CN101518258B - Method for preparing matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation - Google Patents
Method for preparing matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation Download PDFInfo
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Abstract
The invention discloses a preparation method and use of a matrine/ carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation. The method comprises the following steps: (1) preparing phosphonic chitosan; and (2) preparing matrine/ carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation. The method overcomes the water insoluble drawback of chitosan and provides a reference of the new agricultural use of the chitosan and derivatives thereof; An pesticide nanoparticle aqueous dispersion preparation is advantageous overa simple water aqueous solution preparation in insect killing effect; after a botanical pesticide is nano-sized, the nano particles can protect and stabilize the pesticide to allow the pesticide to r elease slowly in a controlled way; the preparation method is easy to implement and avoids use of organic solvent and assistant; and degradation products of the chitosan and the derivatives of the chitosan can adjust the growth of vegetables, and nitrogen and phosphor in the degradation products are fertilizers of vegetables, so the preparation of the invention is a real environmentally-friendly pesticide.
Description
Technical field
The invention belongs to natural macromolecule modification and agriculture pesticidal preparations field, the preparation method and its usage of particularly a kind of matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation.
Background technology
Having cationic natural polysaccharide---shitosan receives people's favor because of its unique biological performance.Yet the character that shitosan can only be dissolved in acid solution is restricted its direct application.On the one hand, as pharmaceutical carrier, acid medium is easy to cause to the toxicity of organism with to the interference of pharmaceutical properties; On the other hand, chitosan molecule can be precipitated out in the aqueous solution of pH neutral.This performance is restricted its application as agricultural chemicals and pharmaceutical carrier.Therefore, seeking the water-soluble approach of shitosan, prepare its soluble derivative, is to use the key of shitosan as the stroma ground substance of agricultural chemicals and medicament nano medicine carrying particle.
Matrine (Matrin) is to separate the alkaloid that obtains the root, stem from the cassia leguminous plant kuh-seng, is generally Banlangen, and is the highest with the content of matrine, oxymatrine.Matrine belongs to quinolizine pyridine analog derivative (structural formula is seen Fig. 1).Matrine can be used as medicine and botanical pesticide, insect is had tag, stomach poison function.In a single day insect touches this medicament, can make its food refusal, nervous centralis paralysis, and polypide protein solidifies, and insect is choked to death.Matrine has good killing effect to insects such as cabbage caterpillar, aphid, diamond-back moth, two spotted spider mite, thrips, liriomyza bryoniaes.
Matrine has broad spectrum disinfestation, characteristics that pest resistance to insecticide is low, to non-target organism safety, and to the person poultry harmless, environmental friendliness, and the Regional Distribution of plant is wide, and the source is abundant, and cost is low, and this makes matrine more deep as the research of pesticidal preparations.But compare with synthetic pesticide, also have the common deficiency that exists of botanical pesticide: the performance drug effect is slow, and active component is prone to decompose, and to photo-labile, the duration is short.Wherein, Stability Control is a difficult problem of generally acknowledging.Botanical pesticide mostly need be used artificial additive synthesis except that minority is water-soluble in addition, and the preparation complicated component is unfavorable for environmental protection.Improving the insecticidal effect of matrine to insect, make it have slowly-releasing, long-acting, is the target of the development pursuit of botanical pesticide preparation.
Summary of the invention
In order to solve the weak point of above-mentioned prior art, primary and foremost purpose of the present invention is to provide the preparation method of a kind of matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation.
Another object of the present invention is to provide the purposes of the matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation of method for preparing.
The object of the invention is realized through following technical proposals: the preparation method of a kind of matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation comprises following operating procedure:
The preparation of matrine/carboxymethyl chitosan/phosphonic chitosan (Mat/CMC/PCS) nanoparticle aqueous dispersion preparation: with 5～10ml concentration is the matrine water solution of 1.0～2.0mg/ml and the CMC aqueous solution that 5～15ml concentration is 0.25～0.5mg/ml; Under stirring condition; Above-mentioned mixed liquor is dropwise joined in the aqueous solution that 5～15ml concentration is 0.5～1.0mg/ml step (1) gained phosphonized chitosan (PCS), obtain matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation.
