CN117256624A - Silicon dioxide-zinc oxide quantum dot-salicylic acid composite material and preparation method and application thereof - Google Patents
Silicon dioxide-zinc oxide quantum dot-salicylic acid composite material and preparation method and application thereof Download PDFInfo
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- CN117256624A CN117256624A CN202311337364.4A CN202311337364A CN117256624A CN 117256624 A CN117256624 A CN 117256624A CN 202311337364 A CN202311337364 A CN 202311337364A CN 117256624 A CN117256624 A CN 117256624A
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- zinc oxide
- quantum dot
- oxide quantum
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- salicylic acid
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- 229960004889 salicylic acid Drugs 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- MPLOKIFXJVNKGW-UHFFFAOYSA-N [O-2].[Zn+2].[Si](=O)=O Chemical compound [O-2].[Zn+2].[Si](=O)=O MPLOKIFXJVNKGW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 113
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011787 zinc oxide Substances 0.000 claims abstract description 54
- 239000002096 quantum dot Substances 0.000 claims abstract description 51
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 claims abstract description 28
- ZAJSWGDRWVXLES-UHFFFAOYSA-N [O-2].N[Zn+2] Chemical compound [O-2].N[Zn+2] ZAJSWGDRWVXLES-UHFFFAOYSA-N 0.000 claims abstract description 23
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- 230000008878 coupling Effects 0.000 claims description 13
- 238000010168 coupling process Methods 0.000 claims description 13
- 238000005859 coupling reaction Methods 0.000 claims description 13
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000005576 amination reaction Methods 0.000 claims description 9
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 8
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
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- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims 2
- 208000035240 Disease Resistance Diseases 0.000 abstract description 6
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- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 36
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- 230000000694 effects Effects 0.000 description 23
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 10
- 102000003992 Peroxidases Human genes 0.000 description 10
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- 238000009777 vacuum freeze-drying Methods 0.000 description 10
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 9
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- 239000011701 zinc Substances 0.000 description 9
- 229930002875 chlorophyll Natural products 0.000 description 8
- 235000019804 chlorophyll Nutrition 0.000 description 8
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910017976 MgO 4 Inorganic materials 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 208000015181 infectious disease Diseases 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 208000024891 symptom Diseases 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QSQFARNGNIZGAW-UHFFFAOYSA-N 2-methylsulfonyloxyethyl methanesulfonate Chemical compound CS(=O)(=O)OCCOS(C)(=O)=O QSQFARNGNIZGAW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
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- 239000000725 suspension Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 241000353135 Psenopsis anomala Species 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
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- 238000011068 loading method Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 240000008027 Akebia quinata Species 0.000 description 1
- 235000007756 Akebia quinata Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920000018 Callose Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 230000011664 signaling Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
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- -1 zinc amino oxide Chemical compound 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P21/00—Plant growth regulators
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention belongs to the technical field of zinc oxide quantum dots, and particularly relates to a silicon dioxide-zinc oxide quantum dot-salicylic acid composite material, and a preparation method and application thereof. The invention provides a silicon dioxide-zinc oxide quantum dot-salicylic acid composite material, which comprises silicon dioxide nano particles and zinc oxide quantum dot conjugate coated on the surfaces of the silicon dioxide nano particles; the zinc oxide quantum dot conjugate comprises an amino zinc oxide quantum dot and salicylic acid coupled with the amino zinc oxide quantum dot. The salicylic acid in the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material provided by the invention can directly enter the inside of plants, so that the toxic effect caused by externally applying the salicylic acid is relieved, and the disease resistance of the plants is improved.
Description
Technical Field
The invention belongs to the technical field of zinc oxide quantum dots, and particularly relates to a silicon dioxide-zinc oxide quantum dot-salicylic acid composite material, and a preparation method and application thereof.
Background
Salicylic acid is one of the endogenous hormone signaling molecules necessary for plant allergic necrosis and systemic acquired resistance, and its external application has been demonstrated to activate the natural defenses of the plant itself against pathogenic bacteria, enhancing the level of resistance of the plant to pathogenic bacteria. However, foliar application of high concentrations of salicylic acid severely affects the growth and development of plants.
In recent years, embedding an agrochemical in a polymer macromolecule has attracted attention from the scholars because it can prevent the active substance from being directly exposed to the environment. However, the traditional pesticide microcapsule has the defects of overlarge volume and small surface, once the surface packaging is broken, the internal medicine is lost once, and the active ingredients cannot be released as required, so that an effective strategy is developed to relieve the toxic effect of salicylic acid on plants and release the salicylic acid into the plants to improve the disease resistance of the plants, and the development of an effective strategy is of great importance.
Disclosure of Invention
In view of the above, the invention provides a silicon dioxide-zinc oxide quantum dot-salicylic acid composite material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a silicon dioxide-zinc oxide quantum dot-salicylic acid composite material, which comprises silicon dioxide nano particles and zinc oxide quantum dot conjugates coated on the surfaces of the silicon dioxide nano particles; the zinc oxide quantum dot conjugate comprises an amino zinc oxide quantum dot and salicylic acid coupled with the amino zinc oxide quantum dot.
