CN105230612B - Chlorpyrifos composite microsphere - Google Patents
Chlorpyrifos composite microsphere Download PDFInfo
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- CN105230612B CN105230612B CN201510470245.5A CN201510470245A CN105230612B CN 105230612 B CN105230612 B CN 105230612B CN 201510470245 A CN201510470245 A CN 201510470245A CN 105230612 B CN105230612 B CN 105230612B
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- Prior art keywords
- humic acid
- chlopyrifos
- sodium alginate
- microsphere
- complex microsphere
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- 239000004005 microsphere Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title abstract description 8
- 239000005944 Chlorpyrifos Substances 0.000 title abstract 3
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 title abstract 3
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 75
- 239000004021 humic acid Substances 0.000 claims abstract description 72
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000661 sodium alginate Substances 0.000 claims abstract description 70
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 70
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000001110 calcium chloride Substances 0.000 claims abstract description 17
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003814 drug Substances 0.000 abstract description 34
- 229940079593 drug Drugs 0.000 abstract description 18
- 239000003431 cross linking reagent Substances 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- -1 humic acid modified sodium alginate Chemical class 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000003337 fertilizer Substances 0.000 abstract description 3
- 239000000575 pesticide Substances 0.000 abstract description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract 1
- 235000015097 nutrients Nutrition 0.000 abstract 1
- 206010042674 Swelling Diseases 0.000 description 15
- 230000008961 swelling Effects 0.000 description 15
- 239000000499 gel Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- 239000011806 microball Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003905 agrochemical Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000002574 poison Substances 0.000 description 5
- 231100000614 poison Toxicity 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000011805 ball Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000000648 calcium alginate Substances 0.000 description 3
- 235000010410 calcium alginate Nutrition 0.000 description 3
- 229960002681 calcium alginate Drugs 0.000 description 3
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000003937 drug carrier Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005847 immunogenicity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010999 medical injection Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention discloses a chlorpyrifos composite microsphere. The composite microsphere is prepared by taking humic acid modified sodium alginate as a composite matrix material to load chlorpyrifos and calcium chloride (CaCl)2) Prepared as a cross-linking agent. The invention forms a novel composite matrix material by mixing humic acid and sodium alginate. The interaction of humic acid and sodium alginate is utilized to improve the microsphere structure, so that the composite microsphere network structure becomes dense, the microsphere skeleton density is increased, the drug amount capable of being carried is increased, and the drug embedding capacity is enhanced, thereby improving the drug loading performance of the microsphere. Humic acid can also be used as a nutrient component of plants, so that the composite microspheres have the function of integrating pesticide and fertilizer.
Description
Technical field
The invention belongs to the technical field of composite, more particularly, to a kind of chlopyrifos complex microsphere.
Background technology
Chlopyrifos is the maximum kind of sales volume in insecticide in the world at present, its as the insecticide being widely used,
With it is efficient the advantages of, prevention effect is excellent, has wide market prospects.But it has, and toxicity is higher, peculiar smell is larger lacks
Point.
Microballoon is using natural or artificial synthesized high polymer material, and the medicine of the inside parcel is solid or liquid, shape
Into load medicinal gel microballoon.In field of biological pesticide, because many agricultural chemicals have no idea directly to use, or it is directly used
Effect it is bad, if it is desired that the effect of agricultural chemicals reaches best, it is necessary to strengthen the system, one of which by other approach
Exactly using high polymer material come embedding medicinal, so that drug bearing microsphere be made.This high polymer material is down to the toxicity of medicine
It is minimum, and agricultural chemicals is fully utilized.The effect of so allowing for medicine is with regard to that can reach most strong best.The best load of performance at present
Medicine microballoon should possess following performance：（1）Biodegradability and nontoxicity；（2）Targeting；（3）Insoluble drug release controllability；（4）
Hydrophily and（5）Good biocompatibility.
Sodium alginate is the sodium salt of alginic acid, have alginic acid gelling properties, Gelation Conditions are gentle, to pH value, temperature,
Ionic strength has certain response, is the good material for making intelligent aqueous gel.The hydrogel of making is nontoxic to body, has good
Good biocompatibility and can biology solution property, non-immunogenicity, thus be excellent drug carrier material.With sodium alginate by poison
Dead tick embedding gets up to form gel micro-ball, can solve chlopyrifos very well and see the problems such as light decomposes, toxicity is higher, peculiar smell is larger.
