CN112262850A - PH-responsive pyraclostrobin controlled-release agent and preparation method and application thereof - Google Patents
PH-responsive pyraclostrobin controlled-release agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a pH response pyraclostrobin controlled release agent, a preparation method and application thereof, and amino functionalized mesoporous silica nanoparticle MSNs-NH2As a carrier material, the bactericide pyraclostrobin is loaded to MSNs-NH by a physical adsorption method2In the mesoporous pore canal of the nano particle, the coordination action of tannic acid TA and metal ions is utilized to carry medicine MSNs-NH2And depositing on the surfaces of the nanoparticles to form a metal-polyphenol network structure to block the mesopores, and preparing to obtain the pH response pyraclostrobin controlled release agent. The UV photolysis experiment result shows that the product has shielding pyridineThe pyraclostrobin performs the function of ultraviolet photolysis; the controlled release kinetics shows that the drug-loaded nano particles have different release performances under different pH conditions, have the same bacteriostatic activity as the original drug when diseases occur, and have good application prospect in the field of precision agriculture as novel agricultural bactericides.
Description
Technical Field
The invention belongs to the technical field of pesticide formulations, and particularly relates to a pH-responsive pyraclostrobin controlled release agent, and a preparation method and application thereof.
Background
Rice sheath blight disease (Rhizoctonia solani) is one of the most serious diseases of rice, and can cause 25-40% reduction of rice yield every year (Srivastava et al, 2016). At the early stage of the disease, the pathogenic bacteria of sheath blight of rice can secrete oxalic acid to make the sheath of the lower leaf of rice have water stain-like disease spots (Karmakar et al, 2016; Nagarajkumar et al, 2005). Oxalic acid, as an important pathogenic factor, can acidify host tissues to reduce the local pH of plants to about 4.5, is beneficial to enhancing the extracellular enzyme activity of pathogenic fungi, and accelerates the degradation of plant cell walls under the synergistic action of the oxalic acid and cell wall degrading enzymes to finally cause the diffusion and spread of diseases (Abdullah et al, 2017; Jinglan and Kangsheng, 2003).
Pyraclostrobin (PYR) is a strobilurin fungicide, has the characteristics of broad spectrum, low toxicity and high efficiency, can inhibit mitochondrial respiration of pathogenic bacteria, reduces ATP (adenosine triphosphate) generation of cells, and causes cell energy supply deficiency of the pathogenic bacteria to die (Kim and Xiao, 2011; Mercader et al, 2008). Currently, pyraclostrobin is widely used as a protective and therapeutic bactericide for preventing and treating a series of fungal diseases such as cucumber powdery mildew, wheat scab, sugarcane brown rust, rice sheath blight and sclerotinia sclerotiorum of rape (Chaulagain et al, 2019; Chen et al, 2012; He et al, 2019; Liang et al, 2014; Uppala and Zhou, 2018). However, the photolytic properties of pyraclostrobin have resulted in multiple sprays to ensure efficacy when applied in the field, which has greatly limited its practical utility (Fulcher et al, 2014). Therefore, there is an urgent need to create an effective method to improve the stability of pyraclostrobin and ensure an effective bioactive concentration at the target site.
Disclosure of Invention
The purpose is as follows: in order to overcome the defects in the prior art, the invention provides a pH response pyraclostrobin controlled release agent, a preparation method and application thereof, and amino functionalized mesoporous silica nanoparticles(MSNs-NH2) The pyraclostrobin controlled-release agent (PYR @ MSNs-TA-Cu) with pH response is prepared as a carrier material by utilizing the characteristic that tannic acid and metal ions can form a film on the surface of an object through coordinate bond deposition, the prepared carrier and preparation are characterized by means of Transmission Electron Microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), Zeta potential, nitrogen adsorption, thermogravimetric analysis (TGA) and the like, the influences of pyraclostrobin loading and pH value on pesticide slow-release kinetics are determined by utilizing HPLC, and the ultraviolet shielding performance, antibacterial activity and the like of the preparation are also evaluated.
Tannic Acid (TA), a natural phenolic compound, is widely present in plant secondary metabolites and plays multiple roles in plant defense. Meanwhile, the complex metal complex can be quickly coordinated with metal ions to form a polyphenol-metal complex shell layer, does not relate to a complex and toxic reaction process, and is a simple and green coating strategy. More importantly, the tannin-metal complex can generate the decomposition of coordinate bonds under the acidic condition and show the pH response performance. Therefore, the tannin-metal complex can be used as a shell layer to plug the medicine carrying pore canals of the MSNs.
The technical scheme is as follows: in order to solve the technical problems, the technical scheme adopted by the invention is as follows:
in a first aspect, a pH response pyraclostrobin controlled release agent is provided, and amino functionalized mesoporous silica nanoparticles MSNs-NH are used2As a carrier material, the bactericide pyraclostrobin is loaded to MSNs-NH by a physical adsorption method2In the mesoporous pore canal of the nano particle, the coordination action of tannic acid TA and metal ions is utilized to carry medicine MSNs-NH2And depositing on the surfaces of the nanoparticles to form a metal-polyphenol network structure to block the mesopores, and preparing to obtain the pH response pyraclostrobin controlled release agent.
