CN101390513B - Uniconazole-cyclodextrin clathrate, preparation method and use thereof - Google Patents
Uniconazole-cyclodextrin clathrate, preparation method and use thereof Download PDFInfo
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- CN101390513B CN101390513B CN2008102243500A CN200810224350A CN101390513B CN 101390513 B CN101390513 B CN 101390513B CN 2008102243500 A CN2008102243500 A CN 2008102243500A CN 200810224350 A CN200810224350 A CN 200810224350A CN 101390513 B CN101390513 B CN 101390513B
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Abstract
The invention provides a plant growth regulator, wherein, uniconazole is dissolved in an appropriate amount of organic solvent to have inclusion reaction with cyclodextrin or the derivatives thereof, and then dried to obtain the regulator. The solubility, sustained-release performance and bioavailability of the uniconazole-cyclodextrin inclusion compound are greatly improved, so that the plant growth regulator can effectively regulate wheat, soybean, corn, rice and other crops, control node elongation and prevent over-luxuriant growth and lodging.
Description
Technical field
The invention belongs to agricultural technology field, relate to the cyclodextrin inclusion compound of a plant growth regulators, the invention still further relates to the Preparation method and use that changes inclusion compound.
Background technology
The application of plant growth regulator is the important new technical means (Wei Fuxiang, Anhui agricultural, 1999,3,11) that improves crop-producing power.Along with becoming increasingly conspicuous of environmental problem, chemical pesticide all faces immense pressure in producing and selling and application, and international food and agricultural organization (FAO) and countries in the world are also improving constantly the limitation standard of residue of pesticide.Conventional formulation is often used a large amount of organic solvents simultaneously because the percent of loss that volatilization, photodissociation, hydrolysis or leaching loss etc. cause reaches 50%-60% in process, not only increased the preparation cost, and increased the possibility of environment pollution in wide area.Adopting novel environment friendly material and preparation technique, improve the performance and the bioavailable efficiency of agricultural chemicals, is to solve agricultural chemicals to use one of important channel with environmental problem contradiction.
Uniconazole P is that a kind of agricultural is used plant growth retardent very widely, crops such as wheat, paddy rice, fruit tree have been widely used in, but there are problem (Duan Liusheng such as poorly water-soluble (solvability only is 8.41mg/L in 25 ℃ of water), easy photodissociation and optical siomerism inactivation in it, crop chemistry control principle and technology, the China Agricultyre University Press, 2005).At present the commodity preparation of uniconazole P is mainly missible oil and wetting powder, convert the water dilution when spraying the crop blade face bioavailable efficiency low, increased target external loss and application cost.
Cyclodextrin is the general name that is acted on a series of cyclic polysaccharide compounds that starch obtains by the cyclodextrin glucoside transferase.Glucopyranose in the cyclodextrin molecular is with α-1,4 glycosidic bonds combine, because it has unique nonpolar hydrophobic cavity structure, easy and hydrophobicity " object " molecule forming bag mixture has been widely used on food, pharmaceutical preparation, cosmetics, agricultural and the chemical industry.Particularly on the pharmaceutical preparation, by medicine cyclodextrin encapsulated being used for strengthening its dissolubility, chemical stability or bioavailability (Wen X.-H.et al.J.Pharmaceutical andBiomedical Analysis, 2004,34,517).
The present invention adopts the cyclodextrin or derivatives thereof of natural degradable as the host molecule material, by certain preparation condition and technology, prepare uniconazole P-cyclodextrin inclusion compound, solved the difficult problem that uniconazole P is poorly soluble, stability is bad, improved solvability in the water of uniconazole P, make to be suitable for more conveniently, improved bioavailability, reduced the environmental pollution when using.
Summary of the invention
The purpose of this invention is to provide the cyclodextrin inclusion compound of uniconazole P and the method for preparing the cyclodextrin inclusion compound of uniconazole P.
