CN107513077B - Active enzyme mimics and foliar fertilizer, synergist and synergist application method based on the compound - Google Patents

Active enzyme mimics and foliar fertilizer, synergist and synergist application method based on the compound Download PDF

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CN107513077B
CN107513077B CN201710676674.7A CN201710676674A CN107513077B CN 107513077 B CN107513077 B CN 107513077B CN 201710676674 A CN201710676674 A CN 201710676674A CN 107513077 B CN107513077 B CN 107513077B
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enzyme mimics
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CN107513077A (en
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刘艳博
廖展如
孟祥高
李骥
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    • A01CPLANTING; SOWING; FERTILISING
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    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract

The present invention provides a kind of active enzyme mimics and foliar fertilizer, synergist and synergist application method based on the compound, belong to biochemical field.Active enzyme mimics form activated centre by the coupling of organic ligand and metal ion, and then start the degeneration-resistant mechanism of crop itself by a variety of reaction mechanisms, it can be used in the different times of crop growth, realize crop insect pest, sterilization, anti-stain, drought resisting, cold-resistant, increasing both production and income.The activity enzyme mimics reach 500~1000ppm using concentration, and apparent side effect is not shown to plant when being used for pest-resistant calamity.

Description

Active enzyme mimics and foliar fertilizer, synergist and synergy based on the compound Agent application method
Technical field
The invention belongs to agricultural technology field, in particular to active enzyme mimics and the blade face based on the compound Fertilizer, synergist and synergist application method.
Background technique
With the continuous development in city, the contradiction in population and arable land is more and more prominent, how to improve per unit area yield to support increasingly Demand of the population of growth to grain will become an important problem.The application of chemical fertilizer is the effective hand for improving grain yield One of section, but basic chemical fertilizer (urea, ammonium nitrate, monoammonium phosphate, Diammonium phosphate (DAP), potassium sulfate, potassium chloride etc.) is excessively used and will lead to Soil hardening pollutes environment.By the builder product of biological inducing action, the degeneration-resistant mechanism of crop itself can be started, not only It is able to achieve increasing both production and income, while can also reduce the usage amount of chemical fertilizer, pesticide and fungicide, reduces peasant burden.
All kinds of common bio-hormones with synergistic effect not only have that synthesis or extraction process are complicated, together When can only be applicable in most cases under specific crop and specific environment.Endogenous tune is relied on therefore, it is necessary to search out Control is the Novel synergistic agent of mechanism of action.
Summary of the invention
The purpose of the present invention is to provide a kind of active enzyme mimics and foliar fertilizer, synergist based on the compound And synergist application method.
The present invention is to be achieved through the following technical solutions:
A kind of active enzyme mimics making plant stress-resistance synergy, including organic ligand, metal ion and anion;
Wherein, organic ligand is one of ligand 1~12 or a variety of, and the structure of ligand 1~12 is as follows:
Wherein, R isOne of or it is a variety of;
Wherein, metal ion Cu2+、Zn2+、Fe3+、Fee2+、Mg2+、Mo2+、Co2+、Mn2+、Mn3+And Mn4+One of or It is a variety of;
Wherein, anion NO3 -、Cl-、H2PO3 -、HPO3 2-、SO4 2-And ClO4 -It is one or more;
Wherein, the positive charge total amount of metal ion band is equal to the negative electrical charge total amount of anion band;
Wherein, according to molar amount, organic ligand: metal ion=1:(1~3).
Preferably, the active enzyme mimics further include solvent molecule, and the solvent molecule is water, methanol, second One of alcohol, propyl alcohol, ethylene glycol, glycerine, pyridine, DMF, DMSO and phenol are a variety of;
Wherein, according to molar amount, ratio≤3 of organic ligand and solvent molecule.
A kind of plant multifunction synergist, including the active enzyme mimics;It further include solvent, the solvent is One of DMF, DMSO, ethylene glycol are a variety of;Active enzyme mimics are dissolved or suspended in solvent;Wherein, according to matter Amount calculates, active enzyme mimics: solvent=1:(5~50).
A kind of application method of plant multifunction synergist, comprising steps of plant multifunction synergist is diluted with water to 4 Then~30ppm soaks seed to vegetable seeds or to plant-spraying;Wherein, the plant is cereal crops or industrial crops;It sprays Time when including that plant germination phase, plant meet with drought, when plant meets with stain calamity or when plant meets with sick calamity.
Preferably, if plant needs are overwintering, before plant is overwintering or when plant turns green, plant-spraying plant multifunction is increased Imitate agent.
Preferably, it is perhaps transplanted after grafting or transplanting if plant is grafted, to plant-spraying plant multifunction Synergist.
Preferably, the cereal crops are rice, wheat, soybean, corn or sorghum etc.;The industrial crops are sweet Sugarcane, eggplant, edible gourd, apple, cotton, herbage or fresh flower etc..
A kind of application method of plant multifunction synergist, comprising steps of plant multifunction synergist is diluted with water to 500~1000ppm, then to plant-spraying;Wherein, the plant is cereal crops or industrial crops;The opportunity sprayed is to plant When object meets with the plague of insects.
Preferably, the cereal crops are rice, wheat, soybean, corn or sorghum etc.;The industrial crops are sweet Sugarcane, eggplant, edible gourd, apple, cotton, herbage or fresh flower etc..
A kind of compound foliar fertilizer, including foliar fertilizer further include the active enzyme mimics;Wherein, organized enzyme mould The mass ratio of type compound is 0.1~0.5%.The compound foliar fertilizer can be commercially available foliar fertilizer and organized enzyme model chemical combination The mixture of object is also possible to after composition on the basis of existing commercially available foliar fertilizer to wherein nutritional ingredient and content adjustment simultaneously It joined the compound foliar fertilizer of active enzyme mimics.