The metal ions are copper ions, iron ions, aluminum ions, vanadium ions, chromium ions, manganese ions, cobalt ions, nickel ions, zinc ions, zirconium ions, molybdenum ions, ruthenium ions, rhodium ions, cadmium ions, cerium ions, europium ions, gadolinium ions or terbium ions.
In a second aspect, a preparation method of the pH-responsive pyraclostrobin controlled-release agent is provided, which comprises the following steps:
step a, modifying the surface of mesoporous silica nanoparticles MSNs by using 3-Aminopropyltriethoxysilane (APTES) to obtain amino-functionalized mesoporous silica nanoparticles MSNs-NH2；
B, taking amino functionalized mesoporous silica nanoparticles as a carrier, and loading bactericide pyraclostrobin by adopting a physical adsorption method to prepare medicine-loaded MSNs-NH2Nanoparticles (PYR @ MSNs-NH)2)；
Step c, preparing medicine-carrying MSNs-NH2Nanoparticles (PYR @ MSNs-NH)2) Adding tannic acid and metal ions, and coordinating with tannic acid TA and metal ions to carry medicine MSNs-NH2And forming a metal-polyphenol network structure on the surface of the nano particles to obtain the pH response pyraclostrobin controlled release agent.
In some embodiments, the step a specifically includes: dispersing MSNs in ethanol, adding APTES, continuously stirring at room temperature for reaction for a period of time (6-72h, preferably 24h), centrifuging to collect the product, washing with ethanol and water respectively, and vacuum drying to obtain MSNs-NH2Nanoparticles.
In the step a, the mass-to-volume ratio of the added mesoporous silica nanoparticles MSNs to the 3-aminopropyltriethoxysilane APTES is as follows: 400 μ L of APTES was added per 100mg of MSNs.
The step c comprises the following steps: loading MSNs-NH2Nanoparticles (PYR @ MSNs-NH)2) Dispersing in deionized water, adding tannic acid and metal ions, uniformly mixing, adding a Tris buffer solution to adjust the pH of the system to be alkaline, and washing with the deionized water to remove unreacted tannic acid and metal ions, thereby obtaining the pH response pyraclostrobin controlled release agent.
In the step c, the molar ratio of the tannic acid to the metal ions is 0.6-1.6, preferably 1.
The metal ions are copper ions, iron ions, aluminum ions, vanadium ions, chromium ions, manganese ions, cobalt ions, nickel ions, zinc ions, zirconium ions, molybdenum ions, ruthenium ions, rhodium ions, cadmium ions, cerium ions, europium ions, gadolinium ions or terbium ions, and more preferably, the metal ion reagent is copper chloride or ferric chloride.
The mesoporous silica nano particle MSNs can be purchased or manufactured by self, and the preparation method of the MSNs in the application comprises the following steps: the mesoporous silica nano particle MSNs are prepared under the alkaline condition by taking cetyl trimethyl ammonium bromide CTAB as a template, tetraethoxysilane TEOS as a silicon source and ethyl acetate as a morphology control agent of the mesoporous silica nano particle MSNs.
Further, the preparation method of the MSNs comprises the following specific steps: first, 0.35mL of aqueous sodium hydroxide (2M) was added to 50mL of deionized water containing 100mg of CATB, heated with stirring at 80 ℃ for 30min, and then 0.5mL of TEOS was added dropwise. After 1min, 0.5mL of ethyl acetate was added and the mixture was stirred for an additional 2 h. The precipitate was collected by centrifugation and washed several times with ethanol. To remove the surfactant CTAB in the pore channels, the obtained precipitate was dispersed in acidic ethanol (2mL HCl in 100mL ethanol), refluxed at 80 ℃ for 12h, and this process was repeated four times. Finally, the MSNs were collected by centrifugation, washed three times with ethanol and dried overnight under vacuum.
The pH-responsive pyraclostrobin controlled-release agent is prepared by the preparation method of the pH-responsive pyraclostrobin controlled-release agent.
In a third aspect, the application of the pH-responsive pyraclostrobin controlled-release agent in preparation of a drug for preventing and/or treating rice sheath blight is provided.
Has the advantages that: according to the pH-responsive pyraclostrobin controlled-release agent and the preparation method and application thereof, the prepared pH-responsive pyraclostrobin controlled-release agent is prepared by utilizing non-covalent bonding, and UV photolysis experiment results show that the product has the function of shielding pyraclostrobin ultraviolet photolysis; the controlled release kinetics shows that the drug-loaded nano particles have different release performances under different pH conditions, have the same bacteriostatic activity as the original drug when diseases occur, and have good application prospect in the field of target application as novel agricultural bactericide. Performing physicochemical characteristic characterization on the newly prepared MSNs-TA-Cu nanoparticles through TEM, XPS, EDX, FTIR, TGA, Zeta potential and nitrogen adsorption; selecting pyraclostrobin as a model drug, and determining the drug loading rate of PYR @ MSNs-TA-Cu nanoparticles; controlled release kinetics at different pH conditions; the stability of the drug-loaded nanoparticles under UV light irradiation is researched; the biological activity of the PYR @ MSNs-TA-Cu nanoparticles is measured by taking the pathogenic bacteria of the rice sheath blight as a target biological model, and the experimental result is as follows:
(1) the MSNs-NH is prepared by carrying out amination modification on the MSNs nano particles prepared by the base catalysis method by using APTES2The particles are prepared by loading pyraclostrobin serving as a bactericide by a physical adsorption method, and then forming metal-polyphenol network structure plugging mesopores on the surfaces of the MSNs through the strong coordination action of tannic acid and copper ions.