The preparation of described phosphonized chitosan comprises following operating procedure: it is in 1%～1.5% the acetic acid solution that 5～10g shitosan is dissolved in 250～500ml concentration expressed in percentage by volume; Be warming up to 60～75 ℃, adding mass and size concentration is the phosphoric acid solution of 0.25～0.5g/ml; Adding 6～15ml mass percent is 37～40% formalin, in 70～80 ℃ of following stirring reaction 1～5.5h; With precipitating in the reactant liquor impouring absolute ethyl alcohol, filter, collecting precipitation embathes 2～3 times with absolute ethyl alcohol, at-30～-10 ℃ of freeze drying 24～48h, obtains phosphonized chitosan.
The viscosity average molecular weigh of described shitosan is 3.0 * 10
4～2.2 * 10
5, deacetylation>=90%.
The viscosity average molecular weigh of described CMC is 6.1 * 10
4～5.3 * 10
5
A kind of matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation according to method for preparing.
Above-mentioned matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation is applied to pesticidal preparations, can kill pests.
The relative prior art of the present invention has following advantage and beneficial effect: (1) phosphonized chitosan can be dissolved in the neutral aqueous solution as the derivative of shitosan fully; Not only overcome the general water-fast shortcoming of shitosan and derivative thereof, for shitosan and the application of derivative on agricultural thereof provide reference; The Application of Chitosan field has also further been expanded in the introducing of new functional group phosphate; (2) the present invention is a farm chemical carrier with CMC and phosphonized chitosan, has prepared matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation, has effectively improved the drug effect and the stability of matrine.The matrine molecule is carried on the inside or the surface of the nano particle that is formed by chitosan derivatives, and nano particle has played protection, stabilization to agricultural chemicals, makes said preparation demonstrate slowly-releasing, the long-acting function that gets.Not only overcome the defective of matrine water solvent, and pesticide nanoparticle aqueous dispersion preparation of the present invention is superior to simple aqueous formulation to the killing effect of insect; (3) in this pesticide nanoparticle aqueous formulation, the size of particle is in 100～300nm scope, and the quantity of nano particle is many, and surface area is big, has both increased the dispersiveness and the contact area of pesticide molecule, also helps adhesion and infiltration to plant leaf blade and organism; (4) botanical pesticide nanoparticle aqueous dispersion preparation of the present invention is a kind of novel formulations of pesticide; Not only the preparation method is prone to row; Avoided the use of organic solvent and other auxiliary agent; And the catabolite of chitosan derivatives has regulating action to plant growing, and its nitrogen, P elements also are the fertilizer of plant, make it become the environment friendly agricultural of real meaning.The invention of this botanical pesticide preparation provides new research thinking for the eco-friendly pesticidal preparations of development.
Description of drawings
Fig. 1 is the chemical structural formula of matrine.
Fig. 2 is that (a is a shitosan for the infared spectrum of phosphonized chitosan; B is a phosphonized chitosan).
Fig. 3 is the nuclear magnetic resonnance figure of phosphonized chitosan.