Compared with prior art, the invention has the following beneficial technical effects:
The active enzyme mimics provided by the invention for making plant stress-resistance synergy pass through organic ligand and metal ion Coupling form activated centre, and then pass through the degeneration-resistant mechanism that a variety of reaction mechanisms start crop itself.In wheat test of suffering from drought Middle discovery, the photosynthetic rate of wheat can be improved in such active enzyme mimics, and reduces transpiration rate, improves the water of wheat Divide utilization rate, and realizes the purpose of volume increase;Wheat endure cold rice shoot test in, discovery can significantly improve wheat survival rate, Facilitate the overwintering of plant cold resistance and overwintering plant;In the simulation experiments of various crop, pass through seed dressing and the seedling spraying work Property enzyme mimics, can be obviously improved various crop yield.It is found in antibiotic property test, the activity enzyme mimics Also there is good antibacterial action.Moreover, active enzyme mimics provided by the invention in crop important growth period and When encountering the disasters such as disease, drought, stain, dosage is 4~40ppm, and when encountering the plague of insects, it can be played in 500~1000ppm good Good combats a natural disaster to act on, and when at concentrations up to 500~1000ppm, does not show apparent side effect.
Plant multifunction synergist provided by the invention, for the concentrate of active enzyme mimics, user is direct It can be used after being diluted with water to suitable concentration, it is easy to use.
The application method of plant multifunction synergist provided by the invention is used in the different times of crop growth, real Existing crop insect pest, sterilization, anti-stain, drought resisting, cold-resistant, increasing both production and income.
A kind of compound foliar fertilizer provided by the invention can promote liquid level to improve fertilizer to the absorption and utilization of fertilizer Utilization rate.
Detailed description of the invention
Fig. 1 is the X-ray single crystal diffraction figure of active enzyme mimics 1.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and It is not to limit.
Embodiment 1
The preparation of active enzyme mimics 1
1,2- cyclohexylamine tetraacethyl (cellulose triacetic acid, CTA) and 2- mercaptoaniline by amount of substance it It than 1:4, mills and enters converter after mixing, 170 DEG C of heat togethers are condensed 8 hours until dry-steam is released.Condensation product After being cooled to 50 DEG C, put into etc. stirring in quality dehydrated alcohol stand, filtering, obtain after crude product respectively with distilled water, second Pure and mild ether washing, low temperature drying obtain white powder, are ligand 4C, conversion ratio 67%.The structure of ligand 4C are as follows:.
Wherein, R is
HRMS(ESI+)m/z calculated for C38H35N6S4(M+H):703.1806,found703.1811.
Ligand 4C and Fe (NO3)3·9H2O is mixed according to the ratio between amount of substance 1:1.3, is added in 95% ethyl alcohol of 2 times of quality, After being stirred to react 4 hours at 60 DEG C, cooling, filtering, drying obtain solid powder and the orange-yellow transparent stillness of night.Orange solids Powder is final products, conversion ratio 96%.It is [Fe (ligand 4C)] through X-ray single crystal diffraction measurement product cationic structural (NO3)3
Embodiment 2:
Diethylenetriamine pentaacetic acid (diethylenetriaminepentaacetic acid, DTPA) and o-phenylenediamine press object The ratio between amount of matter 1:5 mills and enters converter after mixing, and 200 DEG C of heat togethers are condensed 24 hours until dry-steam is released. After condensation product is cooled to 50 DEG C, put into etc. stirring in quality dehydrated alcohol stand, filtering, obtain after crude product respectively with steaming Distilled water, ethyl alcohol and ether washing, low temperature drying obtain white powder, are ligand 6A, conversion ratio 72%.The structure of ligand 6A Are as follows:
Wherein, R is
HRMS(ESI+)m/z calculated for C44H44N13(M+H):754.3843,found754.3845.
Ligand 6A and MnCl2·4H2O is mixed according to the ratio between amount of substance 1:1, is added in the ethylene glycol of 2 times of quality, at 60 DEG C Under be stirred to react 4 hours after, it is cooling, filtering, dry, obtain solid powder and the transparent stillness of night.Solid powder is final products, is turned Rate is 93%.It is [Mn (ligand 6A)] Cl through determination of elemental analysis product2
Embodiment 3:
Disodium salt (EDTA) and o-phenylenediamine are milled by the ratio between the amount of substance 1:4 and are entered converter after mixing, 180 DEG C of heat togethers are condensed 16 hours until dry-steam is released.After condensation product is cooled to 50 DEG C, it is anhydrous the quality such as to put into Stirring stands, filters in ethyl alcohol, is washed respectively with distilled water, ethyl alcohol and ether after obtaining crude product, low temperature drying obtains white Powder is ligand 1 A, conversion ratio 69%.The structural formula of ligand 1 A are as follows:
Wherein, R is
HRMS(ESI+)m/z calculated for C34H33N10(M+H):581.2890,found581.2891.
Ligand 1 A and CuSO4·4H2O is mixed according to the ratio between amount of substance 1:1.1, is added in the DMF of 2 times of quality, at 60 DEG C After being stirred to react 4 hours, cooling, filtering, drying obtain solid powder and the transparent stillness of night.Solid powder is final products, conversion Rate is 92%.Through elemental analysis, product is [Cu (ligand 1 A)] SO4
Embodiment 4:
Bis- (the 2- amino-ethyl ether) tetraacethyls (EGTA) of ethylene glycol and 2- mercaptoaniline are milled by the ratio between the amount of substance 1:4 Enter converter after mixing, 170 DEG C of heat togethers are condensed 16 hours until dry-steam is released.Condensation product is cooled to 50 DEG C Afterwards, put into etc. stirring in quality dehydrated alcohol stand, filtering, obtain after crude product respectively with glycerine, distilled water, ethyl alcohol and Ether washing, low temperature drying obtain white powder, are ligand 5C, conversion ratio 66.7%.The structural formula of ligand 5C are as follows:
Wherein, R is
HRMS(ESI+)m/z calculated for C38H37N6O2S4(M+H):737.1861,found737.1865.