Preferably, the mass ratio of the amino zinc oxide quantum dot to the salicylic acid is 1.5-2: 1.
preferably, the mass ratio of the zinc oxide quantum dot conjugate to the silica nanoparticle is 10: 15-25.
The invention also provides a preparation method of the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material, which comprises the following steps:
(1) Dispersing zinc oxide quantum dots and 3-aminopropyl trimethoxy silane in N, N-dimethylformamide, and amination to obtain amino zinc oxide quantum dots;
(2) Dispersing the amino zinc oxide quantum dot, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, N-hydroxysuccinimide and salicylic acid in N, N-dimethylformamide, and performing coupling to obtain a zinc oxide quantum dot conjugate;
mixing and coating the dispersion liquid of the silicon dioxide nano particles and the zinc oxide quantum dot conjugate under alkaline conditions to obtain the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material; the pH value of the alkaline condition is 7.2-7.5.
Preferably, the amination temperature is 110-150 ℃ and the time is 12-18 min.
Preferably, the temperature of the coupling is 20-30 ℃ and the time is 18-30 h.
Preferably, in the step (1), the dosage ratio of the zinc oxide quantum dots to the 3-aminopropyl trimethoxysilane is 0.8-1.2 mg:1 mul.
Preferably, in the step (2), the mass ratio of the amino zinc oxide quantum dot to the 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide to the n-hydroxysuccinimide to the salicylic acid is 200: 170-175: 130 to 135:100.
the invention also provides an application of the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material or the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material prepared by the preparation method in inhibiting plant pathogenic bacteria.
Preferably, the phytopathogen is a. Citrulli.
The invention provides a silicon dioxide-zinc oxide quantum dot-salicylic acid composite material, which comprises silicon dioxide nano particles and zinc oxide quantum dot conjugates coated on the surfaces of the silicon dioxide nano particles; the zinc oxide quantum dot conjugate comprises an amino zinc oxide quantum dot and salicylic acid coupled with the amino zinc oxide quantum dot. The salicylic acid in the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material provided by the invention can directly enter the inside of plants, the silicon dioxide nano particles and the zinc oxide quantum dots can play a role in bacteriostasis, and the salicylic acid can activate the resistance of the plants. The salicylic acid is coupled by an amide bond, and can be released according to pH, and the plant is acid after being infected by pathogenic bacteria, at the moment, the amide bond is partially broken, and the salicylic acid is slowly released, so that the toxic effect caused by externally applying the salicylic acid is relieved, and the disease resistance of the plant is improved.
Drawings
FIG. 1 shows ZnO QDs, znO-NH of example 1 2 ZnO-SA and SiO 2 HRTEM diagram of @ ZnO-SA;
FIG. 2 is a diagram of ZnO QDs, znO-NH of example 1 2 ZnO-SA and SiO 2 FTIR spectrum of @ ZnO-SA;
FIG. 3 is SiO of example 1 2 NPs and SiO 2 XRD spectrum of @ ZnO-SA;
FIG. 4 shows ZnO QDs, znO-NH of example 1 2 ZnO-SA and SiO 2 Ultraviolet-visible light absorption spectrum of @ ZnO-SA;
FIG. 5 is ZnO-NH of example 1 2 Wherein A is ZnO-NH 2 Is a full spectrum of (3);
FIG. 6 shows XPS spectrum A of ZnO-SA as a full spectrum of ZnO-SA;
FIG. 7 is SiO 2 XPS spectrum of @ ZnO-SA;
FIG. 8 is a three-dimensional fluorescence spectrum of SA and ZnO QDs;
FIG. 9 is ZnO-NH 2 ZnO-SA and SiO 2 Three-dimensional fluorescence spectrogram of @ ZnO-SA, wherein A is ZnO-NH 2 Is a three-dimensional fluorescence spectrum of (2);
FIG. 10 shows SA, znO-NH concentrations 2 ZnO-SA and SiO 2 A growth curve of pathogenic bacteria after being treated by the @ ZnO-SA;
FIG. 11 shows ZnO-NH at various concentrations 2 ZnO-SA and SiO 2 Colony images after 36h of pathogen cells are treated by @ ZnO-SA;
FIG. 12 is ZnO-NH 2 ZnO-SA and SiO 2 Antibacterial rate of @ ZnO-SA on pathogenic bacteria;
FIG. 13 shows foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 Change plot of plant image after @ ZnO-SA;
FIG. 14 shows foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 A graph of change in area under disease development curve (AUDPC value) after @ ZnO-SA;
FIG. 15 shows foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 Graph of total chlorophyll content (SPAD value) after @ ZnO-SA;
FIG. 16 shows foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 A change chart of root length, stem length, root fresh weight and stem fresh weight after @ ZnO-SA;
FIG. 17 foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 Change patterns of MDA content, CAT activity, POD activity and SOD activity after @ ZnO-SA;
FIG. 18 shows foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 Graph of change in Zn, fe, ca, mg and Mn nutrient content in aerial parts of melon seedlings after @ ZnO-SA.
Detailed Description
The invention provides a silicon dioxide-zinc oxide quantum dot-salicylic acid composite material, which comprises silicon dioxide nano particles and zinc oxide quantum dot conjugates coated on the surfaces of the silicon dioxide nano particles; the zinc oxide quantum dot conjugate comprises an amino zinc oxide quantum dot and salicylic acid coupled with the amino zinc oxide quantum dot.