Fig. 4 is the sem photograph of matrine/carboxymethyl chitosan/phosphonic chitosan nano particle.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
At first following to the explanation of experiment material:
Shitosan, deacetylation (DD)>=90%, viscosity average molecular weigh (M
v) be respectively 2.2 * 10
5, 8.5 * 10
4, 3.0 * 10
4Formaldehyde (A.R., Guangzhou Chemical Reagent Factory), ethanol (A.R., Tianjin Da Mao chemical reagent factory); Phosphorous acid (A.R., Chemical Reagent Co., Ltd., Sinopharm Group); Matrine (the Shaanxi prosperous biotechnology of gold Co., Ltd); (viscosity average molecular weigh is 6.1 * 10 to CMC
4, substitution value is 0.66, Zhejiang Austria Co., Ltd that makes the science and technology prosperous; Viscosity average molecular weigh 5.3 * 10
5, substitution value is 0.65, is this laboratory self-control, the preparation method sees Liu Zonghua, " research of natural polysaccharide and derivates nanometer medicine-carried system thereof ", doctorate paper, the 2nd chapter,, Ji'nan University in 2007)
Embodiment 1
(1) preparation of phosphonized chitosan: with the 5g viscosity average molecular weigh is 8.5 * 10
4, deacetylation be 95% shitosan to be dissolved in the 250ml concentration expressed in percentage by volume be in 1% the acetic acid solution, to be warming up to 60 ℃, adding mass and size concentration is the phosphorous acid solution of 0.25g/ml; Adding 15ml mass percent is 37% formalin, in 70 ℃ of following stirring reaction 1h; With precipitating in the reactant liquor impouring absolute ethyl alcohol, filter, collecting precipitation embathes 2 times with absolute ethyl alcohol, at-20 ℃ of freeze drying 24h, obtains phosphonized chitosan;
(2) preparation of matrine/carboxymethyl chitosan/phosphonic chitosan nanoparticle aqueous dispersion preparation: with 5ml concentration is that matrine (chemical structural formula of matrine the is as shown in Figure 1) aqueous solution and the 5ml concentration of 1.5mg/ml is the CMC aqueous solution of 0.35mg/ml, and the viscosity average molecular weigh of said CMC is 5.3 * 10
5Under stirring condition; Above-mentioned mixed liquor is dropwise joined in the aqueous solution that 5ml concentration is 0.5mg/ml step (1) gained phosphonized chitosan (aqueous solution of phosphonized chitosan contains positive charge), obtain matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation.
Embodiment 2
(1) preparation of phosphonized chitosan: with the 10g viscosity average molecular weigh is 8.5 * 10
4, deacetylation be 95% shitosan to be dissolved in the 500ml concentration expressed in percentage by volume be in 1.5% the acetic acid solution, to be warming up to 75 ℃, adding mass and size concentration is the phosphorous acid solution of 0.5g/ml; Adding 6ml mass percent is 40% formalin, in 80 ℃ of following stirring reaction 5.5h; With precipitating in the reactant liquor impouring absolute ethyl alcohol, filter, collecting precipitation embathes 3 times with absolute ethyl alcohol, at-30 ℃ of freeze drying 48h, obtains phosphonized chitosan;
(2) preparation of matrine/carboxymethyl chitosan/phosphonic chitosan nanoparticle aqueous dispersion preparation: with 10ml concentration is the matrine water solution of 1.0mg/ml and the CMC aqueous solution that 15ml concentration is 0.5mg/ml, the viscosity average molecular weigh 6.1 * 10 of said CMC
4Under stirring condition, above-mentioned mixed liquor is dropwise joined in the aqueous solution that 15ml concentration is 1.0mg/ml step (1) gained phosphonized chitosan, obtain matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation.
Embodiment 3
(1) preparation of phosphonized chitosan: with the 8g viscosity average molecular weigh is 2.2 * 10
5, deacetylation be 92% shitosan to be dissolved in the 350ml concentration expressed in percentage by volume be in 1.2% the acetic acid solution, to be warming up to 65 ℃, adding mass and size concentration is the phosphorous acid solution of 0.45g/ml; Adding 10ml mass percent is 38% formalin, in 75 ℃ of following stirring reaction 2h; With precipitating in the reactant liquor impouring absolute ethyl alcohol, filter, collecting precipitation embathes 2 times with absolute ethyl alcohol, at-10 ℃ of freeze drying 38h, obtains phosphonized chitosan;
(2) preparation of matrine/carboxymethyl chitosan/phosphonic chitosan nanoparticle aqueous dispersion preparation: with 8ml concentration is the matrine water solution of 2.0mg/ml and the CMC aqueous solution that 10ml concentration is 0.25mg/ml, the viscosity average molecular weigh 5.3 * 10 of said CMC
5Under stirring condition, above-mentioned mixed liquor is dropwise joined in the aqueous solution that 10ml concentration is 0.8mg/ml step (1) gained phosphonized chitosan, obtain matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation.
