CN115380898A - Mesoporous hollow SiO based on pH response 2 Nano drug-loading system and preparation method and application thereof - Google Patents
Mesoporous hollow SiO based on pH response 2 Nano drug-loading system and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to application and development of nanotechnology in the field of pesticides, in particular to an environment-friendly mesoporous hollow SiO based on pH response 2 A nano drug-carrying system, a preparation method and application thereof. The nano drug-loading system adopts mesoporous hollow SiO 2 Loading active component of biological pesticide as carrier, passing chitosan through silicon under acidic condition with 3- (2, 3-epoxypropoxy) propyl trimethoxy silane as cross-linking agentThe oxygen bond is connected to the surface of the mesoporous hollow silica nano drug-carrying system. The nano drug-loaded system disclosed by the invention has pH responsiveness, and can promote the rapid release of the pesticide under an alkaline condition. Meanwhile, the non-toxic and biodegradable chitosan has good rain erosion resistance, can improve the retention and adhesion capacity of pesticide liquid drops on plant leaves, and reduces the loss of liquid medicine. And biological activity tests show that the Spodoptera frugiperda has good insecticidal activity.
Description
Technical Field
The invention relates to application and development of nanotechnology in the field of pesticides, in particular to an environment-friendly mesoporous hollow SiO based on pH response 2 A nano drug-carrying system, a preparation method and application thereof.
Background
Agricultural chemicals in modern agriculture play an irreplaceable role in controlling weeds, resisting plant diseases and insect pests, improving crop yield and the like. At present, the types of pesticide on the market are various. However, the traditional pesticide preparation has the defects of poor dispersibility, easy loss, quick release of active ingredients, short duration of pesticide effect and the like, and the utilization rate is extremely low; moreover, a large amount of pesticide with the traditional formula brings irreversible damage to ecological environment and non-target organisms, and the long-term use of the pesticide can cause the prevention and treatment objects to generate certain drug resistance. Therefore, the development of efficient pesticides with good control effect, low cost and little harm to the environment is urgently needed. It is reported that the solubility and stability of pesticides are improved by modifying functional groups of the pesticides by glycosylation, nitrosylation and the like, but the activity of the pesticides is reduced after modification, so that higher dosage is required to achieve similar insecticidal effect. The nanometer pesticide is prepared by loading the traditional pesticide in the nanometer material by utilizing the nanometer technology, and has great potential for solving a plurality of defects of the traditional pesticide. The nano material has the advantages of small size, large specific surface area, strong adsorption capacity, novel physical, chemical and mechanical properties and the like, can obviously improve the stability of the pesticide when being used for loading the pesticide, and is beneficial to improving the solubility and the permeability of the pesticide in a target tissue. In addition, the nano pesticide developed by aiming at agricultural prevention and control has targeted responsiveness, such as pH, illumination, temperature, enzyme and the like, can control the release rate and release amount of the pesticide under the action of internal and external environments, and reduces the pollution of the pesticide to the environment on the basis of improving the utilization rate and the pesticide effect of the pesticide.
The chitosan is a product of chitin after N-acetyl removal, has rich preparation resources, no toxicity, good tissue compatibility and biodegradability. The chitosan molecular chain contains a large amount of amino and hydroxyl, so that the chitosan has good pH sensitivity. The pH value of the intestinal environment of phytophagous lepidoptera pests such as spodoptera frugiperda is 8-11, and the phytophagous lepidoptera pests belong to alkalinity, so that the development of the pH response type nano drug loading system has potential application value for targeted killing of the spodoptera frugiperda.
Disclosure of Invention
In view of the above problems, the present invention provides a mesoporous hollow SiO based on pH response 2 The nano drug-loaded system has pH responsiveness, good rain erosion resistance and good killing effect on spodoptera frugiperda.
In order to achieve the aim, the mesoporous hollow SiO based on pH response provided by the invention 2 The nano medicine carrying system includes pesticide active component and mesoporous hollow SiO 2 A nano carrier, wherein the pesticide active component is loaded on the mesoporous hollow SiO 2 On a nano-carrier, the mesoporous hollow SiO 2 The surface of the nano carrier is modified with a pH response agent; wherein the active component of the pesticide is emamectin benzoate or novaluron.
Further, the pH response agent is chitosan, and the chitosan is connected to the mesoporous hollow SiO through the silicon-oxygen bond of the cross-linking agent under the acidic condition 2 The surface of the nano carrier, preferably the pH response agent is natural extract chitosan, the deacetylation degree is 98%, and the molecular weight is low.