In the present invention, the size of the silica nanoparticle is preferably 50 to 200nm, more preferably 50nm. In the invention, the mass ratio of the amino zinc oxide quantum dot to the salicylic acid is preferably 1.5-2: 1, more preferably 1.7 to 1.8:1. in the invention, the mass ratio of the zinc oxide quantum dot conjugate to the silicon dioxide nanoparticle is preferably 10:15 to 25, more preferably 1:2.
the invention also provides a preparation method of the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material, which comprises the following steps:
(1) Dispersing zinc oxide quantum dots and 3-aminopropyl trimethoxy silane in N, N-dimethylformamide, and amination to obtain amino zinc oxide quantum dots;
(2) Dispersing the amino zinc oxide quantum dot, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, N-hydroxysuccinimide and salicylic acid in N, N-dimethylformamide, and performing coupling to obtain a zinc oxide quantum dot conjugate;
(3) Mixing the dispersion liquid of the silicon dioxide nano particles and the zinc oxide quantum dot conjugate under alkaline conditions to obtain the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material; the pH value of the alkaline condition is 7.2-7.5.
According to the invention, zinc oxide quantum dots and 3-aminopropyl trimethoxy silane are dispersed in N, N-dimethylformamide for amination to obtain the amino zinc oxide quantum dots.
In the invention, the zinc oxide quantum dot is preferably sold in the market or self-made, and the self-making method is preferably as follows:
734mg of C under magnetic stirring 4 H 6 O 4 Zn and 86mg C 4 H 6 MgO 4 ·4H 2 Disperse in 60mL ethanol (80 ℃) and stir for 30min. Simultaneously, 200mg of NaOH was sonicated in 30mL of ethanol. After that, the two solutions were placed in a refrigerator at 4℃for 15min after the preparation was completed. Finally, the solution containing NaOH is slowly added into C 4 H 6 O 4 Zn and C 4 H 6 MgO 4 After stirring at room temperature for 8h, n-hexane was added to precipitate. The obtained sedimentCentrifuging at 12000rpm, discarding supernatant, washing with absolute ethanol for three times, and drying in oven at 60deg.C to obtain zinc oxide quantum dot.
In the invention, the dosage ratio of the zinc oxide quantum dot to the 3-aminopropyl trimethoxysilane is preferably 0.8-1.2 mg: 1. Mu.L, more preferably 1mg:1 μl; the dosage ratio of the zinc oxide quantum dot to the N, N-Dimethylformamide (DMF) is preferably 0.8-1.2 mg:10mL, more preferably 1mg:10mL.
In the present invention, the temperature of the amination is preferably 100 to 150 ℃, more preferably 120 ℃; the time is preferably 10 to 20 minutes, more preferably 15 minutes.
In the present invention, the amination is preferably further carried out by centrifuging the product obtained by amination, and washing the solid phase obtained by centrifugation with DMF and drying. In the present invention, the number of times of washing is preferably 3 times; the drying is preferably vacuum freeze drying. In the present invention, the conditions for vacuum freeze-drying are not particularly limited, and DMF on the surface of the product may be removed.
After the amino zinc oxide quantum dot is obtained, the amino zinc oxide quantum dot, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDS), N-hydroxysuccinimide (NHS) and salicylic acid are dispersed in N, N-dimethylformamide for coupling to obtain the zinc oxide quantum dot conjugate.
In the invention, the mass ratio of the amino zinc oxide quantum dot, EDS, NHS and salicylic acid is 200: 170-175: 130 to 135:100, more preferably 200:172:132:100. in the invention, the ratio of the salicylic acid to the DMF is preferably 80-120 mg:10mL, more preferably 100mg:10mL.
In the present invention, the temperature of the coupling is preferably 20 to 30 ℃, more preferably 25 ℃; the time is preferably 18 to 30 hours, more preferably 24 hours. In the present invention, the coupling is preferably performed under stirring at a rotation speed of preferably 300 to 800rpm, more preferably 500rpm.
In the present invention, the coupling is preferably further performed by centrifuging the coupled product, and drying the solid phase obtained by centrifugation after washing with absolute ethanol. In the present invention, the number of times of washing is preferably 3 times; the drying is preferably vacuum freeze drying. In the present invention, the conditions for vacuum freeze-drying are not particularly limited, and absolute ethanol on the surface of the product may be removed.
After obtaining a zinc oxide quantum dot conjugate, the invention mixes a dispersion liquid of silicon dioxide nano particles with the zinc oxide quantum dot conjugate under alkaline condition to obtain the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material; the pH value of the alkaline condition is 7.2-7.5.
In the present invention, the preparation of the silica nanoparticle preferably includes the steps of:
100mL of ultrapure water, 20mL of absolute ethanol, 1.5mL of ammonia water, 1000mg of CTAB were sequentially added to the beaker, and the above mixed solution was sonicated for 30min, followed by stirring at 200r/min for 30min. Subsequently, a mixed solution of 20mL of absolute ethyl alcohol and 0.2g of ethyl orthosilicate is added into the solution, and the solution is stirred for 2 hours at room temperature to obtain white precipitate, and the obtained sample solution is subjected to vacuum freeze drying until solid powder is the silicon dioxide nano particles.