(2) The physical and chemical properties of the preparation process and the product are characterized by adopting methods and means such as TEM, TEM mapping, XPS, FTIR, Zeta potential analysis, BET, TGA, HPLC and the like, and the result shows that the metal-polyphenol network structure formed by tannic acid and copper ions is coated on MSNs-NH through coordination bond action2Nanoparticle surface, MSNs-NH2The specific surface area of the nanoparticles was 751.74m2The aperture is 2.95nm, and the effective component loading rate in the PYR @ MSNs-TA-Cu nano particles is 15.7 percent.
(3) The UV photolysis experiment result shows that the pyraclostrobin original drug can be completely photolyzed in 4 hours, and only 9.69% of effective components are decomposed after the PYR @ MSNs-TA-Cu nano particles are irradiated by UV light for 24 hours, so that the prepared carrier material has the effect of shielding the pyraclostrobin ultraviolet photolysis; the controlled release kinetics show that the drug-loaded nanoparticles have different release performances under different pH conditions, and when the pH is 7.4, only 8.54% of pyraclostrobin is released after 7 d; in an acid environment with the pH value of 6.0 and 4.5 respectively, the release amount of the pyraclostrobin after 7d is 37.02% and 82.48%, which shows that the PYR @ MSNs-TA-Cu nano particle has better pH response performance; general model Mt/Mz＝ktnSimulation results show that the values of the diffusion coefficients n are all less than 0.5, which indicates that the drug release in the nanoparticles is mainly controlled by diffusion.
(4) The biological activity experiment result shows that pyraclostrobin original drug and PYR @ MSNs-TA-Cu nanoparticles have the effect of treating pathogenic bacteria EC of rice sheath blight50Respectively at 0.391mg/L (95% confidence interval: 0.307-0.533 mg/L; r20.99) and 0.440mg/L (95% confidence interval: 0.347-0.592 mg/L; r is20.92), the two are not obviously different, which indicates that the drug-loaded nanoparticles have the same bacteriostatic activity as the original drug when the disease occurs. Therefore, the PYR @ MSNs-TA-Cu nano particles have a good application prospect in the field of precision agriculture as a novel agricultural bactericide.
Drawings
FIG. 1 is a preparation process of PYR @ MSNs-TA-Cu nanoparticles and a mechanism that pathogenic bacteria trigger the PYR @ MSNs-TA-Cu nanoparticles to release pyraclostrobin in the embodiment;
FIG. 2 shows MSNs-NH in the examples2TEM images of nanoparticles (A) and MSNs-TA-Cu nanoparticles (C), (B) and (D) are magnified images of (A) and (C);
FIG. 3 is a TEM mapping image (B-D) of MSNs-TA-Cu nanoparticles in example (scale: 50 nm);
FIG. 4 shows MSNs-NH in example2XPS survey spectra of nanoparticles (A) and MSNs-TA-Cu nanoparticles (B); MSNs-NH2EDX spectra of nanoparticles and MSNs-TA-Cu nanoparticles (C); MSNs and MSNs-NH2FTIR spectra (D) of nanoparticles and MSNs-TA-Cu nanoparticles;
FIG. 5 shows MSNs and MSNs-NH in the example2Nanoparticles and MSNs-TA-Cu nanoparticles Zeta potential (A), TGA curve (B), nitrogen adsorption-desorption isotherm (C) and BJH pore size (D);
FIG. 6 is a graph showing the effect of pH on the release of pyraclostrobin from PYR @ MSNs-TA-Cu nanoparticles in examples (A); stability results (B) of pyraclostrobin original drug and PYR @ MSNs-TA-Cu nanoparticles under UV irradiation;
FIG. 7 shows the antibacterial activity of pyraclostrobin prodrug and PYR @ MSNs-TA-Cu nanoparticles on Rhizoctonia solani in the examples;
FIG. 8 is a mechanism for preparing the pH-responsive pyraclostrobin controlled-release agent in the examples.
Detailed Description
The present invention will be further described with reference to the following drawings and specific examples, but the present invention is not limited to the following examples. If not stated otherwise, the experimental methods described in the invention are all conventional methods; the chemical reagents are all available from commercial sources.
Example (b):
1 materials and methods
1.1 reagents and materials
Pyraclostrobin bulk drug (97.5% pure) was purchased from basf european corporation (Limburgerhof, germany); cetyl Trimethyl Ammonium Bromide (CTAB), ethyl acetate, sodium hydroxide, tetraethyl orthosilicate (TEOS), Tannic Acid (TA), 3-Aminopropyltriethoxysilane (APTES), copper chloride, Tris (hydroxymethyl) aminomethane (Tris), hydrochloric acid, acetic acid, methanol and ethanol, all of analytical purity, purchased from the national pharmaceutical group chemical reagents beijing, ltd (beijing, china); chromatographic grade methanol was purchased from j.t.baker corporation (philips burg, usa); all experimental waters were Milli-Q water, purified from Milli-Q ultrapure water preparation system, Millipore Inc., USA (Billerica, USA).