The inventor selects by cyclodextrin, the Subjective and Objective ratio of research cyclodextrin and uniconazole P, and organic solvent kind and clathrate process have prepared the cyclodextrin inclusion compound of uniconazole P, have finished the present invention.
The present invention prepares the method for the cyclodextrin inclusion compound of uniconazole P, is uniconazole P is dissolved in the appropriate amount of organic, and with the cyclodextrin or derivatives thereof, through inclusion reaction, drying makes again.
Inclusion compound of the present invention, wherein the mol ratio of uniconazole P and cyclodextrin or derivatives thereof is 0.1～10: 1; Preferred molar ratio is 0.25～2: 1.
Inclusion compound of the present invention, the organic solvent that wherein dissolves uniconazole P is acetone, ethanol, dimethyl formamide, ethyl acetate, n-butanol; Preferred acetone and ethanol.
Inclusion compound of the present invention, wherein cyclodextrin is any water miscible cyclodextrin or derivatives thereof, as beta-schardinger dextrin-, HP-, methyl-beta-schardinger dextrin-or hydroxyethyl-; Preferred beta-schardinger dextrin-.
The invention provides and a kind ofly prepare the method for described inclusion compound by saturated water solution method, it comprises the steps:
(1) at room temperature in an amount of organic solvent (as ethanol, dimethyl formamide, acetone, ethyl acetate), slowly add the former medicine of uniconazole P, and abundant stirring and dissolving, till can not continuing dissolving, to filter, filtrate is saturated solution A;
(2) at room temperature, in suitable quantity of water, slowly add cyclodextrin, and abundant stirring and dissolving, till can not continuing dissolving, to filter, filtrate is saturated solution B;
(3) merge saturated solution A and B, stir and react a period of time;
(4) filtration, washing, drying.
The invention provides and a kind ofly prepare the method for described inclusion compound by supercritical ultrasonics technology, it comprises the steps:
(1) solvent with 10 times of weight dissolves uniconazole P fully, stirs, and makes solution A;
(2) at room temperature, in certain water gaging, slowly add cyclodextrin, and abundant stirring and dissolving, till can not continuing dissolving, to filter, filtrate is solution B;
(3) merge solution A and B, handle and reaction a period of time with ultrasonic disruption instrument or supersonic wave cleaning machine;
(4) filtration, washing, drying.
It is a kind of by being total to the method that polishing prepares described inclusion compound that the present invention also provides, and it comprises the steps:
(1) gets cyclodextrin and add the grinding of 1/2 weight water evenly;
(2) adding continues to be ground to white emulsion with the uniconazole P of the dissolution with solvents of 10 times of weight again;
(3) add the water mixing, centrifugal, the supernatant freeze-drying.
Inclusion compound of the present invention is a white powder.
The purposes of inclusion compound of the present invention is characterized in that, described inclusion compound is dissolved in water is applied to crop, by reducing the usage amount of organic solvent, improves the solvability and the bioavailability of uniconazole P, and to regulate growth, the elongation of control stipes prevents and treats prosperous length and lodging; Wherein crop is wheat, soybean, corn, paddy rice etc.
The invention has the advantages that: (1) invention has prepared having of not appearing in the newspapers and has improved that bioavailability, water-soluble are strong, the uniconazole P-cyclodextrin inclusion compound of slowly-releasing; (2) uniconazole P-cyclodextrin of invention preparation has higher safety and biologically active than other conventional formulation; (3) uniconazole P-cyclodextrin of invention preparation reduces the use of organic solvent significantly than other conventional formulation, and can obtain by different preparation methods.
Description of drawings
Fig. 1: inclusion compound X-ray diffractogram;
Fig. 2: inclusion compound sem photograph;
Fig. 3: the release of inclusion compound in water is dynamic.
Embodiment
The preparation experiment of following mask body and effect experiment example are only made detailed description to the present invention, but are not limited the present invention.