Ligand 5C and Co (NO3)2·6H2O、Ni(NO3)2·6H2O is mixed according to the ratio between amount of substance 1:1.1:1.1, is added 2 It is cooling, filtering, dry after 4 hours are stirred to react at 60 DEG C in the pyridine of times quality, obtain solid powder and the transparent stillness of night. Solid powder is final products, conversion ratio 81%.Through elemental analysis, product is [Co-Ni (ligand 5C)] (NO3)4
Embodiment 5:
Ethylenediamine tetrapropionic acid (EDTP) and ethylenediamine are milled by the ratio between the amount of substance 1:4 and are entered converter after mixing, 210 DEG C of heat togethers are condensed 24 hours until dry-steam is released.After condensation product is cooled to 50 DEG C, it is anhydrous the quality such as to put into In ethyl alcohol stirring stand, filtering, obtain after crude product that spent glycol, methanol, ethyl alcohol and ether washing, low temperature drying obtain respectively White powder is ligand 1 0B, conversion ratio 62.5%.The structure of ligand 1 0B are as follows:
Wherein, R is
HRMS(ESI+)m/z calculated for C22H33N10(M+H):437.2890,found437.2888.
Ligand 1 0B and MnCl2·6H2O、FeCl3·6H2O is mixed according to the ratio between amount of substance 1:1.1:1.1, and 2 times of matter are added In the phenol of amount, after 4 hours are stirred to react at 60 DEG C, cooling, filtering, drying obtain solid powder and the transparent stillness of night.Solid Powder is final products, conversion ratio 86%.Through elemental analysis, product is [Fe-Mn (ligand 1 0B)] Cl5
Embodiment 6:
The ratio between the amount of five propionic acid of Diethylenetriamine and o-phenylenediamine substance 1:5 mills and enters converter after mixing, and 170 DEG C Heat together is condensed 24 hours until dry-steam is released.After condensation product is cooled to 50 DEG C, the quality dehydrated alcohol such as put into Middle stirring stands, filters, and is washed respectively with phenol, benzene and ether after obtaining crude product, low temperature drying obtains white powder, is Ligand 1 2A, conversion ratio 70.5%.Wherein, the structural formula of ligand 1 2A are as follows:
Wherein, R is
HRMS(ESI+)m/z calculated for C49H54N13(M+H): 824.4625, found 824.4628. match Body 12A and MgCl2·6H2O is mixed according to the ratio between amount of substance 1:2.5, is added in the benzene of 2 times of quality, is stirred to react 4 at 60 DEG C After hour, cooling, filtering, drying obtain solid powder and the transparent stillness of night.Solid powder is final products, conversion ratio 84%. It is [Mg through elemental analysis product2(ligand 1 2A)] Cl4
Embodiment 7:
Five propionic acid of Diethylenetriamine and 2- mercaptoaniline are milled by the ratio between the amount of substance 1:5 and are entered converter after mixing, 170 DEG C of heat togethers are condensed 24 hours until dry-steam is released.After condensation product is cooled to 50 DEG C, it is anhydrous the quality such as to put into Stirring stands, filters in ethyl alcohol, uses glycerine, ethylene glycol and ethanol washing respectively after obtaining crude product, low temperature drying obtains white Color powder is ligand 1 2C, conversion ratio 70.5%.The structural formula of ligand 1 2C are as follows:
Wherein, R is
HRMS(ESI+)m/z calculated for C49H49N8S5(M+H): 909.2684, found909.2683. match Body 12C and CuHPO3、Zn(ClO4)2·6H2O is mixed according to the ratio between amount of substance 1:1.1:1.1, is added in the phenol of 2 times of quality, After being stirred to react 4 hours at 60 DEG C, cooling, filtering, drying obtain solid powder and the transparent stillness of night.Solid powder is final Product, conversion ratio 87%.Through elemental analysis, product is [Cu-Zn (ligand 1 2C)] HPO3·(ClO4)2
Embodiment 8:
1,3- trimethylen-edinitrilo-tetraacetic acid and 3- mercaptoaniline are milled by the ratio between the amount of substance 1:4 and are entered converter after mixing, 180 DEG C of heat togethers are condensed 12 hours until dry-steam is released.After condensation product is cooled to 50 DEG C, it is anhydrous the quality such as to put into Stirring stands, filters in ethyl alcohol, is washed respectively with distilled water, ethyl alcohol and DMSO after obtaining crude product, low temperature drying obtains white Powder is ligand 3C, conversion ratio 56.5%.The structural formula of ligand 3C are as follows:
Wherein, R is
HRMS(ESI+)m/z calculated for C36H33N6S4(M+H): 677.1650, found677.1651. match Body 3C and Fe (ClO4)3It is mixed according to the ratio between amount of substance 1:2, is added in the DMF of 2 times of quality, is stirred to react at 60 DEG C 4 hours Afterwards, cooling, filtering, drying, obtain solid powder and the transparent stillness of night.Solid powder is final products, conversion ratio 79.2%.Through Elemental analysis, product are [Fe (ligand 3C)] (ClO4)3·3H2O。
Embodiment 9:
The ratio between the amount of 1,3- propane diamine dipropyltin diacetate acid and o-phenylenediamine substance 1:4, milling to enter after mixing turns Furnace, 220 DEG C of heat togethers are condensed 12 hours until dry-steam is released.After condensation product is cooled to 50 DEG C, the quality such as put into Stirring stands, filters in dehydrated alcohol, is washed respectively with distilled water, ethyl alcohol and DMSO after obtaining crude product, low temperature drying obtains White powder is ligand 9A, conversion ratio 56.5%.The structural formula of ligand 9A are as follows:
Wherein, R is
HRMS(ESI+)m/z calculated for C36H37N10(M+H): 609.3203, found 609.3206. match Body 3A and ZnCl2、MnCl4It is mixed according to the ratio between amount of substance 1:1:1, is added in the ethyl alcohol of 2 times of quality, is stirred to react 4 at 60 DEG C After hour, cooling, filtering, drying obtain solid powder and the transparent stillness of night.Solid powder is final products, conversion ratio 93%. Through elemental analysis, product is [Mn-Zn (ligand 9A)] Cl4
Embodiment 10:
Bis- (the 2- amino-ethyl ether) tetraacethyls (EGTA) of ethylene glycol and ethylenediamine are by the ratio between the amount of substance 1:4, mixing of milling Enter converter after uniformly, 170 DEG C of heat togethers are condensed 16 hours until dry-steam is released.After condensation product is cooled to 50 DEG C, Put into etc. stirring in quality dehydrated alcohol stand, filtering, obtain after crude product respectively with glycerine, distilled water, ethyl alcohol and second Ether washing, low temperature drying obtain white powder, are ligand 5B, conversion ratio 66.7%.The structural formula of ligand 5B are as follows:
Wherein, R is
HRMS(ESI+)m/z calculated for C22H33N10O2(M+H):469.2788,found469.2789.