Embodiment 4
(1) preparation of phosphonized chitosan: with the 6g viscosity average molecular weigh is 3.0 * 10
4, deacetylation be 98% shitosan to be dissolved in the 450ml concentration expressed in percentage by volume be in 1.4% the acetic acid solution, to be warming up to 70 ℃, adding mass and size concentration is the phosphorous acid solution of 0.45g/ml; Adding 12ml mass percent is 37% formalin, in 78 ℃ of following stirring reaction 4h; With precipitating in the reactant liquor impouring absolute ethyl alcohol, filter, collecting precipitation embathes 2 times with absolute ethyl alcohol, at-15 ℃ of freeze drying 45h, obtains phosphonized chitosan;
(2) preparation of matrine/carboxymethyl chitosan/phosphonic chitosan nanoparticle aqueous dispersion preparation: with 9ml concentration is the matrine water solution of 1.7mg/ml and the CMC aqueous solution that 13ml concentration is 0.3mg/ml, the viscosity average molecular weigh 6.1 * 10 of said CMC
4Under stirring condition, above-mentioned mixed liquor is dropwise joined in the aqueous solution that 14ml concentration is 1.0mg/ml step (1) gained phosphonized chitosan, obtain matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation.
Embodiment 5
(1) preparation of phosphonized chitosan: with the 9g viscosity average molecular weigh is 8.5 * 10
4, deacetylation be 95% shitosan to be dissolved in the 400ml concentration expressed in percentage by volume be in 1.1% the acetic acid solution, to be warming up to 65 ℃, adding mass and size concentration is the phosphorous acid solution of 0.5g/ml; Adding 15ml mass percent is 37% formalin, in 72 ℃ of following stirring reaction 3h; With precipitating in the reactant liquor impouring absolute ethyl alcohol, filter, collecting precipitation embathes 3 times with absolute ethyl alcohol, at-25 ℃ of freeze drying 30h, obtains phosphonized chitosan;
(2) preparation of matrine/carboxymethyl chitosan/phosphonic chitosan nanoparticle aqueous dispersion preparation: with 10ml concentration is the matrine water solution of 1.0mg/ml and the CMC aqueous solution that 11ml concentration is 0.5mg/ml, the viscosity average molecular weigh 5.3 * 10 of said CMC
5Under stirring condition, above-mentioned mixed liquor is dropwise joined in the aqueous solution that 5ml concentration is 0.9mg/ml step (1) gained phosphonized chitosan, obtain matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation.
Embodiment 6
The structural analysis of phosphonized chitosan:
Embodiment 1 material therefor shitosan is carried out infrared spectrum measurement, and the result is shown in Fig. 2 a; Embodiment 1 step (1) gained phosphonized chitosan is carried out infrared spectrum measurement, and the result is shown in Fig. 2 b; B line and a line compare, and be visible, 1400～1100cm
-1The P=O stretching vibration absorption band in zone obviously strengthens 1025.91cm
-1The stretching vibration absorption band of the P-O-C at place also obviously strengthens, at 2915.21cm
-1The antisymmetric stretching vibration absorption band of methylene, 1630.92cm obviously appear in the place
-1The strong amino absorption band at place still exists, and explains that phosphorylation reaction mainly occurs on the hydroxyl.
Embodiment 1 step (2) gained phosphonized chitosan is carried out nuclear magnetic resonance measuring hydrogen spectrum, as shown in Figure 3, phosphonized chitosan proton chemical shifts: δ=4.77 (H
1), δ=3.56～3.84 (H
2H
3H
4H
5H
6), δ=2.0 (N-COCH
3), δ=3.10 (CH
2-).