Embodiment 1: the preparation of uniconazole P-cyclodextrin
Take by weighing 11.35 gram beta-schardinger dextrin-s and place mortar, adding 5ml water grinds evenly, add 0.292 gram uniconazole P (mol ratio of uniconazole P and cyclodextrin is 0.1:1) again with the 2ml acetone solution, continue to be ground to the white emulsion of formation, after emulsion adds 10 ml water mixings, 4000 rev/mins centrifugal 10 minutes, get supernatant liquor, precipitation adds 10 milliliters of washings again, gets supernatant after centrifugal once more, twice supernatant merged, 4 ℃ of placements are spent the night, and freeze drying obtains white powder and is inclusion compound of the present invention to constant weight, the inclusion compound yield is 62.4%, and active ingredient uniconazole P content is 1.8%.
Embodiment 2: the preparation of uniconazole P-cyclodextrin
Take by weighing 5.700 gram beta-schardinger dextrin-s and place mortar, adding 2.5ml water grinds evenly, add 0.292 gram uniconazole P (mol ratio of uniconazole P and cyclodextrin is 0.25:1) again with the 1.5ml dissolve with ethanol, continue to be ground to the white emulsion of formation, after emulsion adds 10 ml water mixings, 4000 rev/mins centrifugal 10 minutes, get supernatant liquor, precipitation adds 10 milliliters of washings again, gets supernatant after centrifugal once more, twice supernatant merged, 4 ℃ of placements are spent the night, and freeze drying obtains white powder and is inclusion compound of the present invention to constant weight, the inclusion compound yield is 79.3%, and active ingredient uniconazole P content is 11.6%.
Embodiment 3: the preparation of uniconazole P-cyclodextrin
Take by weighing beta-schardinger dextrin-3.800 grams, be dissolved in 200 ml distilled waters, stir and be mixed with saturated solution A, take by weighing uniconazole P 0.978 gram again, (mol ratio of uniconazole P and cyclodextrin is 1:1) is dissolved in the acetone, is mixed with saturated solution B.Under 800 rev/mins of stirrings of room temperature, solution B is slowly splashed in the solution A, continue to stir 4 hours.With gained suspension suction filtration, filter cake is used absolute ethyl alcohol, water washing successively after the end, and vacuum drying gets white powder and is inclusion compound of the present invention, and the inclusion compound yield is 63.2%, and active ingredient uniconazole P content is 12.5%.
Embodiment 4: the preparation of uniconazole P-cyclodextrin
Take by weighing beta-schardinger dextrin-1.900 grams, be dissolved in 100 ml distilled waters, stir and be mixed with saturated solution A, take by weighing uniconazole P 0.978 gram (mol ratio of uniconazole P and cyclodextrin is 2:1) again, be dissolved in the acetone, be mixed with saturated solution B.Under 800 rev/mins of stirrings of room temperature, solution B is slowly splashed in the solution A, continue to stir 4 hours.With gained suspension suction filtration, filter cake is used absolute ethyl alcohol, water washing successively after the end, and vacuum drying gets white powder and is inclusion compound of the present invention, and the inclusion compound yield is 61.3%, and active ingredient uniconazole P content is 11.2%.
Embodiment 5: the preparation of uniconazole P-cyclodextrin
Take by weighing beta-schardinger dextrin-0.760 gram, be dissolved in 40 ml distilled waters, again to wherein adding the uniconazole P solution (mol ratio of uniconazole P and cyclodextrin be 10:1) of 1.956 grams with the dissolving of 6ml dimethyl formamide, under 300 watts of power of room temperature, ultrasonic 1 hour, after the end with gained suspension suction filtration, filter cake is used absolute ethyl alcohol, water washing successively, vacuum drying gets white powder and is inclusion compound of the present invention, and the inclusion compound yield is 28.2%, and active ingredient uniconazole P content is 1.1%.