In the present invention, the dispersion of silica nanoparticles includes silica nanoparticles, ethanol, and water. In the present invention, the preparation of the dispersion of silica nanoparticles preferably comprises:
and adding the silica nanoparticles into absolute ethanol and water, and performing ultrasonic dispersion to obtain a dispersion liquid of the silica nanoparticles.
In the invention, the ultrasonic frequency of the ultrasonic dispersion is preferably 30-50 KHz, and the time is preferably 10-20 min.
In the present invention, the mixing means is preferably stirring, and the rotation speed of the stirring is preferably 300 to 800rpm, more preferably 500rpm, and the time is preferably 23 to 25 hours, more preferably 24 hours.
In the present invention, the mixing preferably further comprises centrifuging the mixed product, and washing and drying the solid phase obtained by centrifugation. In the present invention, the rotational speed of the centrifugation is preferably 10000 to 15000rpm, more preferably 12000rpm. In the present invention, the washed reagent is preferably absolute ethanol, and the number of times of washing is preferably 3. In the present invention, the drying is preferably vacuum freeze-drying. In the present invention, the conditions for vacuum freeze-drying are not particularly limited, and absolute ethanol on the surface of the product may be removed.
The invention also provides an application of the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material or the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material prepared by the preparation method in inhibiting plant pathogenic bacteria. In the present invention, the plant pathogenic bacteria is a. Citrulli.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of ZnO QDs:
734mg of C under magnetic stirring 4 H 6 O 4 Zn and 86mg C 4 H 6 MgO 4 ·4H 2 Disperse in 60mL ethanol (80 ℃) and stir for 30min. Simultaneously, 200mg of NaOH was sonicated in 30mL of ethanol. After that, the two solutions were placed in a refrigerator at 4℃for 15min after the preparation was completed. Finally, the solution containing NaOH is slowly added into C 4 H 6 O 4 Zn and C 4 H 6 MgO 4 After stirring at room temperature for 8h, n-hexane was added to precipitate. Centrifuging the obtained precipitate at 12000rpm, discarding supernatant, washing with absolute ethanol for three times, and drying in oven at 60deg.C.
SiO 2 Preparation of NPs (silica nanoparticles)
100mL of ultrapure water, 20mL of absolute ethanol, 1.5mL of ammonia water, 1000mg of CTAB were sequentially added to the beaker, and the above mixed solution was sonicated for 30min, followed by stirring at 200r/min for 30min. Subsequently, a mixed solution of 20mL of absolute ethanol and 0.2g of ethyl orthosilicate was added to the above solution, and stirred at room temperature for 2 hours to obtain a white precipitate. The obtained sample solution was freeze-dried in vacuo to a solid powder.
200mg of ZnO QDs are accurately weighed and dispersed in 10mL of DMF and heated to 12Adding 200 μl of APTS at 0deg.C, stirring at 120deg.C for 15min, centrifuging at 12000rpm, and washing with DMF for 3 times, and vacuum freeze drying the precipitate to obtain solid powder, namely zinc amino oxide quantum dot (ZnO-NH) 2 )。
172mg of EDS and 132mg of NHS were dissolved in 10mL of DMF containing 100mg of salicylic acid and vigorously stirred for 30min. Then ZnO-NH 2 Adding into the mixed solution, slowly stirring for 24h, centrifuging at 12000rpm, and washing with absolute ethanol for three times, and vacuum freeze-drying the obtained precipitate to obtain solid powder, namely zinc oxide quantum dot conjugate (marked as ZnO-SA)
200mg of SiO 2 Adding NPs into 10mL of absolute ethyl alcohol and 10mL of ultrapure water, performing ultrasonic dispersion for 15min, adding 100mg of ZnO-SA to adjust the pH to 7.4, continuously stirring for 6 hours, centrifuging at 12000rpm, washing with absolute ethyl alcohol for three times, and performing vacuum freeze-drying on the obtained precipitate to obtain solid powder, namely the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material (marked as SiO 2 @ZnO-SA)。
FIG. 1 shows ZnO QDs, znO-NH of example 1 2 ZnO-SA and SiO 2 HRTEM diagram of @ ZnO-SA, wherein fig. 1A is HRTEM diagram of ZnO QDs; b is ZnO-NH 2 HRTEM images of (a); c is the HRTEM image of ZnO-SA, D is SiO 2 HRTEM plot of @ ZnO-SA. As can be seen from fig. 1: the original ZnO QDs are well dispersed and have a size of about 4nm (FIG. 1A), while APTES (ZnO-NH) 2 ) The modified ZnO QDs have little dimensional change, are still well dispersed, and have no aggregation phenomenon (FIG. 1B). Along with SA coupling, znO QDs remained well dispersed, yielding stable conjugates with particle sizes of about 4nm (FIG. 1C). In addition, the conjugate is loaded to about 50nm of SiO 2 NPs vector (FIG. 1D). Fig. 1 is obtained by a high resolution transmission electron microscope (HRTEM, TECNAI SPIRIT, FEI).