Ligand 5B and Mg (H2PO3)2·6H2O is mixed according to the ratio between amount of substance 1:2, is added in the DMSO of 2 times of quality, 60 After being stirred to react 4 hours at DEG C, cooling, filtering, drying obtain solid powder and the transparent stillness of night.Solid powder is final products, Conversion ratio is 74%.Through elemental analysis, product is [Mg (ligand 5B)] (H2PO3)2
Embodiment 11
Handled and suffered from drought wheat using above-described embodiment 1-10 activity enzyme mimics, and to plant leaf physical signs into Row detection, the results are shown in Table 1.
Table 1 suffer from drought wheat test
Embodiment 12
It is endured cold rice shoot using above-described embodiment 1-10 activity enzyme mimics processing wheat, after spraying one day, to plant Physiological Index in Leaves is detected, and the results are shown in Table shown in 2.
Table 2 is endured cold rice shoot physiology, changes of biochemical indexes (wheat does not apply the micro- fertilizer of quasi- enzyme relatively)
Embodiment 13
It is suffered from drought rice shoot using above-described embodiment 1-10 activity enzyme mimics processing cotton, after spraying one day, to plant Physiological Index in Leaves is detected, and the results are shown in Table shown in 3.
Table 3 is suffered from drought cotton test
Embodiment 14
It handles cotton respectively using above-described embodiment 1-10 activity enzyme mimics to suffer from drought rice shoot, and not arid with sufficient water Cotton rice shoot carries out physiology, biochemical indicator control, as a result see the table below shown in 4.
4 different disposal cotton leaf physiology of table, changes of biochemical indexes situation (according to arid control, ± %)
The above result shows that active enzyme mimics can play long term, amount of activated enzyme to cotton rice shoot of suffering from drought After the arid cotton crop of model compound (embodiment 3 and embodiment 7) processing, physiology, biochemical indicator are even better than sufficient water not Arid cotton crop.
Note: (1) it by the plant proline content of drought stress is will increase.
(2) the case where the rupture of relative conductivity reaction plant cell, value is higher, and reaction plant membrane permeability is higher, injured Evil degree is more serious.
(3) water stress reduces chlorophyll content of plant.
(4) SOD, CAT and POD are three kinds of important Protective enzyme in plant.SOD mono- as water stress increases, in plant As can present first reduce after raised trend;POD enzymatic makes chlorophyll degradation, photosynthesis rate decline.
Embodiment 15
In the middle part of the field in Plain, 2 mu of adjacent soils, unobstructed, no river around soil are chosen;Soil is divided into 4 Block, equal plant cotton.The certainly local seed stations of cotton seed purchase.It is handled as follows using enzyme is intended described in embodiment 5:
The cotton seed in plot 1 intends enzyme by 4ppm activity and soaks seed 24 hours;The cotton in plot 2 sprays 13ppm activity in seedling stage Quasi- enzyme, the amount of spraying are 50L;The cotton seed in plot 3 intends enzyme by 4ppm activity and soaks seed 24 hours, and it is living that cotton sprays 13ppm in seedling stage Property quasi- enzyme, the amount of spraying is 50L;The cotton plants and cotton seed in plot 4 do not do special processing.The cotton of two mu of grounds is in other management Aspect is identical without exception.The result of test is shown in table 5, the results show that the yield of cotton can be improved in the quasi- enzyme of activity, especially After carrying out seed soaking to cotton seed simultaneously and spraying in seedling stage, output of cotton amplification reaches 23.4%.
5 Yield Increase In Cotton test result of table
Embodiment 16
In the middle part of the field in Plain, 4 mu of adjacent soils, unobstructed, no river around soil are chosen;Soil is divided into 4 Block, plantation peanut.The certainly local seed stations of peanut species purchase.It is handled as follows using enzyme is intended described in embodiment 4:
Normally specially treated is not done in plantation in plot one;The peanut species in plot two intend enzyme by 4ppm activity and soak seed 24 hours; The peanut in plot three sprays 13ppm activity in seedling stage and intends enzyme, and the amount of spraying is 50L;The peanut species in plot four are quasi- by 4ppm activity Enzyme is soaked seed 24 hours, and peanut sprays 13ppm activity in seedling stage and intends enzyme, and the amount of spraying is 50L.The cotton of two mu of grounds is in other management Aspect is identical without exception.The result of test is shown in table 7, the results show that the yield of peanut can be improved in the quasi- enzyme of activity, especially After carrying out seed soaking to cotton seed simultaneously and spraying in seedling stage, output of cotton amplification reaches 14.1%.