Embodiment 6: the preparation of uniconazole P-cyclodextrin
Take by weighing 2.620 gram methyl-beta-schardinger dextrin-s and place mortar, adding 2ml water grinds evenly, add 0.292 gram uniconazole P (mol ratio of uniconazole P and cyclodextrin is 0.5:1) again with the 2ml acetic acid ethyl dissolution, continue to be ground to the white emulsion of formation, after emulsion adds 10 ml water mixings, 4000 rev/mins centrifugal 10 minutes, get supernatant liquor, precipitation adds 10 milliliters of washings again, gets supernatant after centrifugal once more, twice supernatant merged, 4 ℃ of placements are spent the night, and freeze drying obtains white powder and is inclusion compound of the present invention to constant weight, the inclusion compound yield is 80.2%, and active ingredient uniconazole P content is 2.9%.
Embodiment 7: the preparation of uniconazole P-cyclodextrin
Take by weighing hydroxyethyl-5.420 grams, be dissolved in 50 ml distilled waters, again to wherein adding the uniconazole P solution (mol ratio of uniconazole P and cyclodextrin be 1:1) of 0.978 gram with the dissolving of 3ml dimethyl formamide, under 300 watts of power of room temperature, ultrasonic 1 hour, after the end with gained suspension suction filtration, filter cake is used absolute ethyl alcohol, water washing successively, vacuum drying gets white powder and is inclusion compound of the present invention, and the inclusion compound yield is 68.2%, and active ingredient uniconazole P content is 7.1%.
Embodiment 8: the preparation of uniconazole P-cyclodextrin
Take by weighing HP-5.940 grams, be dissolved in 10 ml distilled waters, stir and be mixed with saturated solution A, take by weighing uniconazole P 0.489 gram (mol ratio of uniconazole P and cyclodextrin is 0.5:1) again, be dissolved in the ethanol, be mixed with saturated solution B.Under 800 rev/mins of stirrings of room temperature, solution B is slowly splashed in the solution A, continue to stir 4 hours.After the end gained suspension atomized drying is got white powder and be inclusion compound of the present invention, the inclusion compound yield is 72.7%, and active ingredient uniconazole P content is 11.1%.
Embodiment 9: the preparation of uniconazole P-cyclodextrin
Take by weighing HP-8.940 grams, be dissolved in 50 ml distilled waters, again to wherein adding 0.489 gram with the uniconazole P solution (mol ratio of uniconazole P and cyclodextrin is 0.33:1) of 6.5ml acetone solution, under 300 watts of power of room temperature, ultrasonic 1 hour, after the end with the gained suspension, 4 ℃ of placements are spent the night, and freeze drying obtains white powder and is inclusion compound of the present invention to constant weight, the inclusion compound yield is 78.3%, and active ingredient uniconazole P content is 8.2%.
Inclusion compound detects example
The structure of inclusion compound, can pass through X-ray diffractogram (accompanying drawing 1) and sem photograph (accompanying drawing 2) characterizes, Fig. 1 and Fig. 2 show respectively is the X-ray diffractogram and the sem photograph of the inclusion compound that makes of embodiment 2, shows that uniconazole P and beta-schardinger dextrin-form new inclusion structure.
The inclusion compound that makes among the embodiment 2 dissolves in 25 ℃ of standard water, and the solvability of uniconazole P active ingredient is 121.1mg/L, increases by 14.4 times than solvability under the uniconazole P equal conditions.Inclusion compound discharges in water dynamically sees accompanying drawing 3, shows certain slow release effect.