FIG. 2 is a diagram of ZnO QDs, znO-NH of example 1 2 ZnO-SA and SiO 2 FTIR spectra of @ ZnO-SA, as can be seen from FIG. 2: at 456cm -1 Or 470cm -1 The nearby peaks are attributed to Zn-O bonds of ZnO QDs. ZnO-NH 2 Is at 1050cm -1 And 1580cm -1 Peak values appear, respectively due to the stretching vibration of Si-O-Si and the bending vibration of N-H, indicating successful branching of ATPES with ZnO QDs. Through SAAfter tidying at 1650cm -1 The position shows stronger-NH-CO-vibration, which indicates ZnO-NH 2 Amidation reaction with SA is successful. Furthermore, the conjugate is supported on SiO 2 After NPs at 1065cm -1 Strong peaks appear due to the stretching vibration of Si-O-Si, indicating successful loading of the conjugate on SiO 2 NPs. FIG. 2 is a Fourier transform IR spectrum obtained from a Tensor27 spectrophotometer (Bruker).
FIG. 3 is SiO of example 1 2 NPs and SiO 2 XRD spectra of @ ZnO-SA, as can be seen from FIG. 3: siO (SiO) 2 NPs have phases of orthogonal crystal structure (PDF#44-1394) which occur at SiO 2 On ZnO-SA. ZnO QDs have wurtzite-type phases which also occur in SiO 2 On ZnO-SA. The results show that the prepared SiO 2 The @ ZnO-SA is a composite material consisting of zinc oxide of wurtzite structure and silicon dioxide of orthorhombic crystal structure. FIG. 3 was obtained by testing with an X-ray diffraction spectrometer (XRD, smartLab-9, rikagu Corp).
FIG. 4 shows ZnO QDs, znO-NH of example 1 2 ZnO-SA and SiO 2 The ultraviolet-visible light absorption spectrum of @ ZnO-SA is shown in FIG. 4: znO QDs, znO-NH 2 The same absorbance at 350nm as ZnO-SA, while SiO 2 The absorbance peak of @ ZnO-SA was blue shifted to 360nm. This may be SiO 2 NPs loading reduces surface defects of ZnO QDs, affecting their optical properties. The data of the ultraviolet visible spectrum (UV-vis, TU-1950, perse) of FIG. 4 were recorded between 600-200nm in 2nm steps.
FIG. 5 is ZnO-NH of example 1 2 Wherein A is ZnO-NH 2 Is a full spectrum of (3); B. c, D, E and F are high resolution X-ray photoelectron spectra of C1s, O1s, N1s, si 2p and Zn2p, respectively;
FIG. 6 shows XPS spectrum A of ZnO-SA as a full spectrum of ZnO-SA; B. c, D, E and F are high resolution X-ray photoelectron spectra of C1s, O1s, N1s, si 2p and Zn2p, respectively; as can be seen from fig. 5 to 6: peaks of ZnO QDs appearing at 101.7eV and 399.8eV are respectively attributed to Si 2p and N1s, which indicate that the functionalization of the amino groups on the surfaces of ZnO QDs is successful. ZnO-NH 2 Corresponding to amide bonds appeared at 288.3eV and 531.6eVPeaks, due to C1s and O1s, respectively, indicating ZnO-NH 2 The salicylic acid was successfully coupled.
FIG. 7 is SiO 2 XPS spectrum of @ ZnO-SA, wherein A is SiO 2 Full spectrum of @ ZnO-SA; B. c, D, E and F are high-resolution X-ray photoelectron spectra of C1s, O1s, N1s, si 2p and Zn2p, respectively, as can be seen from FIG. 7: znO-SA supported on SiO 2 After NPs, the coupling carrier shows peaks of O1s, C1s, si 2p and Zn2p, which indicates that SA and ZnO QDs after amino functionalization are subjected to amidation reaction and then successfully loaded to SiO 2 NPs。
As can be seen from fig. 5 to 7: znO-ZnO-NH 2 ZnO-SA and SiO 2 The @ ZnO-SA shows peaks of Zn2p, O1s, C1s and Si 2 p. Fig. 5 to 7 are obtained by analyzing the composition structure of quantum dots by X-ray photoelectron spectroscopy (XPS, nexsa, thermo).
FIG. 8 is a three-dimensional fluorescence spectrum of SA and ZnO QDs, wherein A is a three-dimensional fluorescence spectrum of SA and B is a three-dimensional fluorescence spectrum of ZnO QDs.
FIG. 9 is ZnO-NH 2 ZnO-SA and SiO 2 Three-dimensional fluorescence spectrogram of @ ZnO-SA, wherein A is ZnO-NH 2 B is a three-dimensional fluorescence spectrum of ZnO-SA, C is SiO 2 Three-dimensional fluorescence spectrum of @ ZnO-SA.
As can be seen from fig. 8 to 9: znO-NH 2 ZnO-SA and SiO 2 The three-dimensional fluorescence spectrum of @ ZnO-SA has the characteristics of partial SA and ZnO QDs, which indicates that the preparation of the coupling load is successful.