The test of 6 peanut yield increasing of table
Embodiment 17
In the middle part of the field in Plain, 60 mu of adjacent soils, unobstructed, no river around soil are chosen;Soil is divided into 4 Block, equal rice cultivation.Plot one is handled using quasi- enzyme described in embodiment 3 and common chemical fertilizer;Plot two is increased using commercially available humic acid It imitates fertilizer AA and substitutes common chemical fertilizer;It only applies common chemical fertilizer and does not do specially treated in plot three.
The seed rice in plot 1 intends enzyme by 4ppm activity and soaks seed 24 hours, and sprays 13ppm activity in Grain Filling and intend Enzyme, the amount of spraying are 50L;Plot 2 is Humic acid synergistic fertilizer, normal 25 kgs/acre of application;Plot 3 is Common compound fertilizer, usage amount 25 kgs/acre.The result of test is shown in table 6, the results show that the quasi- enzyme of activity can significantly improve the efficiency of common chemical fertilizer, Increasing production of rice amplitude is up to 20.99%.
6 increasing production of rice of table comparison (comparison AA, 20 mu of grades)
Embodiment 18
1,5, the 8 quasi- enzyme of the activity of embodiment has antibacterial effect.Rice, cotton, wheat, apple and asparagus are screened respectively, Foliage-spray is carried out, test is compared with carbendazim antibacterial agent foliage-spray effect, as a result see the table below 8.
8 antibiotic property of table test (comparison carbendazim antibacterial agent, sterilizing rate %)
Note: sterilizing rate=(initial bacterium amount number-application for 24 hours afterwards survive bacterium amount number)/initial bacterium amount number.
On the basis of the mechanism of action to the quasi- enzyme of activity, Production of Large Fields are verified, inventor by microcellular test after The continuous quasi- enzyme of verifying activity acts on the reverse-resisting yield-increasing of other crops, and specific Experimental results show is in embodiment 19~35.
In microcellular test, used test method is as follows:
A certain plot, soil environment, moisture environment, sunlight and the ventilated environment of whole block are divided in experimental field It is almost the same.Several adjacent micro-assay cells, the area and shape base of each micro-assay cell are marked off from plot This is identical, and area is 4~6 square metres, and boundary is clearly demarcated between each micro-assay cell.Different micro-assay cell conducts Different processing groups, establishes specific label.
Processing group includes control group and several experimental groups, and plant or seed in control group do not pass through organized enzyme modelling The processing of object is closed, and the plant or seed in experimental group pass through the processing that " method " column is indicated in embodiment 19~35.It needs It should be noted that in the same embodiment, each processing group undergoes same or similar disaster-stricken process, i.e. control group calculates Yield be it is disaster-stricken after crop yield, the calculated yield of experimental group be also it is disaster-stricken after crop yield.All processing Group is all made of identical seed, carries out same investment and identical field management.With conventional calculation method, processing is calculated Rate of growth of the group relative to control group.
In embodiment 19~35, there are three types of different disaster-stricken situations, i.e. drought, stain calamity and the plague of insects in total.
Drought is by controlling the irrigation realization to each micro-assay cell, and the mode of irrigation is sprinkling.
Stain calamity is simulated by spraying high concentration salt water to each micro-assay cell, this pollutes plot And damage, therefore only several critical active enzyme mimics are verified.
The plague of insects is simulated by the pest of active release capture, when the plague of insects carries out, each micro-assay cell Between pass through gauze be isolated.Wherein, the wheat plague of insects, the rice plague of insects, the cotton plague of insects, the peanut plague of insects, the tomato plague of insects, the eggplant plague of insects, The capsicum plague of insects, the cucumber plague of insects, the Kidney bean plague of insects, edible gourd plague of insects, the balsam pear plague of insects, the sponge gourd plague of insects are simulated using bollworm;Three-coloured amaranth The plague of insects, the bengal dayflower herb plague of insects, the romaine lettuce plague of insects and the radish plague of insects are simulated using cabbage caterpillar.
In embodiment 19~35, unless being illustrated, active enzyme mimics are first dissolved in 10 times of quality DMF in, be then diluted with water to experimental concentration again.Active enzyme mimics are when to crop applying, other than seed dressing It is all made of and sprays, the amount sprayed is 30L/ mus.
Embodiment 19
It selects the active enzyme mimics of embodiment 1 to carry out simulation experiments under the conditions of 5ppm, as a result shows in table 9.
The application of 9 synergist of table and volume increase result (rate of growth %)
Crop/method Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 5ppm concentration 2.03 3.74 3.14 2.14 0.98 3.9 2.22 0.78 - 0.72 3.77 1.89
5ppm concentration seedling stage applies 6.9 2.77 3.78 2.57 4.11 7.7 1.09 3.19 0.46 - 5.49 3.98
The application of 5ppm concentration drought 4.2 3.65 5.95 1.17 2.09 4.7 2.13 3.84 - 1.98 11.3 4.24
It uses above 5.75 5.21 7.17 3.99 4.17 5.56 3.39 4.98 0.42 2.22 13.21 7.01
Embodiment 20
The volume increase examination for selecting the active enzyme mimics of embodiment 1 to apply under 10ppm seed dressing and 10ppm other conditions It tests, as a result shows in table 10.
The application of 10 synergist of table and volume increase result (rate of growth %)
Crop/method Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 10ppm concentration 2.9 5.7 4.8 3.3 3.5 3.9 4.1 4.3 1.3 2.6 17.3 9.5
10ppm concentration seedling stage applies 6.9 10.2 7.3 6.5 5.9 7.7 6.4 4.7 1.2 4 27 10.8
The application of 10ppm concentration drought 4.2 9.4 8.5 4.2 6.5 4.7 7.7 6.2 2.2 3.8 21.4 8.7
It uses above 7.5 11.7 10.2 7.3 7.6 7.6 7.2 6.5 2.1 4.9 33.2 11.7
Embodiment 21
It selects the active enzyme mimics of embodiment 3 to carry out simulation experiments under the conditions of 5ppm, as a result shows in table 11.