Further, the cross-linking agent is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane.
Mesoporous hollow SiO based on pH response 2 The preparation method of the nano drug-loaded system comprises the step of preparing the mesoporous hollow SiO based on pH response 2 The method of the nano medicine carrying system includes the following steps:
s1, mesoporous hollow SiO 2 Preparation of nanocarriers
S101, dissolving a template agent and a silicon source into ammonia water, water and ethanol in a certain proportion, and synthesizing the silicon-containing composite material with uniform size at a certain time and temperatureMesoporous SiO 2 (ii) a Specifically, a spontaneous self-conversion method is adopted, a template agent and a silicon source are dissolved in ammonia water, water and ethanol with different proportions, and mesoporous SiO with uniform size is synthesized at proper time and temperature 2 ；
S102, taking water as an etching agent, and treating the mesoporous SiO in the step S101 2 Redispersed in 160mL of water, incubated for 48h, centrifuged, and washed with ethanol for 3 times to obtain mesoporous hollow SiO 2 A nano-carrier;
s103, dispersing the mesoporous hollow silica nano-carrier obtained in the step S102 in ethanol and concentrated hydrochloric acid, reacting for 3 hours at 60 ℃, washing for 3 times by using ethanol, and drying in vacuum to obtain mesoporous hollow SiO with uniform size and uniform aperture 2 A nano-carrier;
preferably, the mesoporous hollow SiO of the invention 2 The nano carrier is prepared by reacting undecyl trimethyl ammonium bromide and ethyl tetrasilicate in water, ethanol and ammonia water at a certain ratio at 35 deg.C for 24 hr, incubating in water at 70 deg.C with water as etching agent, removing template agent in ethanol and concentrated hydrochloric acid, centrifuging, washing with ethanol for three times to obtain white powdery solid, i.e. mesoporous hollow SiO 2 A nano-carrier.
S2, mesoporous hollow SiO 2 Preparation of nano drug-carrying system
Dissolving the active component of the pesticide in an ethanol solution, and then adding the mesoporous hollow SiO of the step S1 into the solution 2 Stirring the nano carrier for 6 hours under the condition of water bath at the temperature of 60 ℃, and carrying out vacuum freeze drying to obtain mesoporous hollow SiO 2 A nano drug-loaded system;
preferably, the mesoporous hollow SiO of the invention 2 Preferable mesoporous hollow SiO of nano drug-carrying system 2 Stirring with emamectin benzoate or novaluron in ethanol solution at room temperature for 14 hours, centrifuging to remove the solvent, and drying at 50 ℃ to obtain mesoporous hollow SiO 2 A nano drug-loaded system;
s3, mesoporous hollow SiO based on pH response 2 Preparation of nano drug-carrying system
Connecting the pH response agent to the mesoporous hollow SiO of the step S4 through the silicon-oxygen bond of the cross-linking agent under the acidic condition 2 The mesoporous hollow SiO based on pH response is obtained on the surface of a nano drug-loaded system 2 A nano drug-loading system.
Preferably, the pH-response-based mesoporous hollow SiO of the invention 2 Synthesis of nano drug-loaded system preferably selects chitosan and mesoporous hollow SiO 2 A nano medicine-carrying system is prepared through connecting 3- (2, 3-epoxypropoxy) propyl trimethoxy silane (GPTMS) as cross-linking agent by silicon-oxygen bond under acidic condition, reacting at room temp for 12 hr, centrifugal separation, washing with alcohol and water to obtain mesoporous hollow SiO based on pH response 2 A nano drug-loading system.
Further, an insecticide active component and the mesoporous hollow SiO 2 The concentration ratio of the nano-carrier is 2.
Further, the reaction conditions in step S3 are: reacting the pH response agent with the cross-linking agent at room temperature for 24 hours, and then reacting with mesoporous hollow SiO 2 The nano drug-loaded system reacts for 12 hours at room temperature, and then is centrifuged, washed by ethanol and washed by water to obtain mesoporous hollow SiO based on pH response 2 A nano drug-loading system.
Further, the mass ratio of the pH response agent to the cross-linking agent in the step S3 is 6.
Further, mesoporous hollow SiO 2 The average particle diameter of the nano-carrier is 100-200nm, and the average pore diameter is 2-4nm.
Mesoporous hollow SiO based on pH response 2 The application of a nano drug-carrying system is to use the mesoporous hollow SiO based on pH response 2 The nano drug-loading system is applied to the control of spodoptera frugiperda.