The invention determines SiO 2 The in vitro antibacterial activity of the @ ZnO-SA is as follows:
study of ZnO-NH by employing growth Curve method and plate count method 2 ZnO-SA and SiO 2 Antibacterial Activity of @ ZnO-SA on A.citrulli. The citrulli was cultured in King's B (KB) medium at 28 ℃. After incubation for 24h, 40. Mu.L of the bacterial suspension was added to a solution containing 40mL of ZnO-NH at different concentrations (19, 37.5, 75, 150 and 300 mg/L), respectively 2 ZnO-SA and SiO 2 KB broth at ZnO-SA. Ultrapure water and SA were used as control treatments. For the growth inhibition test, the different treatments described above were placed at 28℃at 200rpmAfter culturing for 1h, 2h, 3h, 5h, 7h, 9h and 12h, respectively, samples were taken on an ultra-clean bench and placed in a microplate reader, and the absorbance at a wavelength of 600nm was measured to monitor bacterial growth. Subtracting the measured absorbance value from SA, znO-NH 2 ZnO-SA and SiO 2 Background absorbance values caused by the @ ZnO-SA solution. SA, znO-NH is calculated according to the formula (1) 2 ZnO-SA and SiO 2 Antibacterial ratio of @ ZnO-SA. For the CFU test, the bacterial suspension after 24h incubation was diluted 10 with sterile water 5 Multiple times, 100. Mu.L of the bacterial suspension was then added homogeneously to SA, znO-NH containing different concentrations (19, 37.5, 75, 150 and 300 mg/L), respectively 2 ZnO-SA and SiO 2 KB solid culture plates at ZnO-SA. After 36h of incubation in the biochemical incubator, bacterial colonies were observed in the different treatments.
FIG. 10 shows SA, znO-NH concentrations 2 ZnO-SA and SiO 2 Growth curve of pathogenic bacteria after @ ZnO-SA treatment, wherein A-D are SA and ZnO-NH with different concentrations respectively 2 ZnO-SA and SiO 2 The growth curve of pathogenic bacteria after @ ZnO-SA treatment is shown in FIG. 10: SA, znO-NH with different concentrations 2 ZnO-SA and SiO 2 The growth curves of all @ ZnO-SA treated A.citrulli cells were found to change significantly after 7 h. The results showed that SA had some inhibition of growth at higher concentrations (300 mg/L) only during 12h of co-incubation with A.citrulli cells (FIG. 10A). Through ZnO-NH 2 After treatment, inhibition of A.citrulli cell growth was observed within 7-12h at concentrations of 150-300mg/L (FIG. 10B). ZnO-SA and SiO 2 The @ ZnO-SA has obvious inhibition effect on the growth of A.citrulli cells, and no bacteria grow in a long time after 300mg/L treatment. Especially with the same concentration of SA, znO-NH 2 SiO compared with ZnO-SA 2 The @ ZnO-SA has higher antibacterial activity.
FIG. 11 shows ZnO-NH at various concentrations 2 ZnO-SA and SiO 2 Colony images after 36h treatment of pathogenic bacterial cells with ZnO-SA.
FIG. 12 is ZnO-NH 2 ZnO-SA and SiO 2 Antibacterial rate of @ ZnO-SA on pathogenic bacteria. As can be seen from fig. 11 to 12: after 36h incubation on KB agar plates, siO 2 The @ ZnO-SA treatment still showed a higher concentration of ZnO-NH than the same concentration 2 And ZnO-SA treatment has better antibacterial effect.
The invention researches SiO by using potting test 2 The @ ZnO-SA improves the disease resistance of melon seedlings, and the experimental method is as follows: melon seeds were treated with 2% (W/V) sodium hypochlorite solution for 20min and then washed three times with ultrapure water. Uniformly spreading the sterilized melon seeds in a seedling tray, and placing in a greenhouse (temperature: 27+ -2 ℃ and humidity: 65%) for light-proof germination treatment. After germination, melon seedlings are transferred into a plastic box containing a Mucun B culture solution for continuous culture. After the plant grows to the five-leaf period, spraying 300mg/L SA and ZnO-NH on the leaf surfaces respectively 2 ZnO-SA and SiO 2 The @ ZnO-SA solution was run-off until run-off was formed. After 24 hours of foliage spraying, melon seedlings are inoculated with bacterial fruit blotch germs. Each melon seedling was covered with a plastic bag for 24 hours. Subsequently, the plastic was to be removed and melon seedlings transferred to the greenhouse for two weeks of continued cultivation. The severity of bacterial fruit blotch of melon was evaluated using a scale of 1-5. Disease severity grade: grade 1 = asymptomatic; grade 2 = 1-15% of leaves present symptoms; grade 3 = 16-50% of leaves present symptoms; grade 4 = 51-80% of leaves present symptoms; grade 5 =>80% or even all leaves present symptoms. The extent of disease was recorded every two days. The disease course of bacterial fruit blotch of melon was calculated according to formula (2) using the area under the disease development curve (AUDPC). In addition, the total chlorophyll content of all treatments was recorded using a hand-held chlorophyll meter, and the fresh and dry weights of melon seedling roots and stems, root length, and stem length were recorded.