But sodium alginate hydrophily is strong, gel aperture is big, low to hydrophobic drug drugloading rate, and drug release rate is fast, and prominent release easily occurs.
In addition, sodium alginate gel microsphere bad mechanical property, microsphere surface easily caves inward in manufacture or drying process, degradable
Drug carrying ability is caused to decline with a large amount of swellings of water are met, and sodium alginate gel contains substantial amounts of hydrophilic radical, to organic
The load capacity of medicine is not high.In order to expand application of the sodium alginate in terms of drug carrier material, it is necessary to be carried out to sodium alginate
It is modified, to lift drugloading rate and envelop rate of the drug carrier material to medicine, and improve its Release Performance, to reach sustained release and control
The effect released.
The content of the invention
The technical problems to be solved by the invention are the defects of overcoming existing sodium alginate cladding chlopyrifos to exist and technology
Deficiency, chlopyrifos is loaded using humic acid modified sodium alginate as compound matrix material, there is provided a kind of humic acid/sodium alginate/
Chlopyrifos complex microsphere, drug carrying ability of the sodium alginate to chlopyrifos can be improved.Meanwhile humic acid is also used as the battalion of plant
Form point, make the complex microsphere that there is the function of medicine fertilizer integration.
It is an object of the invention to provide a kind of humic acid/sodium alginate/chlopyrifos complex microsphere.
Another object of the present invention is to provide the preparation method of above-mentioned complex microsphere.
Above-mentioned purpose of the present invention is to be achieved by the following technical programs：
A kind of chlopyrifos complex microsphere, it is load chlopyrifos using humic acid modified sodium alginate as compound matrix material,
With CaCl2Gained is prepared as crosslinking agent.
Humic acid is polycationic compounds, when being combined with anionic polymer sodium alginate, the carboxyl of its strand with
The hydroxyl of sodium alginate can attract to form plural gel by positive and negative charge.Humic acid not only have carrier possessed by filling,
The effects such as scattered, dilution, absorption, but also there is bioactivity, the stability of agricultural chemicals can be improved, and reduce agricultural chemicals in soil
Loss.Therefore, the drug carrying ability of gel micro-ball system can be improved using humic acid.Due to the phase of humic acid and sodium alginate
Interaction makes complex microsphere network structure become close, and during micro-sphere crosslinked, it is molten that chlopyrifos from matrix penetrates into crosslinking agent
Liquid medium-rate is slower, therefore increase tendency is presented in drugloading rate, and the ability of embedding medicinal also accordingly increases.Further, since humic acid
With colloidal property, larger specific surface area and abundant microcellular structure, therefore also there is preferable suction-operated, it can be poison
Dead tick is preferably supported on carrier, so as to reduce the loss of chlopyrifos.
Meanwhile humic acid has multi-functional group, make it possess good ion-exchange performance and complexing with it is sequestering
Can, cotton-shaped gel can be formed with crosslinking agent, crosslink density can be increased, improves micro-sphere structure, improves drug carrying ability.
Inventor also found, the ratio of humic acid and sodium alginate has shadow to properties such as the drugloading rate of microballoon, envelop rates
Ring.
Preferably, in the chlopyrifos complex microsphere, the mass ratio of humic acid and sodium alginate is 10 ~ 60%.
It is highly preferred that in the complex microsphere, the mass ratio of humic acid and sodium alginate is 40%.On this condition, can obtain
Obtain more preferably drugloading rate, envelop rate.
Preferably, in the complex microsphere, crosslinking agent CaCl2Quality and humic acid and sodium alginate gross mass quality
Than for 4 ~ 14:1.
Preferably, by CaCl2It is prepared into CaCl2Solution, then mixed with humic acid and sodium alginate.
The preparation method of the chlopyrifos complex microsphere, it may be referred to the existing method for preparing complex microsphere.According to need
The amount wanted, it can select to note drop method（Laboratory scale）Or spray drying（Industrial production）The methods of be prepared.