The application of 11 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 5ppm concentration 1.29 0.85 1.63 0.65 0.79 1.46 1.22 0.83 0.38 1.52 0.87 0.30 0.14 0.28 1.47 0.74
5ppm concentration seedling stage applies 1.69 2.23 2.06 1.11 2.28 0.91 1.25 0.85 1.36 2.54 0.36 1.05 0.15 0.51 1.81 1.31
The application of 5ppm concentration stain calamity 1.78 1.67 2.70 1.73 1.76 1.53 2.50 0.49 0.88 1.97 0.89 1.61 0.05 0.83 4.75 1.78
It uses above 1.95 2.70 2.53 1.75 1.67 1.51 2.08 1.16 1.21 1.61 0.98 1.44 0.12 0.64 3.83 2.03
Embodiment 22
Select simulation experiments of the active enzyme mimics of embodiment 3 under 10ppm seed dressing and 40ppm other conditions, knot Fruit shows in table 12.
The application of 12 synergist of table and volume increase result (rate of growth %)
Embodiment 23
It selects the active enzyme mimics of embodiment 5 to carry out simulation experiments under the conditions of 10ppm, as a result shows in table 13 In.
The application of 13 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 10ppm concentration 3.32 2.17 4.19 1.67 2.03 3.74 3.14 2.14 0.98 3.9 2.22 0.78 - 0.72 3.77 1.89
10ppm concentration seedling stage applies 5.11 6.76 6.25 3.36 6.9 2.77 3.78 2.57 4.11 7.7 1.09 3.19 0.46 - 5.49 3.98
The application of 10ppm concentration drought 4.23 3.98 6.43 4.11 4.2 3.65 5.95 1.17 2.09 4.7 2.13 3.84 - 1.98 11.3 4.24
It uses above 6.71 9.3 8.72 6.02 5.75 5.21 7.17 3.99 4.17 5.56 3.39 4.98 0.42 2.22 13.21 7.01
Embodiment 24
Select simulation experiments of the active enzyme mimics of embodiment 5 under 20ppm seed dressing and 100ppm other conditions, knot Fruit shows in table 14.
The application of 14 synergist of table and volume increase result (rate of growth %)
Crop/method Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 20ppm concentration 1.93 3.73 1.49 1.81 3.33 2.79 1.90 0.87 3.47 1.98 0.69 0.11 0.64 3.36 1.68
100ppm concentration seedling stage applies 5.75 5.31 2.86 5.87 2.35 3.21 2.18 3.49 6.55 0.93 2.71 0.39 1.05 4.67 3.38
The application of 100ppm concentration drought 4.10 6.62 4.23 4.33 3.76 6.13 1.21 2.15 4.84 2.19 3.96 0.21 2.04 11.64 4.37
It uses above 8.93 8.37 5.78 5.52 5.00 6.88 3.83 4.00 5.34 3.25 4.78 0.40 2.13 12.68 6.73
Embodiment 25
It selects the active enzyme mimics of embodiment 6 to carry out simulation experiments under the conditions of 5ppm, as a result shows in table 15.
The application of 15 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 5ppm concentration 3.00 1.96 3.78 1.51 1.83 3.38 2.84 1.94 0.88 3.52 2.01 0.70 0.33 0.65 3.42 1.71
5ppm concentration seedling stage applies 4.07 5.37 4.97 2.67 5.49 2.20 3.01 2.05 3.27 6.13 0.87 2.54 0.37 0.83 4.37 3.17
The application of 5ppm concentration drought 4.52 4.25 6.86 4.38 4.49 3.89 6.36 1.26 2.23 5.02 2.28 4.10 0.20 2.12 12.06 4.52
It uses above 8.42 11.67 10.94 7.56 7.22 6.53 9.00 5.00 5.23 6.98 4.25 6.24 0.52 2.78 16.57 8.80
Embodiment 26
Select simulation experiments of the active enzyme mimics of embodiment 6 under 10ppm seed dressing and 30ppm other conditions, knot Fruit shows in table 16.
The application of 16 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 10ppm concentration 3.13 2.04 3.94 1.58 1.91 3.53 2.96 2.01 0.92 3.68 2.08 0.74 0.35 0.68 3.55 1.77
30ppm concentration seedling stage applies 3.95 5.23 4.83 2.59 5.33 2.13 2.93 1.99 3.18 5.96 0.84 2.47 0.36 1.21 4.24 3.07
The application of 30ppm concentration drought 4.30 4.04 6.53 4.18 4.26 3.70 6.03 1.19 2.13 4.78 2.17 3.90 0.12 2.01 11.46 4.30
It uses above 7.64 10.60 9.92 6.86 6.55 5.92 8.17 4.55 4.76 6.33 3.87 5.67 0.48 2.53 15.03 7.97
Embodiment 27
It selects the active enzyme mimics of embodiment 6 to carry out simulation experiments under the following conditions, as a result shows in table 17.
The application of 17 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 50ppm concentration 2.12 -3.4 2.07 0.52 3.66 6.89 2.65 1.21 4.85 2.78 0.96 0.45 0.89 4.69 2.36
150ppm concentration seedling stage applies 5.22 6.37 3.43 7.05 2.81 3.86 2.63 4.20 7.85 1.11 3.24 0.46 1.58 5.59 4.05
The application of 150ppm concentration drought 5.14 7.80 5.00 5.09 4.42 7.23 1.42 2.54 5.69 2.57 4.65 0.14 2.40 13.73 5.14
It uses above 6.88 8.93 6.18 5.90 5.33 7.34 4.09 4.27 5.68 3.46 5.08 0.42 2.26 13.52 7.17
The above case shows should not be excessively high using concentration in seed soaking, and 10ppm seed dressing can reach effective result.
