edible 5g of pigment into the material in the step (1) for toning;
(3) and (3) stirring the materials in the step (2), uniformly mixing, and drying to obtain the vitamin B-containing medium and trace element compound fertilizer.
Comparative example 4
"Sijiwang-microelement fertilizer" from Shandong Sijiwang agricultural chemical Co., Ltd.
The trace element fertilizers obtained in examples 1 to 11 and comparative examples 1 to 4 were tested according to the following test methods:
1. experimental Material
Common crops of towel gourd, cucumber and tomato are taken as experimental materials.
2. Experimental methods
Cold resistance: in the pot experiment of the loofah, the cucumber and the tomato, in the embodiment, the trace element compound fertilizer is treated by seed dressing, 5 seedlings are fixed in each pot after the seedlings emerge, the seedlings grow to the 3-leaf stage at the temperature of 18 ℃, then the seedlings grow for 6d at the low temperature of 4 ℃, and the death rate of the seedlings is measured.
Good cold resistance: the death rate of the seedling plant is 0;
the cold resistance is general: the death rate of the seedling plants is 1-3%;
weak cold resistance: the death rate of the seedling plants is more than 3 percent.
Disease resistance: luffa cylindrica, Cucumis sativus (variety: Tokiwa Hikari No. 3, type P), and tomato species at 2-3 leaf stage were used as test samples in pots. In the embodiment, the fertilizer is diluted 3000 times by water respectively, and is sprayed on the front and back leaf surfaces of the first and second leaves of the cucumber, and the dosage is 45ml/3 tank.
The following day, a spore suspension (final concentration 3X 10) containing Botrytis cinerea5/ml, DIFCO potato dextrose broth 1.2%) were sprayed on the front and back leaf surfaces of leaf 1 and 2 for inoculation.
After 5 days, the percentage of the area of the 2 nd, 3 rd and 4 th leaves damaged was investigated, respectively, to determine the occurrence level of disease.
Weak disease resistance: the percentage of the damaged area is more than 80 percent, and the protection value is less than 40 percent;
the disease resistance is general: the percentage of the damaged area is 60-80%, and the protection value is 20-40%;
the disease resistance is good: the percentage of the damaged area is less than 40 percent, and the protection value is more than 60 percent.
Yield and nutrient content: in 2015 (1-4 months), the fertilizer is applied to different crops of towel gourd, cucumber and tomato in Henan Cudrania tricuspidata county for planting experiments.
The yield increase rate is that compared with the yield of the crops after the crops are ripe and harvested, compared with the yield of the crops in the same area, the fertilizer of the crops in the planting field uses the fertilizer in the comparative example 4;
the growth rate of nutrient components is measured by comparing the content of vitamins in crops harvested after using the fertilizer of the invention with the content of vitamins in crops harvested after using the fertilizer of the comparative example 4, relative to the fertilizer of crops in the same area;
the determination method of the vitamins comprises the following steps: the high performance liquid phase determination method comprises the following steps: treating a sample with 0.4 mol/L HCl, hydrolyzing at 120 ℃ and 15PSi for 30 min; column C18, 3.9X 300 mm; ultraviolet and fluorescence series connection of detectors; mobile phase composition methanol: water: heptane sulfonic acid (30: 68: 2); the detection wavelength is 254 nm.
TABLE 1 Performance test results
In summary, it can be seen that the medium trace element compound fertilizer containing vitamin B of the present invention has better cold resistance and disease resistance, and can improve the nutrient content and yield of crops compared with the compound fertilizer containing no vitamin B, no modified oligochitosan, modified oligochitosan with different weight average molecular weights, no vitamin B, no modified oligochitosan, and the cangwang-trace element fertilizer of shandong cangwang agrichemical ltd.
The above examples are merely illustrative and serve to explain some of the features of the invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims not be limited by the choice of examples illustrating features of the invention, and that technological advances will form possible equivalents or sub-substitutes not presently contemplated for reasons of inaccuracy of the linguistic expressions, and that such variations are to be construed as being covered by the appended claims where possible.
Claims (2)
1. A vitamin B-containing medium trace element compound fertilizer is characterized by at least comprising the following components in parts by weight:
wherein, the modified chitosan oligosaccharide is obtained by modifying the chitosan oligosaccharide with piperazinedioic acid and then modifying the modified chitosan oligosaccharide with abscisic acid and salicylic acid;
the vitamin B is vitamin B1, B2 and B16; the mass ratio of the vitamins B1, B2 and B16 is 3: 0.6: 1;
the weight average molecular weight of the modified oligochitosan is 3000-50000;
the grafting rate of the modified chitosan oligosaccharide and the abscisic acid is 1-3%;
the grafting rate of the modified oligochitosan and piperazine diketonic acid is 1-2%;
the grafting rate of the modified chitosan oligosaccharide and salicylic acid is 1-3%.
2. A method for preparing a vitamin B-containing medium trace element compound fertilizer according to claim 1, which comprises the steps of:
immersing chitosan oligomer with the weight average molecular weight of 3000-50000 into 2V 2vt percent acetic acid solution and 2V5wt percent hydrogen peroxide solution according to the parts by weight;
(2) dissolving piperazinedioic acid in 10V methanol according to parts by weight, and adding the solution into the chitosan oligomer solution obtained in the step (1) to obtain a reaction solution;
(3) adjusting the pH of the reaction solution obtained in the step (2) to be neutral by using a 10wt% NaOH aqueous solution, filtering, soaking, washing, filtering and drying intercepted substances;
(4) dispersing the oligochitosan piperazinedioic acid amide synthesized in the step (3) in acetone, adding 20wt% of NaOH aqueous solution for alkalization, then adding abscisic acid and salicylic acid in batches according to parts by weight for grafting reaction, and finally discharging slurry;
(5) adjusting the slurry prepared in the step (4) to be neutral, then distilling under reduced pressure to remove the solvent to obtain a reaction crude product, dissolving the crude product in 6V dimethyl sulfoxide, then carrying out suction filtration, and distilling the filtrate under reduced pressure again to remove the dimethyl sulfoxide to obtain modified chitosan oligosaccharide;
(6) adding EDTA chelated copper, EDTA chelated zinc, EDTA chelated iron, EDTA chelated manganese, EDTA chelated magnesium, sodium borate, vitamin B, diethyl aminoethyl hexanoate, modified chitosan oligomer and EDTA chelated calcium into a reaction container according to the weight parts for mixing;
(7) adding edible pigment into the materials in the step (6) for color matching;
(8) and (4) stirring the materials in the step (7), uniformly mixing, and drying to obtain the vitamin B-containing medium and trace element compound fertilizer.
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| CN105061002A (en) * | 2015-07-21 | 2015-11-18 | 左文 | Novel efficient fertilizer and preparation method thereof |
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