FIG. 13 shows foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 The change pattern of plant image after @ ZnO-SA is shown in FIG. 13: through SA, znO-NH 2 ZnO-SA and SiO 2 After the @ ZnO-SA foliar spray, the infection hazard phenomenon of A.citrulli is reduced, and the SiO therein 2 The control effect of the @ ZnO-SA treatment is optimal.
FIG. 14 shows foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 The graph of the change in area under the disease development curve (AUDPC value) after @ ZnO-SA is shown in FIG. 14: foliar spray of SiO relative to the affected group by AUDPC measurement 2 The @ ZnO-SA energy will cause bacterial fruitThe incidence of plaque was reduced by 68.66%. SA, znO-NH 2 And the incidence rate of diseases can be respectively reduced by 33.52%,33.52% and 57.84% by the treatment of foliage spraying of ZnO-SA.
FIG. 15 shows foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 The graph of the total chlorophyll content (SPAD value) after @ ZnO-SA is shown in fig. 15: thus, with SA, znO-NH 2 Compared with ZnO-SA treatment, the foliage spray of SiO 2 The @ ZnO-SA has the capability of better protecting melon seedlings and reducing the risk of bacterial fruit blotches. Bacterial fruit blotch of melon can lead to serious decrease of photosynthesis, and after infection by A.citrulli, chlorophyll content is reduced by 35.90%. Through SiO 2 After the @ ZnO-SA treatment, the chlorophyll content was increased by 41.31% compared to the infected group.
FIG. 16 shows foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 The change patterns of root length, stem length, root fresh weight and stem fresh weight after @ ZnO-SA, wherein A is the change of root length, B is the change of stem length, C is the change of root fresh weight, and D is the change of stem fresh weight, are shown in FIG. 16: after the melon seedlings are infected by A.citrulli, the biomass of the melon seedlings is reduced by 72.78-82.02 percent. However, the root system length of melon seedlings is not changed, but the root weight is remarkably reduced, probably because the plant transpiration is maintained by the root system still absorbing water due to the reduction of nutrient delivery caused by infection of leaves by A.citrulli. Importantly, via SiO 2 The biomass level of melon seedlings was restored but slightly below healthy level by the @ ZnO-SA treatment. The above results indicate that SiO 2 The @ ZnO-SA has the capability of protecting melon seedlings from being infected by A.citrulli, and can reduce the occurrence of bacterial fruit blotch.
The invention researches SiO 2 Influence of @ ZnO-SA on melon seedling antioxidant defense system, the method is as follows:
reaction of SiO using antioxidant enzyme activity and lipid peroxidation degree 2 Ability of @ ZnO-SA to increase disease resistance of melon seedlings. The content of Malondialdehyde (MDA) and the activities of Peroxidase (POD), catalase (CAT) and superoxide dismutase (SOD) were determined by commercial assay kits (institute of biotechnology, build in south kyo, china). To be sprayed with SiO on leaf surfaces 2 After inoculating A.citrulli to the leaves of melon seedlings for two weeks, the leaves were harvested and washed three times with ultrapure water. Accurately weighing 0.2g, storing in liquid nitrogen, grinding into powder under the liquid nitrogen environment, and adding into 0.2M phosphate buffer solution. Then, shaking and mixing uniformly to prepare plant homogenate, and centrifuging at a differential speed according to the requirements of commercial detection kits. The supernatant was removed and reacted with the relevant reagents to complete the reaction, and the MDA content and the activities of POD, CAT and SOD were measured at 532nm, 420nm, 405nm and 450nm, respectively.
FIG. 17 foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 Changes in MDA content, CAT activity, POD activity and SOD activity after @ ZnO-SA, wherein A-D are changes in MDA content, CAT activity, POD activity and SOD activity, respectively, as can be seen from FIG. 17: compared with healthy group, MDA content of melon seedlings is increased by 216.67% after being infected by A. Citrulli, which shows that lipid peroxidation is serious, and SiO is passed through 2 The MDA content was reduced by 98.68% by ZnO-SA treatment and remained no significant difference from normal plants (fig. 17A). To further study SiO 2 Activity of antioxidant defense System after treatment of melon seedlings with ZnO-SA CAT, POD and SOD activities were measured. The results showed that the activities of CAT, POD and SOD increased by 39.52%,145.60% and 132.95%, respectively, in the healthier group (fig. 17B). This is because the in vivo antioxidant defense system is spontaneously activated to combat the infectious hazard of pathogenic bacteria after melon seedlings are ill. The result of the increased MDA content shows that the oxidation resistance defense system of melon seedlings is not self-resisted from being infected by A.citrulli, so that the chlorophyll content and biomass of melon seedlings are reduced. However, via SiO 2 After the @ ZnO-SA treatment, the activities of CAT, POD and SOD in melon seedlings were reduced by 29.13%,45.04% and 45.47% respectively with respect to the disease-causing agent. This phenomenon suggests that melon seedlings are able to resist attack by pathogenic bacteria without activating a higher antioxidant defense system activity. Therefore, combined with the results of chlorophyll content and biomass changes, the leaf surface was sprayed with SiO 2 The @ ZnO-SA can improve the resistance of melon seedlings to A.citrulli by regulating an antioxidant defense system.