1.2 preparation of PYR @ MSNs-TA-Cu nanoparticles
Synthesis of Mesoporous Silica Nanoparticles (MSNs): MSNs were prepared with slight modifications with reference to the method described by Lee et al (Lee et al, 2010). First, 0.35mL of aqueous sodium hydroxide (2M) was added to 50mL of deionized water containing 100mg of CATB, heated with stirring at 80 ℃ for 30min, and then 0.5mL of TEOS was added dropwise. After 1min, 0.5mL of ethyl acetate was added and the mixture was stirred for an additional 2 h. The precipitate was collected by centrifugation and washed several times with ethanol. To remove the surfactant CTAB in the pore channels, the obtained precipitate was dispersed in acidic ethanol (2mL HCl in 100mL ethanol), refluxed at 80 ℃ for 12h, and this process was repeated four times. Finally, the MSNs were collected by centrifugation, washed three times with ethanol and dried overnight under vacuum.
Amino functionalized mesoporous silica (MSNs-NH)2) And (3) synthesis of nanoparticles: 100mg of MSNs were dispersed in 20mL of ethanol, 400. mu.L of APTES was added and stirring was continued at room temperature for 24 h. Centrifuging to collect the product, washing with ethanol and water for three times, and vacuum drying to obtain MSNs-NH2Nanoparticles.
Synthesizing MSNs-TA-Cu nanoparticles: mixing 10mg MSN-NH2The nanoparticles were ultrasonically dispersed in 1mL of deionized water, 10. mu.L of tannic acid (24mM) and 10. mu.L of copper chloride (24mM) were added, respectively, and immediately mixed vigorously by a vortex shaker for 20s, and about 1mL of Tris buffer (pH 8.5, 0.05M) was added to adjust the pH of the system to alkaline. And washing with deionized water for multiple times to remove unreacted tannic acid and copper ions, and finally obtaining the MSNs-TA-Cu nano particles.
PYR @ MSNs-TA-Cu nanoparticles: adding 10mg of MSN-NH2Ultrasonically dispersing nano particles in 1mL of acetonitrile, adding 20mg of pyraclostrobin, keeping stirring for 24 hours in a dark place, and centrifugally collecting PYR @ MSNs-NH2Nanoparticles were dried in vacuo. Drying PYR @ MSNs-NH2The nanoparticles were dispersed in deionized water, and immediately after adding 10. mu.L of tannic acid (24mM) and 10. mu.L of copper chloride (24mM), respectively, they were vigorously mixed by a vortex shaker for 20s, and about 1mL of Tris buffer (pH 8.5, 0.05M) was added to adjust the pH of the system to alkaline. And washing with deionized water for multiple times to remove unreacted tannic acid and copper ions, and finally obtaining the PYR @ MSNs-TA-Cu nano particles.
1.3 Instrument characterization
The sample morphology and elemental composition were observed by a JEM-2100 Transmission Electron Microscope (TEM) (JEOL, Japan) equipped with an energy dispersive X-ray spectrometer (EDX) at an accelerating voltage of 200 kV. The chemical functionality on each sample was determined by Nexus 670 fourier transform spectrophotometer (FTIR) (Thermo-Fisher, usa) using KBr method. Sample X-ray photoelectron spectroscopy (XPS) was tested using Thermo ESCALAB 250Xi (Thermo-Fisher, USA). The change in sample weight during the temperature ramp from 25 to 800 deg.C (nitrogen atmosphere, ramp rate 10 deg.C/min) was monitored by an SDT-Q600 thermogravimetric analyzer (TA Instruments-Waters LLC, USA). The Zeta potential of the samples was measured using a Nano-zs90 Nanosizer (Malvern Instruments, UK). Samples were tested for nitrogen adsorption/desorption using a TriStar II 3020 specific surface area and porosity analyzer (Micromeritics Instrument Corporation, usa). The specific surface area and pore size of the samples were calculated using the Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH) theories, respectively. .
The content of effective components in the sample is determined by high performance liquid chromatograph (H) equipped with ultraviolet detectorPLC) (Shimadzu, japan). The chromatographic column is Kromasil ODS C18(250 mm. times.4.6 mm, 5 μm; Dikma, USA), the column temperature is room temperature, the UV detection wavelength is 275nm, the mobile phase consists of methanol and 0.1% acetic acid (80: 20, v/v), the flow rate is 1mL/min, and the sample volume is 20 μ L. All solvents and samples used for HPLC measurements were filtered through a 0.45 μm microfiltration membrane filter.
1.4 photolysis test
To evaluate the photostability of the samples, PYR @ MSNs-TA-Cu nanoparticles and pyraclostrobin bulk drug were dispersed in a methanol/water mixed system (30: 70, v/v), respectively. The dispersion was poured into a quartz tube and placed 20cm from an ultraviolet lamp at room temperature. Samples were collected at various times and filtered through a 0.45 μm microfiltration membrane filter. Pyraclostrobin content was analyzed by HPLC. Samples stored in the dark were used as a control. All treatments were repeated three times.