The invention has the beneficial effects that: mesoporous hollow SiO prepared in the invention 2 The nano-carrier has uniform particle size distribution, the pore size is distributed between 2 nm and 4nm, the nano-carrier has good drug loading capacity, and the drug loading rate is 45.3 percent; and under the acidic condition, the mesoporous hollow SiO modified by chitosan 2 The nano-carrier has a pH-responsive release effect.
Under alkaline conditions, the amino group of the chitosan is deprotonated and negatively charged, the emamectin benzoate selected in the invention is negatively charged, and the release rate is caused under alkaline conditions through the electrostatic repulsion between the chitosan and pesticide moleculesThe rate is fast, and the low molecular weight chitosan is easy to swell in an alkaline environment, so that the release of the pesticide is further promoted, and the pH-based responsive release of pesticide molecules is realized. The mesoporous hollow nano drug-loaded system has good blade adhesion and retention capacity through the modification of chitosan, so that the utilization rate of the drug is improved, and the loss can be reduced; simultaneously, under the condition of the same usage amount, based on pH response, the mesoporous hollow SiO 2 The nano drug-carrying system has higher insecticidal activity than that of the commercial insecticide, and particularly has higher insecticidal activity on phytophagous lepidoptera pests such as spodoptera frugiperda, and the pH value of the intestinal environment of the spodoptera frugiperda is 8-11.
Drawings
FIG. 1 is a diagram of mesoporous hollow SiO based on pH response in a preferred embodiment of the present invention 2 A flow chart of a preparation method of the nano drug-carrying system;
FIG. 2 is a diagram of mesoporous hollow SiO based on pH response in the preferred embodiment of the present invention 2 The specific surface area and the aperture distribution diagram of the nano drug-loading system;
FIG. 3 is a diagram of mesoporous hollow SiO based on pH response in a preferred embodiment of the present invention 2 Transmission electron microscope image of nano drug-loaded system;
FIG. 4 is a mesoporous hollow SiO based on pH response in the preferred embodiment of the present invention 2 A confocal microscope picture of the nano drug-loaded system and rhodamine 6G on corn leaves after washing;
FIG. 5 is a diagram of mesoporous hollow SiO based on pH response in a preferred embodiment of the present invention 2 The nano drug-carrying system has a curve diagram of the insect-resistant activity for killing Spodoptera frugiperda.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
The first embodiment is as follows:
(1) Mesoporous hollow SiO 2 Preparing a nano carrier:
the method adopts a spontaneous self-conversion method, firstly mesoporous silica with uniform size is synthesized, then water is used as an etching agent, the temperature and incubation time of the water are controlled, and the mesoporous hollow silica nano-carrier with uniform pores is synthesized.
Specifically, 0.336 g of hexadecyl trimethyl ammonium bromide is dissolved in 112mL of water under the ultrasonic action, 2mL of 28% ammonia water and 39mL of ethanol are added, the temperature is raised to 35 ℃, 2.23mL of ethyl tetrasilicate is rapidly added under vigorous stirring, stirring is continued for 24 hours under 35 ℃, and centrifugal ethanol washing is carried out for three times to obtain mesoporous SiO 2 。
The obtained mesoporous SiO 2 Redispersed in 160mL of water, incubated at 70 ℃ for 48h, stirred in 120mL of ethanol and 240. Mu.L of concentrated hydrochloric acid at 60 ℃ for 3h to further remove the template agent, and washed with centrifugal ethanol three times to obtain mesoporous hollow SiO 2 A nano-carrier;
(2) Mesoporous hollow SiO 2 Preparing a nano drug-loading system:
mixing 10mg/mL of emamectin benzoate or novaluron in ethanol with 60mg of mesoporous hollow SiO 2 Stirring at room temperature for 14h, centrifuging to remove solvent, and drying at 50 deg.C to obtain mesoporous hollow SiO 2 The nano drug-loading system has a drug-loading rate of 45.3%.
(3) Mesoporous hollow SiO based on pH response 2 Preparing a nano drug-loading system;
connecting chitosan to mesoporous hollow SiO by siloxane bond by using 3- (2, 3-epoxypropoxy) propyl trimethoxy silane (GPTMS) as cross-linking agent under acidic condition 2 Constructing mesoporous hollow SiO with pH responsiveness on the surface of the nano carrier 2 A nano drug-loading system.
Specifically, 1% (w/v) of chitosan is dissolved in 1% of acetic acid solution, 5% of GPTMS is dissolved in ethanol, a mixed solution of the chitosan and the GPTMS with the mass ratio of 6 2 The nano drug-loaded system reacts for 12 hours at room temperature, and is centrifuged, washed by ethanol and water to obtain pH response mesoporous hollow SiO 2 A nano drug-loading system.