To sum up, confirm that the proton type of embodiment 1 used shitosan and embodiment 1 step (1) gained phosphonized chitosan is consistent with chemical shift intensity with the following chemical constitution of representing through analyzing:
The chitosan structure formula
R
1＝H，R
2＝CH
2PO
3H
2
R
1＝R
2＝CH
2PO
3H
2
The phosphonized chitosan structural formula
Embodiment 7
The particle diameter and the Zeta potential of nano particle in matrine/carboxymethyl chitosan/phosphonic chitosan (Mat/CMC/PCS) pesticide nanoparticle aqueous dispersion preparation
Table 1 is the influence of matrine solution concentration to nano particle diameter, particle diameter distribution and surface charge.The concentration of CMC (CMC) and phosphonized chitosan (PCS) solution is respectively 1.0 and 0.50mg/ml; The concentration of matrine is respectively 1.0 and 2.0mg/ml.Get isopyknic CMC (CMC) solution and matrine (Mat) solution earlier and mix, the above-mentioned mixed liquor of getting different volumes again splashes into respectively in the PCS solution of equal volume.Visible by table, in the solution concentration scope that provides, the particle diameter of matrine nano particle is at 150nm～220nm, the grain size vary stable, thus the particle diameter narrow distribution, in 0.22～3.22 scope; The Zeta potential value of particle surface is a positive charge.Along with the increase of matrine solution concentration, nano particle diameter, particle diameter distribute and the zeta potential value changes little.But certain when the matrine solution concentration when reducing along with the volume of the required matrine solution of preparation nano particle, presents that nano particle diameter increases gradually, particle diameter distributes and narrows down gradually and trend that the Zeta potential value reduces gradually.
Table 1 matrine is to the influence of nano particle diameter, particle diameter distribution and surface charge
Embodiment 8
The morphosis of matrine/carboxymethyl chitosan/phosphonic chitosan (Mat/CMC/PCS) pesticide nanoparticle
Through the morphosis of scanning electron microscopic observation embodiment 2 resulting matrine/carboxymethyl chitosan/phosphonic chitosan (Mat/CMC/PCS) pesticide nanoparticles, as shown in Figure 4, visible; Gained particle size is than homogeneous; Form is the sphere of rule, and smooth surface can present single dispersion; The reason of adhesion appears in the part particle, is when the preparation electron microscopic sample, because water evaporates, thereby nano particle concentration increase gathering is formed.
Embodiment 9
Outdoor stability to embodiment 3 gained matrine/carboxymethyl chitosan/phosphonic chitosan (Mat/CMC/PCS) pesticide nanoparticle aqueous dispersion preparations is investigated; Test method is following: the nylon calico of 20cm * 20cm is flooded in matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation (concentration 0.25mg/ml) and matrine water pharmaceutical solutions (concentration 0.25mg/ml) respectively; Take out airing under field conditions (factors), fetched at 1,3,5,7,10,15,20 day respectively.In the triangular flask that the 50ml deionized water is housed, under agitation, extracted remaining matrine 5 hours.Extract detects matrine with high performance liquid chromatography (HPLC).Table 2 for matrine residual volume in the nylon calico extract of dipping matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation and matrine water solution over time.
The result shows: under identical outdoor natural conditions, the remaining matrine content on the nylon calico of dipping matrine water pharmaceutical solutions begins higher, but the amplitude that reduces in time is bigger, and the 20th day residual volume was compared with the 1st day and reduced by 45.5%.The trend that reduces in time of remaining matrine content on the nylon calico of dipping matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation is then very mild, compares with the 1st day in the 20th day, has only reduced by 16.5%.