1.5 Release kinetics
The influence of the pH value on the release performance of pyraclostrobin on the PYR @ MSNs-TA-Cu nanoparticles is measured by an HPLC method. 1.5mL of PYR @ MSNs-TA-Cu nanoparticle dispersion (5mg/mL) was transferred into dialysis bags and immersed in methanol/water mixing system (30: 70, v/v) at different pH values (4.5, 7.0 and 7.4) with constant shaking and at different time intervals about 1mL of the mixture was aspirated each time with the same volume of methanol/water mixing solution (30: 70, v/v). Eight pyraclostrobin methanol solutions (0.1-200 mug/mL) with different concentrations are used for fitting a standard curve, and the release amount of pyraclostrobin is calculated, wherein the calculation formula is as follows:
wherein M istIs the total release amount of pyraclostrobin in the nanoparticles at time t; m0Is the initial nanoparticle loading. Further analyzing the release mechanism of pyraclostrobin in PYR @ MSNs-TA-Cu nanoparticles by a Ritger-peppas equation:
wherein M ist/MzRepresents the amount of released active ingredient at time t; k is a release rate constant which is mainly related to the properties of pyraclostrobin original drug and PYR @ MSNs-TA-Cu nanoparticles; n is the diffusion index of the pesticide release mechanism. For spherical samples, Fickian diffusion is performed when n is less than or equal to 0.5, 0.5<n<0.89, non-Fickian or abnormal diffusion; n.gtoreq.0.89 is skeleton corrosion (Cao et al, 2005).
1.6 antibacterial Activity
The toxicity of pyraclostrobin original drug and PYR @ MSNs-TA-Cu nanoparticles to Rhizoctonia solani is measured by a growth rate method. PDA culture medium (0.016, 0.032, 0.064, 0.125, 0.25 and 0.5 mu g/mL calculated by concentration of pyraclostrobin original drug) containing pyraclostrobin original drug and PYR @ MSNs-TA-Cu nanoparticles with different concentrations is prepared by a gradient dilution method. Clear water and MSNs-TA-Cu nanoparticles without medicine are respectively set as controls. Pouring the above culture medium containing medicine into sterilized petri dish (diameter of 9cm), cooling and solidifying the culture medium, inoculating fungus cake with diameter of 5mm, and culturing at 28 deg.C for 72 hr. Three replicates were set for each treatment. The diameter of the colonies was measured using the cross method, and the percentage of inhibition of hyphal growth was calculated by the following formula:
1.7 data analysis
All statistical analyses used SPSS 23.0 statistical analysis software. Calculating confidence interval, correlation coefficient and antibacterial concentration (EC) of pyraclostrobin preparation by probability analysis50). By Duncan test (p)<0.05) data were analyzed and expressed as mean ± standard error of the mean (SEM) of all experiments.
2 results and discussion
2.1 preparation and characterization of MSNs-TA-Cu nanoparticles
The present study prepared a novel pH-responsive pyraclostrobin controlled-release agent, whichThe detailed preparation process is shown in figure 1. Firstly, preparing MSNs under an alkaline condition by taking CTAB as a template, TEOS as a silicon source and ethyl acetate as an MSNs morphology control agent, and then modifying the MSNs surface by using APTES to obtain MSNs-NH2And (3) adding copper chloride and tannic acid into the nano particles in sequence, and forming a metal-polyphenol network structure (MSNs-TA-Cu nano particles) on the surfaces of the MSNs through strong coordination of the copper chloride and the tannic acid.
As shown in FIG. 2, MSNs-NH2TEM images of nanoparticles (A) and MSNs-TA-Cu nanoparticles (C), (B) and (D) are magnified images of (A) and (C), and MSNs-NH prepared2The nano particles present a spherical shape with relatively uniform size, the average particle diameter is 130.4 +/-6.7 nm, and the MSNs-NH2The nano-particle magnified TEM image shows that the pore channel of the nano-particle has an ordered hexagonal pore channel structure and penetrates through the whole sphere; through non-covalent bond on MSNs-NH2After the surface of the nanoparticle is coated with a tannic acid-copper complex shell layer, the mesoporous pore canal can be observed to be blurred, which indicates that the MSNs-TA-Cu nanoparticles are successfully prepared (C and D in figure 2).