Embodiment 28
It selects the active enzyme mimics of embodiment 7 to carry out simulation experiments under the conditions of 10ppm, as a result shows in table 18 In.
The application of 18 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 10ppm concentration 7.79 5.09 9.84 3.92 4.77 8.77 7.37 5.03 2.31 9.15 5.20 1.83 1.77 1.70 8.85 4.43
10ppm concentration seedling stage applies 11.06 14.63 13.52 7.27 14.93 6.00 8.18 5.56 8.90 16.66 2.36 6.91 2.74 3.38 11.87 8.62
The 10ppm concentration stain phase applies 13.06 12.29 19.87 12.69 12.96 11.27 18.37 3.62 6.45 14.52 6.57 11.86 2.45 6.12 23.93 13.10
It uses above 20.01 27.72 25.99 17.94 17.14 15.53 21.37 11.88 12.43 16.58 10.11 14.84 3.32 6.62 26.77 20.90
Embodiment 29
It selects the active enzyme mimics of embodiment 7 to carry out simulation experiments under the conditions of 500ppm, as a result shows in table 19 In.Wherein, it carries out the present embodiment is synchronous with embodiment 28, reference group having the same, 10ppm concentration seed dressing group, 10ppm Concentration seedling stage administration group.
The application of 19 synergist of table and volume increase result (rate of growth %)
Embodiment 30
It selects the active enzyme mimics of embodiment 7 to carry out simulation experiments under the conditions of 800ppm, as a result shows in table 20 In.Wherein, it carries out the present embodiment is synchronous with embodiment 28, embodiment 29, reference group having the same, the seed dressing of 10ppm concentration Group, 10ppm concentration seedling stage administration group.
The application of 20 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 10ppm concentration 7.79 5.09 9.84 3.92 4.77 8.77 7.37 5.03 2.31 9.15 5.20 1.83 1.77 1.70 8.85 4.43
10ppm concentration seedling stage applies 11.06 14.63 13.52 7.27 14.93 6.00 8.18 5.56 8.90 16.66 2.36 6.91 2.74 3.38 11.87 8.62
The application of the 800ppm concentration plague of insects 12.28 11.55 18.68 11.93 12.18 10.59 17.27 3.40 6.06 13.65 6.18 11.15 2.30 5.75 18.78 12.31
It uses above 18.61 16.96 23.03 16.68 15.94 14.44 19.87 8.05 11.56 15.42 9.40 10.80 4.09 6.16 21.84 19.44
Embodiment 31
It selects the active enzyme mimics of embodiment 8 to carry out simulation experiments under the conditions of 10ppm, as a result shows in table 21 In.
The application of 21 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 10ppm concentration 8.02 5.24 10.14 4.04 4.91 9.03 7.59 5.18 2.38 9.42 5.36 2.88 3.82 1.75 9.12 4.56
10ppm concentration seedling stage applies 14.28 16.24 15.01 8.07 16.57 6.66 9.08 6.17 9.88 18.49 2.62 7.67 3.04 3.75 18.18 9.57
The application of 10ppm concentration drought 17.02 11.31 18.28 11.67 11.92 10.37 16.90 3.33 5.93 13.36 6.04 10.91 3.25 5.63 22.02 12.05
It uses above 29.01 19.11 27.29 18.84 18.00 16.31 22.44 12.47 13.05 17.41 10.62 11.58 4.49 6.95 34.11 14.95
Embodiment 32
Select simulation experiments of the active enzyme mimics of embodiment 8 under 10ppm seed dressing and 100ppm other conditions, knot Fruit shows in table 22.
The application of 22 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 10ppm concentration 7.93 6.57 8.76 7.49 4.25 8.84 10.55 4.46 5.04 8.16 4.68 3.62 4.76 2.50 7.90 3.97
100ppm concentration seedling stage applies 10.65 16.11 18.14 6.99 14.38 5.73 7.87 5.37 8.57 16.01 2.27 6.61 2.94 3.22 29.03 8.26
The application of 100ppm concentration drought 14.18 17.45 21.52 13.79 14.04 12.20 19.95 3.92 7.01 15.70 7.09 12.83 2.39 6.62 37.88 14.18
It uses above 18.70 19.90 26.71 16.80 16.04 14.49 19.94 11.12 11.61 15.44 9.41 11.66 4.14 6.14 39.53 19.48
Embodiment 33
The active enzyme mimics of embodiment 9 are selected to carry out simulation experiments under the conditions of 10ppm, wherein used first Beginning dissolution solvent is the DMSO of 10 times of quality, is as a result shown in table 23.
The application of 23 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 10ppm concentration 8.65 5.69 10.92 4.35 5.29 9.79 8.17 5.57 2.54 10.19 5.84 2.02 1.95 1.87 9.85 4.96
10ppm concentration seedling stage applies 10.60 13.99 12.93 6.96 14.31 5.70 7.84 5.34 8.53 15.94 2.25 6.58 1.93 3.21 17.35 8.22
The application of 10ppm concentration drought 11.00 10.34 16.69 10.70 10.89 9.46 15.47 3.04 5.44 12.18 5.50 9.95 1.30 3.14 26.38 11.00
It uses above 14.24 19.73 18.49 12.79 12.21 11.03 15.19 8.47 8.84 11.76 7.16 10.52 2.87 4.68 27.99 14.84
Embodiment 34
Select simulation experiments of the active enzyme mimics of embodiment 9 under 10ppm seed dressing and 40ppm other conditions, knot Fruit shows in table 24.