The invention researches SiO 2 Young melon at ZnO-SAThe method for absorbing the nutrient elements of the seedlings comprises the following steps:
all the treated melon seedling leaves were collected and washed clean, and their fresh tissues were dried at 60 ℃ and ground to a fine powder. 200mg of leaves were accurately weighed and placed in a solution containing 1mL of HClO 4 And 9mL HNO 3 Is then placed in a graphite furnace at 130 ℃ for digestion for 2 hours. Subsequently, the nutrient content was determined by inductively coupled plasma optical emission spectroscopy (ICP-OES) with a constant volume of 25 mL.
FIG. 18 shows foliar spray of SA, znO-NH 2 ZnO-SA and SiO 2 Zn, fe, ca, mg and Mn nutrition content change maps in the aerial parts of melon seedlings after @ ZnO-SA, wherein maps A-D are Zn, fe, ca, mg and Mn nutrition content change maps respectively. As can be seen from fig. 18: spraying SiO on leaf surface 2 After @ ZnO-SA, the zinc content increased by 31.78% compared to the infected group (FIG. 18A). Foliage spraying of SiO 2 The @ ZnO-SA increased the iron content (43.73%) of the infected melon seedlings (FIG. 18B). Spraying SiO on leaf surface 2 After @ ZnO-SA, the calcium content increased by 53.53% compared to the infected group (FIG. 18C). In addition, compared with disease control, foliar spraying drastically increases the content of lignin, callose and ROS by 34%, 30% and 31%, effectively slowing down the occurrence of cucumber anthracnose. In the present study, the leaf surfaces were sprayed with SiO 2 The @ ZnO-SA can respectively improve the magnesium content (33.01%) and the manganese content (1.59%) of the infected melon seedlings. Therefore, the above research results strongly indicate SiO 2 The @ ZnO-SA can promote the absorption of zinc, iron, calcium, magnesium and manganese elements by melons, so that the plant resistance is improved, and the occurrence of bacterial fruit blotch is reduced.
To sum up: siO (SiO) 2 The @ ZnO-SA can effectively inhibit the growth of bacterial cells within 12 hours. Potted plant test results show that the leaf surface is sprayed with SiO 2 The @ ZnO-SA can regulate activities of antioxidant enzymes, namely CAT activity (29.13%), POD activity (45.04) and SOD activity (45.47), and can promote absorption of nutrient elements by melon seedlings (1.59-53.53%). Thus, siO 2 The addition of ZnO-SA improves the disease resistance of melon seedlings by regulating the antioxidant defense system and promoting the absorption of nutrient elements, thereby reducing the occurrence of bacterial fruit blotch (68.66 percent)) Finally, the growth and development of melon seedlings are promoted.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The silicon dioxide-zinc oxide quantum dot-salicylic acid composite material is characterized by comprising silicon dioxide nano particles and zinc oxide quantum dot conjugates coated on the surfaces of the silicon dioxide nano particles; the zinc oxide quantum dot conjugate comprises an aminated zinc oxide quantum dot and salicylic acid coupled with the aminated zinc oxide quantum dot;
the size of the silicon dioxide nano particles is 50-200 nm.
2. The silicon dioxide-zinc oxide quantum dot-salicylic acid composite material according to claim 1, wherein the mass ratio of the amino zinc oxide quantum dot to the salicylic acid is 1.5-2: 1.
3. the silica-zinc oxide quantum dot-salicylic acid composite according to claim 1 or2, wherein the mass ratio of the zinc oxide quantum dot conjugate to the silica nanoparticle is 10: 15-25.
4. A method for preparing the silica-zinc oxide quantum dot-salicylic acid composite material according to any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) Dispersing zinc oxide quantum dots and 3-aminopropyl trimethoxy silane in N, N-dimethylformamide, and amination to obtain amino zinc oxide quantum dots;
(2) Dispersing the amino zinc oxide quantum dot, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, N-hydroxysuccinimide and salicylic acid in N, N-dimethylformamide, and performing coupling to obtain a zinc oxide quantum dot conjugate;
(3) Mixing and coating the dispersion liquid of the silicon dioxide nano particles and the zinc oxide quantum dot conjugate under alkaline conditions to obtain the silicon dioxide-zinc oxide quantum dot-salicylic acid composite material; the pH value of the alkaline condition is 7.2-7.5.
5. The process according to claim 4, wherein the amination is carried out at a temperature of 110 to 150℃for a period of 12 to 18 minutes.
6. The method according to claim 4, wherein the coupling temperature is 20 to 30℃and the coupling time is 18 to 30 hours.
7. The method according to claim 4, wherein in the step (1), the ratio of the zinc oxide quantum dot to the 3-aminopropyl trimethoxysilane is 0.8 to 1.2mg:1 mul.
8. The method according to claim 4, wherein in the step (2), the mass ratio of the amino zinc oxide quantum dot, the 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, the n-hydroxysuccinimide and the salicylic acid is 200: 170-175: 130 to 135:100.
9. use of the silica-zinc oxide quantum dot-salicylic acid composite material according to any one of claims 1 to 3 or the silica-zinc oxide quantum dot-salicylic acid composite material prepared by the preparation method according to any one of claims 4 to 8 for inhibiting plant pathogenic bacteria.
10. The use according to claim 9, wherein the phytopathogen is a.
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