The residual content that the remaining matrine content of dipping matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation generally is lower than dipping matrine water pharmaceutical solutions is that two aspect reasons cause.On the one hand, for the nylon calico of dipping matrine water solution,, can the whole dissolvings of the matrine of remnants be washed out because matrine is water-soluble; And the nylon calico of dipping matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation, because the nano particle of load matrine to the adhesive attraction of fiber, can not all wash out.The electromicroscopic photograph of the nylon calico after the extraction has proved this point, can see many matrine nano particles that stick on the fiber on the nylon fiber.On the other hand, HPLC also possibly can't detect the matrine molecule that is wrapped in inside nanoparticles.Because this two aspect causes the matrine residual content in matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation on apparent, generally to be lower than the matrine water pharmaceutical solutions.But the time dependent trend of matrine residual content shows that under identical outdoor natural conditions, matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation has protection, stabilization to the matrine molecule.
Its residual volume is over time after the outdoor environment airing for the nylon calico of table 2 dipping effects of different matrine aqueous formulation
Embodiment 10
The insecticidal test and the evaluating drug effect of matrine/carboxymethyl chitosan/phosphonic chitosan (Mat/CMC/PCS) pesticide nanoparticle aqueous dispersion preparation
The desinsection test of pesticide effectiveness and the evaluating drug effect of the aqueous dispersion of botanical pesticide nano particle are to carry out in Inst. of Plant Protection, Guangdong Prov. Academy of Agricultural Sciences.Test and evaluation method are all carried out according to national standard or scientific and standard.
(1) matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation is to the insecticidal effect of citrus red mite:
Use running water difference configuration concentration to be the matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation of 25mg/l and the aqueous solution preparation of matrine,, investigate influence the citrus red mite survival to the vigorous oranges and tangerines dispenser of field growing.Test method is established 3 repetitions for each processing.The spraying of blade two sides.Instituted an inquiry the insect population radix in 1 day behind the spray medicine, calculate the survival rate of two spotted spider mite, the result is as shown in table 3.
The desinsection result shows: after the dispenser in 3 days, matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation and matrine water solution to the citrus red mite survival rate to influence difference little; After 3 days, the difference of insecticidal effect begins to manifest, and the aphid survival rate of matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation begins to be lower than the matrine water pharmaceutical solutions; By the 15th day, the former aphid survival rate was 118.4%, and the latter is 140.3%.It is thus clear that matrine pesticide nanoparticle preparation demonstrates slowly-releasing, long-acting insecticidal effect.
Table 3 field matrine is to the survival influence of citrus red mite
Annotate: data are the mean+SD of 3 repetitions in the table
(2) matrine/carboxymethyl chitosan/phosphonic chitosan (Mat/CMC/PCS) pesticide nanoparticle aqueous dispersions is to the inhibition effect of diamond-back moth worm's ovum:
Test method is following: with long cabbage mustard transplantation of seedlings to the plastic cup (cup end diameter is 4cm, and the rim of a cup diameter is 6.5cm, highly is 8cm) that has 3～4, every glass 1 young plant.It is subsequent use to treat that the cabbage mustard seedling grows to 5～6 true leaves.With 50 times of matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation (the agricultural chemicals load factor is 66%, concentration 0.25mg/l) and matrine water pharmaceutical solutions (concentration 0.25mg/l) dilute with waters; With the clear water is blank.Above-mentioned solution evenly is applied in the positive and negative of cabbage mustard seedling leaf respectively; Placed 4 days, the cabbage mustard seedling that will handle in the 5th day is put into dependent insect cage by randomised block design, and (60cm * 60cm * 60cm), each handles 3 repetitions, again 88 pairs of diamond-back moth adults that sprouted wings 3 days is inserted dependent insect cage, puts and shrouds; Every 24h investigation diamond-back moth adult on the cabbage mustard seedling the ovum amount, investigation 96h, the result is as shown in table 4.