The application of 24 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 10ppm concentration 8.57 5.60 10.82 4.31 5.25 9.65 8.11 5.53 2.54 10.07 5.72 2.01 1.95 1.87 9.74 4.87
40ppm concentration seedling stage applies 11.39 15.07 13.93 7.49 15.38 6.18 8.43 5.73 9.17 17.16 2.43 7.12 2.82 2.48 12.23 8.88
The application of 40ppm concentration drought 17.80 32.04 19.47 12.44 12.70 11.04 18.00 3.55 6.32 14.23 6.44 11.62 2.40 3.00 33.45 12.84
It uses above 21.41 29.66 27.81 19.20 18.34 16.62 22.87 12.71 13.30 17.74 10.82 15.88 3.55 4.08 38.64 22.36
Embodiment 35
Select simulation experiments of the active enzyme mimics of embodiment 10 under 10ppm seed dressing and 20ppm other conditions, knot Fruit shows in table 25.
The application of 25 synergist of table and volume increase result (rate of growth %)
Crop/method Wheat Rice Cotton Peanut Tomato Eggplant Capsicum Cucumber Kidney bean Edible gourd Balsam pear Sponge gourd Three-coloured amaranth Bengal dayflower herb Romaine lettuce Radish
The seed dressing of 10ppm concentration 7.71 5.04 9.75 3.88 4.72 8.68 7.29 4.98 2.29 9.06 5.15 1.82 1.75 1.68 8.77 4.39
20ppm concentration seedling stage applies 10.83 14.32 13.23 7.12 14.61 5.87 8.00 5.44 8.71 16.30 2.31 6.76 2.68 3.31 11.62 8.44
The application of 20ppm concentration drought 11.39 15.72 17.33 11.06 11.30 9.83 16.02 3.16 5.63 12.66 5.73 10.35 2.14 3.34 20.87 11.43
It uses above 14.70 18.87 20.58 17.66 16.87 15.29 21.04 11.70 12.24 16.32 9.95 14.61 3.26 4.67 19.14 20.58
Embodiment 19~35 shows that active enzyme mimics provided by the invention can reach the effect of reverse-resisting yield-increasing Fruit.Especially when dressed seed using active enzyme mimics to crop, seedling spraying and it is disaster-stricken when spray be jointly processed by when, Effect of increasing production highly significant.Moreover, in order to cope with the plague of insects, the spraying concentration of the active enzyme mimics of embodiment 7 is selected Reach 500~800ppm, can still reach the effect of volume increase, toxic side effect is small.
The object of the present invention is to provide a kind of plant multifunction synergist, use in the different times of crop growth, real Existing crop insect pest, sterilization, anti-stain, drought resisting, cold-resistant, increasing both production and income.Disease and insect resistance of the present invention, bactericidal effect principle be to pass through Polyphenol oxidase reaction, generates the derivatives such as melanin, flavones, isoflavones, while generating O2·、H2O2Certainly with OH isoreactivity oxygen The pathogen such as bacterium, virus are killed by base, and keep insect digestive tract uncomfortable and food refusal;The anti-stain of the present invention, drought resisting, cold-resistant principle are By decomposing the unsaturated fatty acid in plant, the C such as hexanal, nonyl (alkene) aldehydic acid, laurylene aldehydic acid, malonaldehyde are generated3 , C6 , C9 , C12 Aldehyde, ketone, acid, ester antitoxin signaling molecule, induction crop itself generate degeneration-resistant mechanism.The present invention is applied to cotton, water On the crops such as rice, wheat, fruit tree, vegetables, trees, the effect of upgrading volume increase is realized.The invention discloses a kind of more function of plant Energy synergist can start the degeneration-resistant mechanism of crop itself by the builder product of biological inducing action, convenient with application, Effect of increasing production is prominent, reduces the advantages of usage amount of chemical fertilizer, pesticide and fungicide, has broad popularization and application prospect.

Claims (8)

1. a kind of active enzyme mimics for making plant stress-resistance synergy are [Cu-Zn (ligand 1 2C)] HPO3·(ClO4)2
Wherein, the structural formula of ligand 1 2C isWherein R is
2. a kind of plant multifunction synergist, which is characterized in that including active enzyme mimics described in claim 1;Also Including solvent, the solvent is one of DMF, DMSO, ethylene glycol or a variety of;Active enzyme mimics are dissolved or suspended in In solvent;Wherein, according to Mass Calculation, active enzyme mimics: solvent=1:(5~50).
3. the application method of plant multifunction synergist as claimed in claim 2, which is characterized in that by plant multifunction synergist It is diluted with water to 4~30ppm, is then soaked seed to vegetable seeds or to plant-spraying;Wherein, the plant is cereal crops or warp Ji crop;When the time sprayed includes that plant germination phase, plant meet with drought, when plant meets with stain calamity or plant meets with sick calamity When.
4. the application method of plant multifunction synergist as claimed in claim 3, which is characterized in that if plant needs to get over Winter, before plant is overwintering or when plant turns green, to plant-spraying plant multifunction synergist.
5. the application method of plant multifunction synergist as claimed in claim 3, which is characterized in that if plant is grafted Perhaps transplanting is after grafting or transplanting, to plant-spraying plant multifunction synergist.
6. such as the application method of the described in any item plant multifunction synergist of claim 3-5, which is characterized in that the grain Food crop is rice, wheat, soybean, corn or sorghum;The industrial crops are sugarcane, eggplant, edible gourd, apple, grape, cotton Flower, herbage or fresh flower.
7. the application method of plant multifunction synergist as claimed in claim 2, which is characterized in that by plant multifunction synergist It is diluted with water to 500~1000ppm, then to plant-spraying;Wherein, the plant is cereal crops or industrial crops;It sprays Time be plant meet with the plague of insects when.
8. activity enzyme mimics described in claim 1 are preparing the application in foliar fertilizer, which is characterized in that organized enzyme mould The mass ratio of type compound is 0.1~0.5%.
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