TEM mapping showed the presence of Si, C, O, N and Cu elements in the MSNs-TA-Cu nanoparticles and a spherical distribution, indicating successful modification of amino groups and coating of tannin-copper complexes on the MSNs (FIG. 3). The samples were further analyzed for XPS, EDX and FTIR spectra (FIG. 4: MSNs-NH)2XPS survey spectra of nanoparticles (A) and MSNs-TA-Cu nanoparticles (B); MSNs-NH2EDX spectra of nanoparticles and MSNs-TA-Cu nanoparticles (C); MSNs and MSNs-NH2FTIR spectra (D)) of nanoparticles and MSNs-TA-Cu nanoparticles. The XPS spectral analysis result shows that the MSN-NH2Both nanoparticles and MSNs-TA-Cu nanoparticles present typical peaks for O1s (532.79eV), N1 s (399.94eV), C1 s (285.02eV), and Si 2p (103.25eV) (A and B in FIG. 4); with MSN-NH2In contrast to the nanoparticles, a new peak attributed to Cu 2p appeared at 933.74eV, indicating that the tannic acid-copper complex had successfully coated the MSNs surface (B in fig. 4) (Park et al, 2017). The formation of the tannin-copper complex was also confirmed by the Cu element peak present in the MSNs-TA-Cu nanoparticles in the EDX spectrum (C in FIG. 4). As shown in D in FIG. 4, MSNs are at 466, 796 and 1090cm-1Having strong characteristic absorption attributed to-Si-O-Si bondsA peak; after reaction with APTES, 1556cm-1Has a weak absorption peak of-NH newly appeared, and is 3441cm-1The characteristic peak belonging to-OH is weakened, and the formation of MSNs-NH is proved2Nanoparticles (Fan et al, 2019); in MSN-NH21400-1600cm after formation of tannin-copper complex on the surface-1A series of small peaks appear between the two, which belong to stretching of aromatic compounds in the tannic acid and vibration of substituted benzene rings, and indicate that the tannic acid-copper complex is successfully deposited on the MSN-NH2On the surface of the nanoparticles, MSNs-TA-Cu nanoparticles were formed (Yao et al, 2016).
The change in Zeta potential also demonstrates the formation of tannic acid-copper on the surface of MSNs. As shown in A in FIG. 5, the Zeta potential of MSNs is-27.3 mV; amino modified MSNs-NH2The potential is sharply inverted to +12.8 mV; deposition of tannin-copper on MSN-NH2On the surface of the nanoparticles, the potential was again lowered to-18.4 mV due to the strong negative charge of tannic acid. When the temperature rises to 800 ℃ as shown by B in FIG. 5, MSNs-NH2The nanoparticle and MSNs-TA-Cu nanoparticle weight losses were 8.39%, 14.20%, and 19.14%, respectively. The surface amino modification amount of MSNs is 5.81%, and the tannin-copper deposition amount is 4.94%. Changes of BET specific surface area and BJH pore size distribution in the processes of MSNs surface modification and tannin-copper surface deposition are monitored through a nitrogen adsorption-desorption isotherm. As shown by C, D in FIG. 5 and Table 1, MSNs-NH were deposited in the MSNs pore channels due to APTES modification2The specific surface area of the nano particles is 751.74m of MSNs2The/g is reduced to 658.17m2Per g, pore volume from 0.61m3The/g is reduced to 0.52m3The pore diameter is reduced from 2.95nm to 2.70nm, but the MSNs and the MSNs-NH2The adsorption isotherms of the nanoparticles all accord with IV-type characteristics in IUPAC classification, and the nanoparticles all have mesoporous structures; MSNs-NH2After tannin-copper is deposited on the surfaces of the nano particles, the BET surface area of the MSNs-TA-Cu nano particles is sharply reduced to 163m2Per g, the pore volume is reduced to 0.13m3The/g is accompanied by the disappearance of mesoporous pore canals, which shows that the MSNs are completely blocked by the tannin-copper.
TABLE 1 sample BET and BJH determination
N/A＝Not Applicable
2.2 pesticide Loading Rate and Release kinetics
The PYR @ MSNs-TA-Cu nano particles have the effective component loading rate of 15.7 percent through HPLC measurement. The mechanism of the PYR @ MSNs-TA-Cu nano particles for blocking and releasing the active ingredients is shown in figure 1. Pyraclostrobin is loaded to MSNs-NH through physical adsorption2In the mesoporous pore canal of the nano particles, tannic acid and copper ions are complexed and deposited on the drug-loaded MSNs-NH2Blocked PYR @ MSNs-TA-Cu nanoparticles are formed on the surfaces of the nanoparticles. When the pathogenic bacteria infect plants to secrete oxalic acid, the partial pH is reduced, and the PYR @ MSNs-TA-Cu nano particle surface metal complex is decomposed under an acidic condition and then opens the pore channel, so that the pyraclostrobin is diffused and released from the pore channel, and the development and spread of the pathogenic bacteria are effectively controlled.
TABLE 2 use of the general model Mt/Mz＝ktnAnalyzing data of pyraclostrobin released by PYR @ MSNs-TA-Cu nanoparticles with different pH values
| pH values | n | K | r2 | T50(d) |
| 4.5 | 0.28 | 0.54 | 0.9374 | 0.8 |
| 6.0 | 0.38 | 0.22 | 0.9034 | 8.5 |
| 7.4 | 0.42 | 0.04 | 0.9662 | 382.5 |
As shown in a in fig. 6, the cumulative release rates of pyraclostrobin after 7d were 37.02% and 82.48% when the pH was 6.0 and 4.5, respectively; and at a pH of 7.4, only 8.54% of the pyraclostrobin was released from the PYR @ MSNs-TA-Cu nanoparticles. The faster release rate of the agent under acidic conditions may be due to the tannin-copper complex shell on the surface of MSNs decomposing under acidic conditions, opening the plugged mesoporous channels (Guo et al, 2019). Using a general model Mt/Mz＝ktnThe resulting sustained release data was further fitted. The result shows that the release curve of the pyraclostrobin in the nanoparticles has good correlation (r) with the fitting equation2>0.90). As the pH value is reduced from 7.4 to 4.5, the n value is reduced from 0.42 to 0.28, and all n values are less than 0.5, which indicates that the release of the effective components in the PYR @ MSNs-TA-Cu nanoparticles is mainly Fickian diffusion under different pH conditions. The time (T) required for 50% of the active ingredient to be released is further calculated50) (Table 2). In pH 4.5 buffer, T50The value is 0.8d, and when the pH is 7.4, T50The value is 382.5d, which is obviously higher than that under the acidic condition, and the PYR @ MSNs-TA-Cu nano particles have better pH response performance.