As a kind of exemplary preparation method, above-mentioned chlopyrifos complex microsphere can be prepared in accordance with the following steps：
S1. the mass ratio for determining humic acid and sodium alginate is 10 ~ 60%, and humic acid is added in alkaline solution, is stirred
Fully dissolving, obtains humic acid solution；
S2. chlopyrifos is dissolved in anhydrous alcohol solution, be sufficiently mixed with the humic acid solution obtained by S1；
S3. in humic acid sodium alginate being slowly added into obtained by S2/chlopyrifos mixed liquor, continue stirring until and dissolved
Entirely, bubble removing, obtain that colloidal sol is blended；
S4. blending colloidal sol is added to CaCl20.5 ~ 1.5h balling-up is crosslinked in solution, through being dried under vacuum to perseverance after cleaning
Weight, produces humic acid/sodium alginate/chlopyrifos complex microsphere.
Preferably, alkaline solution described in step S1 is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or bicarbonate
One kind in sodium.
It is highly preferred that alkaline solution described in step S1 is sodium hydroxide.
It is highly preferred that humic acid described in step S1 is 40% with sodium alginate mass ratio.
Preferably, alcohols described in step S2 is one kind in methanol, ethanol, normal propyl alcohol or n-butanol.
It is highly preferred that alcohols described in step S2 is ethanol.
Certain density humic acid/sodium alginate/chlopyrifos blending colloidal sol is added to CaCl by the present invention2Cross-linking agent solution
In, Ca2+Sodium alginate drop is entered by osmosis, the rapid crosslinking curing of drop forms gel micro-ball.Due to sodium alginate
And CaCl2Reaction is crosslinked, forms IPN cross-linked network, makes the complex microsphere base material that there is stable structure.Inventor
It has also been found that CaCl2The concentration of solution has an impact to the swelling ratio of complex microsphere.Work as CaCl2When solution concentration is higher, colloidal sol is blended
Sodium ion and the calcium ion-exchanged rate in solution are high in liquid, the crosslinking degree increase of gel, the calcium alginate being complexed by calcium ion
Gel structure tends to close, and the skeletal density of microballoon is big, causes hydrone to enter the resistance increase of microballoon, and swelling ratio reduces.It is multiple
The swelling ratio of conjunction microballoon is lower, and the structure of complex microsphere is more stable, has more preferable slow release effect.Preferably, described in step S4
CaCl2Solution concentration is 0.3 ~ 1.0mol/L.
It is highly preferred that CaCl described in step S42Solution concentration is 0.9mol/L.
Inventor also found that crosslinking time length also has a certain impact to the swelling ratio of complex microsphere.Preferably, step
Crosslinking time described in S4 is 0.5 ~ 1.5h.
It is highly preferred that crosslinking time described in step S4 is 1h.
Compared with prior art, the invention has the advantages that：
The present invention loads chlopyrifos using humic acid modified sodium alginate as compound matrix material, there is provided and a kind of humic acid/
Sodium alginate/chlopyrifos complex microsphere, drug carrying ability of the sodium alginate to chlopyrifos can be improved, is had the advantage that：
1. the interaction of humic acid and sodium alginate improves micro-sphere structure, complex microsphere network structure is set to become close
Collection, the skeletal density of microballoon is big, and the medication amount that can be carried is more, also enhances the ability of embedding medicinal, so as to improve microballoon
Drug carrying ability；Humic acid has colloidal property, larger specific surface area and more rich microcellular structure, has preferably absorption to make
With it preferably can be maintained at chlopyrifos on carrier, so as to reduce the loss of chlopyrifos.Humic acid is also used as plant
Nutritional ingredient, make the complex microsphere have medicine fertilizer integration function.And humic acid contains substantial amounts of functional group, has
Good ion-exchange performance and complexing and chelating ability, itself and CaCl2Mixing, the crosslink density of micro-sphere structure can be increased,
So as to improve the drug carrying ability of microballoon.
2. sodium alginate and CaCl2Reaction is crosslinked, forms IPN cross-linked network, calcium alginate gel structure is become
To close, the skeletal density of microballoon is big, causes hydrone to enter the resistance increase of microballoon, makes the reduction of complex microsphere swelling ratio, tool
There is stable structure.
3. it is 40% to work as humic acid with sodium alginate mass ratio, crosslinking agent CaCl2Concentration is 0.9mol/L, and crosslinking time is
During 1h, the cross-linked scaffold density of complex microsphere reaches saturation, and drugloading rate and envelop rate reach peak value.
Brief description of the drawings
Fig. 1 is chlopyrifos（a）, humic acid/sodium alginate micro ball（b）, humic acid/sodium alginate/chlopyrifos microballoon（c）'s
FT-IR spectrograms.