The second concrete embodiment:
the difference between this embodiment and the first embodiment is: 60mg of mesopores in step 2Hollow SiO 2 Modified to 80mg mesoporous hollow SiO 2 Other conditions are the same. The obtained pH response mesoporous hollow SiO 2 The nano drug-loading system has the drug loading rate of 35.7 percent.
The third concrete embodiment:
the difference between this embodiment and the first embodiment is: 60mg of mesoporous hollow SiO in step 2 2 Changed into 100mg mesoporous hollow SiO 2 The other conditions are the same. The obtained pH response mesoporous hollow SiO 2 The nano drug-loading system has a drug loading rate of 23.3 percent.
Mesoporous hollow SiO based on pH response 2 Testing of Nanocarrier systems
1. Specific surface area, pore diameter, morphology and particle size test
A transmission electron microscope and a full-automatic physical adsorption instrument are adopted to represent the appearance, the grain diameter, the specific surface area and the pore diameter of the nano medicine-carrying system; as can be seen from FIG. 2, the specific surface area of the nano drug-loaded system is 795.9007m 2 The pore diameter is between 2 and 4 nm; under a transmission electron microscope, the nano drug-loaded system is spherical, has uniform particle size and clear mesoporous and hollow structures, and is shown in figure 3.
2. Mesoporous hollow SiO based on pH response 2 Retention diagram test of nano drug-loaded system and rhodamine 6G co-loaded on corn leaves after water washing
Selecting a fluorescence model drug rhodamine 6G, and loading the rhodamine G to the pH response mesoporous hollow SiO 2 In a nano drug-loaded system, obtaining the fluorescence-labeled pH response mesoporous hollow SiO 2 A nano drug-loading system. Then, the corn leaves are lightly washed with deionized water to remove dust on the surface. After air drying, the fluorescence labeled pH response mesoporous hollow SiO is 2 The nano drug-loaded system (400 mu L,4.0 mg/mL) is sprayed on the surface of a corn leaf, after the leaf is dried, the leaf is cleaned by deionized water (50 mL), air-dried and horizontally adhered on a glass slide, and then fluorescence of rhodamine 6G excited at the wavelength of 555nm by a confocal microscope and fluorescence of chlorophyll is excited at the wavelength of 630 nm. As shown in figure 4, after being washed by deionized water, the red fluorescent signal of rhodamine 6G can still be detected on the corn leaves, which indicates that the rhodamine 6G is improved after being modified by chitosanLeaf adhesion of the nano drug-loaded system.
3. Mesoporous hollow SiO based on pH response 2 Insect resistance activity test of nano drug-loaded system
Taking commercially available emamectin benzoate preparation as control, collecting fresh corn leaves not polluted by pesticide by leaf soaking method, soaking into pre-prepared 0.1mg/L pH response mesoporous hollow SiO 2 The nano medicine-carrying system liquid medicine is taken out for 10 seconds, naturally dried, put into a seasoning box, and a plurality of small holes are arranged on a cover for ventilation. 5 second-instar spodoptera frugiperda larvae are inoculated into the spodoptera frugiperda, the spodoptera frugiperda larvae are placed in an artificial climate chamber (25 +/-1 ℃, RH70% and 14L, 10D), meanwhile, blank controls are set, the number of test insect deaths is observed and recorded, and the rational mortality is calculated. As shown in FIG. 5, compared with commercially available emamectin benzoate emulsifiable concentrate, the pH-responsive mesoporous hollow SiO is obtained 2 The nano drug-loaded system has equivalent lethality 12 hours after being applied, which indicates that emamectin benzoate is loaded to mesoporous hollow SiO 2 The physicochemical property of emamectin benzoate is not changed in the nano carrier; but with the prolonging of time, the pH responds to the mesoporous hollow SiO 2 days after the drug is applied 2 The insecticidal activity of the nano drug-carrying system is superior to that of the commercially available emamectin benzoate emulsifiable solution, probably because the alkaline midgut microenvironment of the nano drug-carrying system is favorable for the rapid release of the insecticide after the nano drug-carrying system enters the bodies of spodoptera frugiperda, and the stomach toxicity effect is exerted, so that the killing effect on the spodoptera frugiperda is improved.
The above additional technical features can be freely combined and used in addition by those skilled in the art without conflict.