2.3 photostability of PYR @ MSNs-TA-Cu nanoparticles
As shown in fig. 6B, under UV irradiation, the photolysis rate of pyraclostrobin original drug is faster, and the active ingredient is completely decomposed after 4h irradiation; the photolysis rate of the PYR @ MSNs-TA-Cu nanoparticles is remarkably lower than that of pyraclostrobin original drug, and the effective ingredients are only degraded by 9.69% after the ultraviolet light irradiation is carried out for 24 hours. In both cases, no decomposition of pyraclostrobin was detected in the dark. Photolysis experiment results show that the PYR @ MSNs-TA-Cu nanoparticles have the function of shielding ultraviolet photolysis of pyraclostrobin, and the mesoporous silica nanoparticles have the capacity of absorbing or reflecting ultraviolet rays, so that system energy is reduced, and the light stability of the pyraclostrobin is improved (Gao et al, 2014; Li et al, 2006).
TABLE 3 Effect of pyraclostrobin bulk drug and PYR @ MSNs-TA-Cu nanoparticles on Rhizoctonia solani hypha growth
Data are shown as mean ± SEM (n ═ 3); lower case letters in the same column indicate significant differences between control and treatment (p <0.05)
2.4 antibacterial Activity
FIG. 7 and Table 3 show the activity of pyraclostrobin prodrug and PYR @ MSNs-TA-Cu nanoparticles on Rhizoctonia solani at different concentrations. The result of the hypha growth rate in the drug-containing culture medium shows that the original drug and the nano particles both have typical dose-dependent characteristics; pyraclostrobin original drug and PYR @ MSNs-TA-Cu nanoparticle EC50The values are 0.391mg/L (95% confidence interval: 0.307-0.533 mg/L; r20.99) and 0.440mg/L (95% confidence interval: 0.347-0.592 mg/L; r is20.92), the growth inhibition rates of the hyphae of the two bacteria are not obviously different, which is mainly because the hyphae of pathogenic bacteria can secrete oxalic acid at the infection point part at the initial occurrence stage of the disease, so that the local pH is reduced to be below 4.5, which is favorable for the decomposition of the metal complex blocked on the surfaces of the PYR @ MSNs-TA-Cu nanoparticles, and the blocked medicine is released from pore channels.
5.4 nodules
The study utilized non-covalent bonding to prepare the pH-responsive pyraclostrobin controlled release agent. Performing physicochemical characteristic characterization on the newly prepared MSNs-TA-Cu nanoparticles through TEM, XPS, EDX, FTIR, TGA, Zeta potential and nitrogen adsorption; selecting pyraclostrobin as a model drug, and determining the drug loading rate of PYR @ MSNs-TA-Cu nanoparticles; controlled release kinetics at different pH conditions; the stability of the drug-loaded nanoparticles under UV light irradiation is researched; the biological activity of the PYR @ MSNs-TA-Cu nanoparticles is measured by taking the pathogenic bacteria of the rice sheath blight as a target biological model, and the experimental result is as follows:
(1) the MSNs-NH is prepared by carrying out amination modification on the MSNs nano particles prepared by the base catalysis method by using APTES2The particles are prepared by loading pyraclostrobin serving as a bactericide by a physical adsorption method, forming metal-polyphenol network structure plugging mesopores on the surfaces of MSNs by the strong coordination action of tannic acid and copper ions, and the preparation mechanism is shown in figure 8.
(2) The physical and chemical properties of the preparation process and the product are characterized by adopting methods and means such as TEM, TEM mapping, XPS, FTIR, Zeta potential analysis, BET, TGA, HPLC and the like, and the result shows that the metal-polyphenol network structure formed by tannic acid and copper ions is coated on MSNs-NH through coordination bond action2Nanoparticle surface, MSNs-NH2The specific surface area of the nanoparticles was 751.74m2The aperture is 2.95nm, and the effective component loading rate in the PYR @ MSNs-TA-Cu nano particles is 15.7 percent.
(3) The UV photolysis experiment result shows that the pyraclostrobin original drug can be completely photolyzed in 4 hours, and only 9.69% of effective components are decomposed after the PYR @ MSNs-TA-Cu nano particles are irradiated by UV light for 24 hours, so that the prepared carrier material has the effect of shielding the pyraclostrobin ultraviolet photolysis; the controlled release kinetics show that the drug-loaded nanoparticles have different release performances under different pH conditions, and when the pH is 7.4, only 8.54% of pyraclostrobin is released after 7 d; in an acid environment with the pH value of 6.0 and 4.5 respectively, the release amount of the pyraclostrobin after 7d is 37.02% and 82.48%, which shows that the PYR @ MSNs-TA-Cu nano particle has better pH response performance; general model Mt/Mz＝ktnSimulation result tableThe values of the bright diffusion coefficients n are all less than 0.5, which indicates that the drug release in the nanoparticles is mainly controlled by diffusion.