Fig. 2 is humic acid/sodium alginate/chlopyrifos microballoon（a）, sodium alginate/chlopyrifos microballoon（b）, chlopyrifos（c）'s
Differential scanning calorimetric curve.
Fig. 3 is influence of the mass ratio of humic acid and sodium alginate to chlopyrifos drugloading rate and envelop rate.
Fig. 4 is crosslinker concentration to the chlopyrifos drugloading rate of complex microsphere and the influence of envelop rate.
Fig. 5 is influence of the mass ratio of humic acid and sodium alginate to complex microsphere swelling ratio.
Embodiment
Present disclosure is further illustrated with reference to specific embodiment, but should not be construed as limiting the invention.
Without departing from the spirit and substance of the case in the present invention, the simple modifications or substitutions made to the inventive method, step or condition,
Belong to the scope of the present invention；Unless otherwise specified, technological means used in embodiment is well known to those skilled in the art
Conventional meanses.
Unless stated otherwise, the reagent of the invention used, method and apparatus for the art conventional reagent, method and are set
It is standby.Unless stated otherwise, agents useful for same and material of the present invention are purchased in market.
Embodiment 1-12 prepares humic acid/sodium alginate/chlopyrifos complex microsphere
By humic acid and the mass ratio of sodium alginate, the quality of fixed sodium alginate, the humic acid of different quality is distinguished
It is dissolved in the mol/LNaOH aqueous solution of 20 mL 0.1, fully dissolving is heated under magnetic agitation；The g of precise 0.6 chlopyrifos
It is dissolved in 5 mL absolute ethyl alcohol, is sufficiently mixed with humic acid solution；Precise 0.3g sodium alginates, are slowly added into rotten plant
In acid/chlopyrifos blended liquid, stop heating, stop stirring after abundant dissolving, ultrasonic disperse bubble removing, obtain humic acid/sea
Mosanom/chlopyrifos blending colloidal sol.The dropwise addition of fixed syringe pump is highly 30 cm, and rate of addition is 50 mLh-1, medical injection
Device specification is 10 mL, and colloidal sol will be blended and be added dropwise to the CaCl that volume is 50mL2Balling-up is crosslinked in solution, vacuum is done after cleaning 3 times
It is dry to constant weight, the humic acid/sodium alginate/chlopyrifos complex microsphere being prepared is listed in Table 1 below.
Table 1 prepares the complex microsphere of humic acid/sodium alginate/chlopyrifos
。
Comparative example 1 prepares sodium alginate/chlopyrifos microballoon
Precise 0.6g chlopyrifos heating is dissolved in 5ml absolute ethyl alcohol；Precise 0.3g sodium alginates, slowly
It is added in chlopyrifos ethanol solution, stops heating, stops stirring after abundant dissolving, ultrasonic disperse bubble removing, obtain marine alga
Sour sodium/chlopyrifos blending colloidal sol.The dropwise addition of fixed syringe pump is highly 30 cm, and rate of addition is 50 mLh-1, injector for medical purpose
Specification is 10 mL, and it is the CaCl that 50mL concentration is 0.9mol/L that blending colloidal sol is added dropwise into volume21h balling-up is crosslinked in solution,
Constant weight is dried under vacuum to after cleaning 3 times, produces sodium alginate/chlopyrifos microballoon.
Comparative example 2 prepares humic acid/sodium alginate micro ball
By humic acid and the mass ratio of sodium alginate, the quality of fixed sodium alginate, the humic acid of different quality is distinguished
It is dissolved in the 20 mL 0.1mol/LNaOH aqueous solution, is fully dissolved under magnetic agitation；Precise 0.3g sodium alginates, slowly add
Enter into humic acid solution, stop stirring after abundant dissolving, ultrasonic disperse bubble removing, obtain humic acid/sodium alginate blending
Colloidal sol.The dropwise addition of fixed syringe pump is highly 30 cm, and rate of addition is 50 mLh-1, injector for medical purpose specification is 10 mL, by altogether
It is the CaCl that 50mL concentration is 0.9mol/L that miscible glue, which is added dropwise to volume,21h balling-up is crosslinked in solution, is dried in vacuo after cleaning 3 times
To constant weight, humic acid/sodium alginate micro ball is produced.