Experimental example 1: the effect test that inclusion compound is handled rice seedling
1, experimental technique
Material is a paddy rice, and kind is for rich more.Seed was with 0.1% liquor natrii hypochloritis's sterilization 30 minutes, and vernalization is 2 days in 30 ℃ of illumination boxs, and the seed of getting long 2 millimeter of bud is transferred on 1% the agar grows, and keeps humidity to continue to cultivate; Treat that first intact leaves top is when first imperfect leaf stretches out 2 millimeter, with the inclusion compound (to call inclusion compound 3 in the following text) among the micro syringe 50 mg/litre uniconazole Ps that drop 1.0 microlitres configure between first intact leaves and first imperfect leaf, 200 mg/litre (amounting to uniconazole P content is 25 mg/litre) the preparation embodiment 3 and the solution of 175 mg/litre cyclodextrin, and be blank with the clear water, every processing repeats 10 strains.Continue to cultivate 4 days, measure the second leaf sheath length (the results are shown in Table 1).
2, experimental result
As shown in table 1, elongation obviously suppresses the control material uniconazole P to rice leaf sheath, and another control material cyclodextrin does not show remarkable influence, and the inhibitory action of 3 pairs of rice leaf sheath elongations of 200 mg/litre (amounting to uniconazole P content is 25 mg/litre) inclusion compound is suitable with 50 mg/litre uniconazole Ps, and the result shows that inclusion compound has improved the biologically active of uniconazole P.
Table 1 uniconazole P and cyclodextrin inclusion compound thereof are to the influence of rice seedling leaf sheath growth
Experimental example 2: inclusion compound is to the effect test of corn seed seed soaking
1, experimental technique
Material is a corn, and kind is Shandong single 981.Seed was with 0.1% liquor natrii hypochloritis's sterilization 30 minutes, soaked seed 12 hours, be respectively the inclusion compound (to call inclusion compound 4 in the following text) among 40 mg/litre uniconazole Ps, 180 mg/litre (amounting to uniconazole P content is 20 mg/litre) the preparation embodiment 4 and the solution of 160 mg/litre cyclodextrin, and be blank with the clear water, the seedling cultivation is carried out with the vertical panel sproutung method in the seed soaking back, and each is handled and repeats 15 more than the seed.4 days " Invest, Then Investigate " seedling root length, seedling length, root and seedling minister degree ratios (the results are shown in Table 2).
2, experimental result
As shown in table 2, corn seed has suppressed growth of seedlings after soaking seed with uniconazole P, has improved root/seedling ratio; The independent use of cyclodextrin does not show above-mentioned effect; The growth effect of 180 mg/litre (amounting to uniconazole P content is 20 mg/litre) 4 pairs of corn seedlings of inclusion compound and root system is remarkable, has improved root/seedling ratio, and the result is better than 40 mg/litre uniconazole Ps.The result shows that inclusion compound has improved the biologically active of object uniconazole P.
Table 2 uniconazole P and cyclodextrin inclusion compound thereof are to the influence of corn seed germination and growth
Experimental example 3: inclusion compound is at the effect test of wheat seed seed soaking
1, experimental technique
Material is a wheat, and kind is an agricultural university 213.Seed was with 0.1% liquor natrii hypochloritis's sterilization 30 minutes, soaked seed 12 hours, be respectively the solution of inclusion compound (to call inclusion compound 9 in the following text) the 275 mg/litre cyclodextrin of 40 mg/litre uniconazole Ps, 300 mg/litre (amount to uniconazole P content and be about 25 mg/litre) preparation embodiment 9, and be blank with the clear water, the seedling cultivation is carried out with the vertical panel sproutung method in the seed soaking back, and each is handled and repeats 20 more than the seed.4 days " Invest, Then Investigate " seedling root length, seedling length, root and seedling minister degree ratios (the results are shown in Table 3).
2, experimental result
As shown in table 3, wheat seed has suppressed growth of seedlings after soaking seed with uniconazole P, has improved root/seedling ratio; The independent result of use of cyclodextrin is not obvious; The growth effect of 300 mg/litre (amounting to uniconazole P content is 25 mg/litre) 9 pairs of wheat seedlings of inclusion compound and root system is remarkable, has improved root/seedling ratio, and result and 40 mg/litre uniconazole Ps are handled quite.The result shows that inclusion compound has improved the biologically active of object uniconazole P.