(4) The biological activity experiment result shows that pyraclostrobin original drug and PYR @ MSNs-TA-Cu nanoparticles have the effect of treating pathogenic bacteria EC of rice sheath blight50Respectively at 0.391mg/L (95% confidence interval: 0.307-0.533 mg/L; r20.99) and 0.440mg/L (95% confidence interval: 0.347-0.592 mg/L; r is20.92), the two are not obviously different, which indicates that the drug-loaded nanoparticles have the same bacteriostatic activity as the original drug when the disease occurs. Therefore, the PYR @ MSNs-TA-Cu nano particles have good application prospect in the field of target application as a novel agricultural bactericide.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. The pH response pyraclostrobin controlled release agent is characterized in that amino functionalized mesoporous silica nanoparticles MSNs-NH2As a carrier material, the bactericide pyraclostrobin is loaded to MSNs-NH by a physical adsorption method2In the mesoporous pore canal of the nano particle, the coordination action of tannic acid TA and metal ions is utilized to carry medicine MSNs-NH2And depositing on the surfaces of the nanoparticles to form a metal-polyphenol network structure to block the mesopores, and preparing to obtain the pH response pyraclostrobin controlled release agent.
2. A preparation method of a pH response pyraclostrobin controlled release agent is characterized by comprising the following steps:
step a, modifying the surface of mesoporous silica nanoparticles MSNs by using 3-Aminopropyltriethoxysilane (APTES) to obtain amino-functionalized mesoporous silica nanoparticles MSNs-NH2；
B, taking amino functionalized mesoporous silica nanoparticles as a carrier, and loading bactericide pyraclostrobin by adopting a physical adsorption method to prepare medicine-loaded MSNs-NH2Nano particleA seed;
step c, preparing medicine-carrying MSNs-NH2Tannic acid and metal ions are added into the nano particles, and the coordination effect of tannic acid TA and the metal ions is utilized to carry medicine MSNs-NH2And forming a metal-polyphenol network structure on the surface of the nano particles to obtain the pH response pyraclostrobin controlled release agent.
3. The method for preparing the pH-responsive pyraclostrobin controlled-release agent according to claim 2, wherein the step a comprises: dispersing MSNs in ethanol, adding APTES, continuously stirring at room temperature for reaction for a period of time, centrifuging to collect products, washing with ethanol and water respectively, and vacuum drying to obtain MSNs-NH2Nanoparticles.
4. The preparation method of the pH-responsive pyraclostrobin controlled-release agent according to claim 3, wherein in the step a, the mass-to-volume ratio of the added mesoporous silica nanoparticle MSNs to the 3-aminopropyltriethoxysilane APTES is as follows: 100-1000. mu.L of APTES, preferably 400. mu.L of APTES, are added per 100mg of MSNs.
5. The method for preparing the pH-responsive pyraclostrobin controlled-release formulation according to claim 2, wherein the step c comprises: loading MSNs-NH2Dispersing the nanoparticles in deionized water, adding tannic acid and metal ions, uniformly mixing, adding a Tris buffer solution to adjust the pH of the system to be alkaline, and washing with the deionized water to remove unreacted tannic acid and metal ions to obtain the pH response pyraclostrobin controlled release agent.
6. The preparation method of the pH-responsive pyraclostrobin controlled-release agent according to claim 2 or 5, wherein the metal ion is copper ion, iron ion, aluminum ion, vanadium ion, chromium ion, manganese ion, cobalt ion, nickel ion, zinc ion, zirconium ion, molybdenum ion, ruthenium ion, rhodium ion, cadmium ion, cerium ion, europium ion, gadolinium ion or terbium ion, and more preferably the metal ion reagent is copper chloride or iron chloride.
7. The method for preparing the pH-responsive pyraclostrobin controlled-release agent according to claim 2 or 5, wherein the molar ratio of the tannic acid to the metal ions added in the step c is 0.6 to 1.6, preferably 1.
8. The preparation method of the pH-responsive pyraclostrobin controlled-release agent according to claim 2, wherein the preparation method of the mesoporous silica nanoparticle MSNs comprises the following steps: the mesoporous silica nano particle MSNs are prepared under the alkaline condition by taking cetyl trimethyl ammonium bromide CTAB as a template, tetraethoxysilane TEOS as a silicon source and ethyl acetate as a morphology control agent of the mesoporous silica nano particle MSNs.
9. A pH-responsive pyraclostrobin controlled-release agent, characterized by being prepared by the preparation method of the pH-responsive pyraclostrobin controlled-release agent of any one of claims 2 to 8.
10. Use of the pH-responsive pyraclostrobin controlled-release formulation as claimed in claims 1 and 9 in the manufacture of a medicament for the prevention and/or treatment of rice sheath blight disease.
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