Structure is carried out to above-described embodiment, comparative example 1, comparative example 2 and chlopyrifos and performance is tested, it is as a result as follows：
The structural characterization of microballoon：
1st, FT-IR measure and analysis：Sodium alginate, humic acid and humic acid/sodium alginate/chlopyrifos complex microsphere crush
Powder, through KBr tablettings, using Spectrum100 type Fourier infrared spectrographs（FT-IR infrared spectrum measurement, scanning) are carried out
Wave-number range is 4000 ~ 500cm-1, scanning times 4 times.
Fig. 1 is chlopyrifos, humic acid/sodium alginate micro ball, the FT-IR of humic acid/sodium alginate/chlopyrifos complex microsphere
Spectrogram.From Fig. 1 c as can be seen that 1549,1412,1170cm-1There is the characteristic absorption peak of chlopyrifos in place, is pyrrole respectively
The C-C in C=C, aromatic series, aromatic P-O-C in pyridine ring, illustrate to have loaded chlopyrifos in complex microsphere.
2nd, means of differential scanning calorimetry (DSC) tracing analysis：Use DSC differential scanning calorimetries, temperature elevating range 20~250
DEG C, heating rate is 20 DEG C of min-1, nitrogen rate 30mL/min, it is compound micro- to determine humic acid/sodium alginate/chlopyrifos
Ball, sodium alginate/chlopyrifos microballoon and the differential scanning calorimetric curve of chlopyrifos.
Fig. 2 is humic acid/sodium alginate/chlopyrifos complex microsphere（a）, sodium alginate/chlopyrifos microballoon（b）, chlopyrifos
（c）Differential scanning calorimetric curve.Occur highly endothermic peak at 43.2 DEG C in curve c, be because of chlopyrifos at this temperature
Fusing, this is consistent with the fusing point of chlopyrifos；Humic acid/sodium alginate/chlopyrifos complex microsphere occurs at 45.4 DEG C in curve a
The melting peak of chlopyrifos；There is the melting peak of chlopyrifos at 41.8 DEG C in sodium alginate/chlopyrifos microballoon in curve b, shows poison
Dead tick is still coated in microballoon with crystalline state.Compared with c, chlopyrifos melting peak is subjected to displacement by curve a, b, and this is due to poison with poison
Tick forms active force with sodium alginate, the intermolecular of humic acid.
The measure of microballoon drugloading rate and envelop rate
1st, the assay method of drugloading rate：Quantitative 30mg microballoons are weighed, are transferred to 25mL volumetric flasks, add a certain amount of 40%
Ethanol solution, it is subsequently placed in ultrasonic cleaner and is cleaned（Ultrasound destruction micro-sphere structure）, then volumetric flask is positioned over perseverance
In tepidarium oscillator, 24h is vibrated in 35 DEG C of waters bath with thermostatic control.Corresponding scale is finally settled to again, after being well mixed, takes upper strata clear
Liquid dilutesxTimes, under λ=290nm wavelength, the absorbance of determination sample solution.
2nd, the assay method of envelop rate：Reference standard concentration curve draws the concentration of chlopyrifos solution, by formula (1) and
(2) agricultural chemicals drugloading rate (LC) and envelop rate (EE) are calculated：
LC=carrying medicaments quality/microspheres quality (1)
Carrying medicament gross mass/total drug quality (2) in EE=microballoons
3rd, interpretation of result：
The drugloading rate and envelop rate of humic acid/sodium alginate/chlopyrifos complex microsphere are listed in Table 2 below.
The drugloading rate and envelop rate of the chlopyrifos complex microsphere of table 2
Influence of the mass ratio of different humic acids and sodium alginate to drugloading rate and envelop rate, as shown in figure 3 and table 2.Knot
Fruit shows that, with the increase of humic acid and sodium alginate mass ratio, the trend of first increases and then decreases is presented in drugloading rate.When ratio is low
When 40%, because the interaction of humic acid and sodium alginate makes complex microsphere network structure become close, microballoon had been crosslinked
Cheng Zhong, it is slack-off that medicine from matrix penetrates into cross-linking agent solution medium-rate, therefore drugloading rate is presented increase tendency, and its embedding medicinal
Ability also accordingly increases.When ratio reaches 40%, drugloading rate reaches peak value 59.52%, and envelop rate reaches peak value 51.42%.When than
When example is higher than 40%, complex microsphere network structure becomes even closer, while complex microsphere can accommodate the space reduction of medicine,
Therefore reduction trend is presented in drugloading rate and envelop rate.