Table 3 uniconazole P and cyclodextrin inclusion compound thereof are to the influence of wheat seeds sprouting growth
Experimental example 4: the effect test that inclusion compound is handled at soybean seedling
1, experimental technique
Material is a soybean, and kind is middle yellow 13.Seed carries out pot experiment with 0.1% liquor natrii hypochloritis's sterilization 30 minutes.Treat to use respectively when growth of seedling to two true leaf launches fully the solution of 50 mg/litre uniconazole Ps, 160 mg/litre (amounting to uniconazole P content is 20 mg/litre) inclusion compound 3 and 140 mg/litre cyclodextrin, and be blank with the clear water, each is handled and repeats more than 10 basins.6 days " Invest, Then Investigate " seedling plant heights calculate growth of seedling speed (the results are shown in Table 4).
2, experimental result
As shown in table 4, uniconazole P has suppressed the growth of soybean seedling, and 160 mg/litre (amounting to uniconazole P content is 20 mg/litre), 3 pairs of soybean seedling growth rates of inclusion compound are better than the processing of 50 mg/litre uniconazole Ps, and the result shows that inclusion compound has improved the biologically active of uniconazole P.
Table 4 uniconazole P and cyclodextrin inclusion compound thereof are to the influence of soybean seedling growth
Claims (5)
1. uniconazole P-Preparation methods of cyclodextrin inclusion complexes, it is that uniconazole P is dissolved in an amount of organic solvent, with the aqueous solution of water miscible cyclodextrin or derivatives thereof, carries out inclusion reaction, drying makes again;
Wherein organic solvent is acetone, ethanol, dimethyl formamide or ethyl acetate;
Described water miscible cyclodextrine derivatives is beta-schardinger dextrin-, HP-, methyl-beta-schardinger dextrin-or hydroxyethyl-;
The mol ratio of described uniconazole P and cyclodextrin or derivatives thereof is 0.25～1: 1;
The ratio of the weight of described volume of organic solvent and uniconazole P is ml: g is 1.5-6.5: 0.292-0.978.
2. method according to claim 1 is characterized in that: described inclusion method is saturated water solution method, supercritical ultrasonics technology or common polishing.
3. method according to claim 1 is characterized in that: the drying means of described inclusion compound is boulton process, freeze-drying or spray drying process.
4. uniconazole P-cyclodextrin inclusion compound of making of each described method of claim 1-3.
5. the purposes of the described uniconazole P-cyclodextrin inclusion compound of claim 4 is characterized in that, inclusion compound is applied on wheat, soybean, corn, the paddy rice, to improve solvability, sustained release performance and the bioavailability of uniconazole P.
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| CN101779626B (en) * | 2010-02-11 | 2013-09-11 | 中国农业大学 | Uniconazole slow-release microcapsules and preparation method thereof |
| CN101966340A (en) * | 2010-10-20 | 2011-02-09 | 无锡正大畜禽有限公司 | Method for producing florfenicol soluble powder |
| CN102084863B (en) * | 2011-03-01 | 2012-03-28 | 宁波市鄞州浩斯瑞普生物科技有限公司 | Slow-release preparation of slow-release thiadiazine substances |
| CN102165952B (en) * | 2011-03-01 | 2012-04-11 | 宁波市鄞州浩斯瑞普生物科技有限公司 | Sustained-release benzothiazole ammonium salt |
| CN112106771B (en) * | 2020-10-29 | 2021-12-21 | 中国农业科学院植物保护研究所 | Dimethyl disulfide cyclodextrin inclusion compound and preparation method and application thereof |
| CN113773136A (en) * | 2021-08-27 | 2021-12-10 | 北京嘉博文生物科技有限公司 | Long-acting multifunctional foliar fertilizer and preparation method thereof |
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