It is to be understood that the present invention has been described with reference to certain embodiments, and that various changes in the features and embodiments, or equivalent substitutions may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. Mesoporous hollow SiO based on pH response 2 The nano medicine carrying system is characterized in that: comprises an insecticide active component and mesoporous hollow SiO 2 Nano carrier, the active component of the pesticide is loaded on the mesoporous hollow SiO 2 On a nano-carrier, the mesoporous hollow SiO 2 The surface of the nano carrier is modified with a pH response agent; wherein the active component of the pesticide is emamectin benzoate or novaluron.
2. The pH-responsive mesoporous-based hollow SiO of claim 1 2 The nano medicine carrying system is characterized in that: the pH response agent is chitosan, and the chitosan is connected to mesoporous hollow SiO through silicon-oxygen bonds of a cross-linking agent under an acidic condition 2 The surface of the nanocarrier.
3. The pH-responsive mesoporous hollow SiO of claim 2 2 The nano medicine carrying system is characterized in that: the cross-linking agent is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane.
4. Mesoporous hollow SiO based on pH response 2 The preparation method of the nano drug-loaded system is characterized by comprising the following steps: preparation of the pH-responsive mesoporous-based hollow SiO of claims 1-3 2 The method of the nano medicine carrying system includes the following steps:
s1, mesoporous hollow SiO 2 Preparation of nanocarriers
S101, dissolving a template agent and a silicon source in ammonia water, water and ethanol according to a certain proportion, and synthesizing mesoporous SiO with uniform size at a certain time and temperature 2 ；
S102, taking water as an etching agent, re-dispersing the mesoporous silicon dioxide obtained in the step S101 in 160mL of water, incubating for 48h, centrifuging, washing with ethanol for 3 times to obtain mesoporous hollow SiO 2 A nano-carrier;
s103, dispersing the mesoporous hollow silica nano-carrier obtained in the step S102 in ethanol and concentrated hydrochloric acid, reacting for 3 hours at 60 ℃, washing for 3 times with ethanol, and drying in vacuum to obtain mesoporous hollow SiO with uniform size and uniform aperture 2 A nano-carrier;
s2, mesoporous hollow SiO 2 Preparation of nano drug-carrying system
Dissolving the active component of the pesticide in an ethanol solution, and then adding the mesoporous hollow SiO of the step S1 into the solution 2 Stirring the nano carrier for 6 hours under the condition of water bath at the temperature of 60 ℃, and carrying out vacuum freeze drying to obtain mesoporous hollow SiO 2 A nano drug-loaded system;
s3, mesoporous hollow SiO based on pH response 2 Preparation of nano drug-carrying system
Connecting the pH response agent to the mesoporous hollow SiO of the step S4 through the silicon-oxygen bond of the cross-linking agent under the acidic condition 2 The mesoporous hollow SiO based on pH response is obtained on the surface of a nano drug-carrying system 2 A nano drug-loading system.
5. The pH-responsive mesoporous-based hollow SiO of claim 4 2 The preparation method of the nano drug-carrying system is characterized by comprising the following steps: the reaction condition of the step S101 is that the reaction is carried out for 24 hours at 35 ℃.
6. The pH-responsive mesoporous hollow SiO of claim 4 2 The preparation method of the nano drug-carrying system is characterized by comprising the following steps: the pesticide active component and the mesoporous hollow SiO 2 The concentration ratio of the nano-carrier is 2.
7. The pH-responsive mesoporous-based hollow SiO of claim 4 2 The preparation method of the nano drug-carrying system is characterized by comprising the following steps: the reaction conditions in step S3 are: reacting the pH response agent with the cross-linking agent at room temperature for 24 hours, and then reacting with mesoporous hollow SiO 2 The nano drug-loaded system reacts for 12 hours at room temperature, and then is centrifuged, washed by ethanol and washed by water to obtain mesoporous hollow SiO based on pH response 2 A nano drug-loading system.
8. The pH-responsive mesoporous-based hollow SiO of claim 7 2 The preparation method of the nano drug-carrying system is characterized by comprising the following steps: the mass ratio of the pH response agent to the cross-linking agent in the step S3 is 6.
9. The pH-responsive mesoporous-based hollow SiO of claim 4 2 The preparation method of the nano drug-loaded system is characterized by comprising the following steps: the mesoporous hollow SiO 2 The average particle diameter of the nano-carrier is 100-200nm, and the average pore diameter is 2-4nm.
10. Mesoporous hollow SiO based on pH response 2 The application of the nano drug-carrying system is characterized in that: the pH-responsive mesoporous hollow SiO of any one of claims 1-3 2 The nano drug-carrying system is applied to the control of spodoptera frugiperda.
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