Influence of the different crosslinker concentrations to drugloading rate and envelop rate, as shown in Fig. 4 and table 2.As a result show, with crosslinking
The trend of increase is presented in the increase of agent concentration, drugloading rate and envelop rate.CaCl2When solution concentration is relatively low, sodium in sol solutionses is blended
Ion is low with the calcium ion-exchanged rate in solution, and the three-dimensional netted gel structure of calcium alginate is more loose, and drugloading rate is low, embeds medicine
Thing ability.And CaCl2When solution concentration is higher, sodium ion and the calcium ion-exchanged rate height in solution in sol solutionses is blended, it is micro-
The skeletal density of ball is big, and the medication amount that can be carried increases, and also enhances its embedding medicinal ability.
Influence of the different crosslinking times to drugloading rate and envelop rate, as shown in table 2.With the increase of crosslinking time, medicine is carried
The trend of first increases and then decreases is presented in amount and envelop rate.This is due to that crosslinking time is longer, and microspherulite diameter, which reduces, causes internal junction
Structure is closer, and microchannel becomes narrow, so as to add hydrone into the resistance inside microballoon.It is micro- but crosslinking time is long
Ball is immersed in the overlong time in water, can cause the swelling behavior of microballoon to increase, and microballoon internal structure is progressively evacuated, and microchannel increases
Greatly, medicine is dissolved into external solution from microballoon again, so that drugloading rate declines, the ability of embedding medicinal also decreases.
Influence of the different mixing speeds to drugloading rate and envelop rate, as shown in table 2, with the increase of mixing speed, carry medicine
The trend of first increases and then decreases is presented in amount and envelop rate.When low whipping speed is 500 r/min, cross-linking reaction is most abundant, carries medicine
Amount and envelop rate reach highest.
Microspheres swell performance evaluation
Microspheres swell performance test methods：The dry microspheres of certain mass are weighed, are placed in medium solution to swelling equilibrium,
Unnecessary liquid is filtered off, the moisture of microsphere surface is blotted with filter paper, is weighed, calculates swelling ratio (SR).Swelling ratio calculation formula (3)
It is as follows：
In formula, WSFor quality (g) of the dry microspheres in water during swelling equilibrium；
WdFor the quality (g) of dry microspheres.
Table 3
。
From table 3 it can be seen that humic acid is added in sodium alginate micro ball, it is possible to reduce the swelling ratio of microballoon.Swelling ratio
Smaller, complex microsphere can obtain more preferably slow release effect.From the foregoing, the addition of humic acid can also influence drugloading rate and encapsulating
Rate, under conditions of embodiment 12, drugloading rate, envelop rate and swelling ratio can be made to obtain good balance.
The above embodiment of the present invention is only to clearly demonstrate example of the present invention, and is not the reality to the present invention
Apply the restriction of mode.For those of ordinary skill in the field, can also make on the basis of the above description other
Various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.All spirit in the present invention
With all any modification, equivalent and improvement made within principle etc., it should be included in the protection domain of the claims in the present invention
Within.
Claims (1)
1. a kind of chlopyrifos complex microsphere, it is characterised in that the complex microsphere is to be prepared via a method which to obtain：
By humic acid and the mass ratio 40% of sodium alginate, fixed sodium alginate 0.3g quality, humic acid is dissolved in 20 mL
Fully dissolving is heated in the 0.1 mol/LNaOH aqueous solution, under magnetic agitation, mixing speed is 500 r/min；Precise 0.6
G chlopyrifos is dissolved in 5 mL absolute ethyl alcohol, is sufficiently mixed with humic acid solution；Precise 0.3g sodium alginates, slowly
It is added in humic acid/chlopyrifos blended liquid, stops heating, stops stirring after abundant dissolving, ultrasonic disperse bubble removing, obtain
Humic acid/sodium alginate/chlopyrifos blending colloidal sol；The dropwise addition of fixed syringe pump is highly 30 cm, and rate of addition is 50 mL h-1, injector for medical purpose specification is 10 mL, and colloidal sol will be blended and be added dropwise to the CaCl that volume is 50mL2Balling-up is crosslinked in solution, when
CaCl2When solution concentration is 0.7 mol/L, crosslinking time is 0.5 hour or works as CaCl2When solution concentration is 0.7 mol/L, hand over
It is 1 hour to join the time, is dried under vacuum to constant weight after cleaning 3 times, chlopyrifos complex microsphere is prepared.
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