Table 4 matrine nanometer system is to the inhibition effect of diamond-back moth worm's ovum
Annotate: data are the mean+SD of 4 repetitions in the table
Result of the test shows that two groups of data are through the new range test of Deng Kenshi significant difference on 0.05 level.At spray medicine after 5 days, matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation becomes worm's ovum that inhibitory action is all arranged with the matrine water pharmaceutical solutions to diamond-back moth, and the former effect is superior to the latter to worm's ovum; In the time of the 8th day, it is 2.25% that the nanometer group the ovum amount, half the less than latter's (4.75%); Demonstrate matrine by nanorize after, nano particle has slowly-releasing, long-acting function to the inhibition of worm's ovum.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. the preparation method of matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation, it is characterized in that comprising following operating procedure: with 5～10ml concentration is the matrine water solution of 1.0～2.0mg/ml and the CMC aqueous solution that 5～15ml concentration is 0.25～0.5mg/ml; Under stirring condition, above-mentioned mixed liquor is dropwise joined in the aqueous solution that 5～15ml concentration is 0.5～1.0mg/ml phosphonized chitosan, obtain matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation.
2. preparation method according to claim 1; It is characterized in that: the preparation of described phosphonized chitosan comprises following operating procedure: it is in 1%～1.5% the acetic acid solution that 5～10g shitosan is dissolved in 250～500ml concentration expressed in percentage by volume; Be warming up to 60～75 ℃, adding mass and size concentration is the phosphorous acid solution of 0.25～0.5g/ml; Adding 6～15ml mass percent is 37～40% formalin, in 70～80 ℃ of following stirring reaction 1～5.5h; With precipitating in the reactant liquor impouring absolute ethyl alcohol, filter, collecting precipitation embathes 2～3 times with absolute ethyl alcohol, at-30～-10 ℃ of freeze drying 24～48h, obtains phosphonized chitosan.
3. preparation method according to claim 2 is characterized in that: the viscosity average molecular weigh of described shitosan is 3.0 * 10
4～2.2 * 10
5, deacetylation>=90%.
4. preparation method according to claim 1 is characterized in that: the viscosity average molecular weigh of described CMC is 6.1 * 10
4～5.3 * 10
5
5. matrine/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation according to each said method preparation of claim 1～4.
6. matrine according to claim 5/carboxymethyl chitosan/phosphonic chitosan pesticide nanoparticle aqueous dispersion preparation is in the pesticidal preparations Application for Field.
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| CN101856432B (en) * | 2010-05-19 | 2012-01-11 | 南京农业大学 | Preparation method of chitosan nanoparticles encapsulated tea polyphenol |
| CN104273179A (en) * | 2013-07-11 | 2015-01-14 | 青岛罗素生物技术有限公司 | Preparation method of oxymatrine aqueous solution |
| CN106962374A (en) * | 2017-03-24 | 2017-07-21 | 孙志廷 | A kind of biomass carbon particle for loading matrine chitosan sustained-release microsphere and preparation method thereof |
| CN112450213B (en) * | 2020-12-02 | 2022-06-24 | 苏州推动者生物科技有限公司 | Nano-carrier-agricultural active agent compound and preparation and application thereof |
| CN115885990B (en) * | 2022-11-04 | 2024-04-23 | 江苏科技大学 | Chitosan-capsaicin microcapsule material and preparation method thereof |
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| CN1727363A (en) * | 2005-07-25 | 2006-02-01 | 中国科学院海洋研究所 | N-substituted carboxymethyl chitosan and preparation method thereof |
| CN1868457A (en) * | 2006-06-08 | 2006-11-29 | 武汉理工大学 | Prepn. method of matrine magnetic micro-ball |
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| CN1727363A (en) * | 2005-07-25 | 2006-02-01 | 中国科学院海洋研究所 | N-substituted carboxymethyl chitosan and preparation method thereof |
| CN1868457A (en) * | 2006-06-08 | 2006-11-29 | 武汉理工大学 | Prepn. method of matrine magnetic micro-ball |
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