CN109354633A - A kind of chitosan oligosaccharide chelates of zinc and its preparation method and application - Google Patents
A kind of chitosan oligosaccharide chelates of zinc and its preparation method and application Download PDFInfo
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- CN109354633A CN109354633A CN201811352622.5A CN201811352622A CN109354633A CN 109354633 A CN109354633 A CN 109354633A CN 201811352622 A CN201811352622 A CN 201811352622A CN 109354633 A CN109354633 A CN 109354633A
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- chitosan oligosaccharide
- zinc
- chelates
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- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 title claims abstract description 94
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 63
- 239000011701 zinc Substances 0.000 title claims abstract description 63
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 241000196324 Embryophyta Species 0.000 claims abstract description 29
- 244000052616 bacterial pathogen Species 0.000 claims abstract description 23
- 239000011787 zinc oxide Substances 0.000 claims abstract description 21
- 201000010099 disease Diseases 0.000 claims abstract description 13
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims abstract description 13
- 240000007594 Oryza sativa Species 0.000 claims abstract description 10
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 10
- 235000009566 rice Nutrition 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 229920000742 Cotton Polymers 0.000 claims abstract description 8
- 241001530056 Athelia rolfsii Species 0.000 claims abstract description 7
- 230000006196 deacetylation Effects 0.000 claims abstract description 7
- 238000003381 deacetylation reaction Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 230000008635 plant growth Effects 0.000 claims abstract description 6
- 244000000010 microbial pathogen Species 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000006228 supernatant Substances 0.000 claims abstract description 3
- 241000894006 Bacteria Species 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000013522 chelant Substances 0.000 claims description 11
- 240000003768 Solanum lycopersicum Species 0.000 claims description 8
- 241000233866 Fungi Species 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 240000001980 Cucurbita pepo Species 0.000 claims description 4
- 244000241257 Cucumis melo Species 0.000 claims description 3
- 240000008067 Cucumis sativus Species 0.000 claims description 3
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- 235000009847 Cucumis melo var cantalupensis Nutrition 0.000 claims description 2
- 235000009852 Cucurbita pepo Nutrition 0.000 claims description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 2
- 240000006365 Vitis vinifera Species 0.000 claims description 2
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 230000002538 fungal effect Effects 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 241000209140 Triticum Species 0.000 claims 2
- 235000021307 Triticum Nutrition 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 241000040710 Chela Species 0.000 claims 1
- 244000241235 Citrullus lanatus Species 0.000 claims 1
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 claims 1
- 241000221785 Erysiphales Species 0.000 claims 1
- 241000192125 Firmicutes Species 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229940084434 fungoid Drugs 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000003612 virological effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 12
- 241000588724 Escherichia coli Species 0.000 abstract description 7
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 7
- 208000036142 Viral infection Diseases 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 description 25
- 229920001661 Chitosan Polymers 0.000 description 9
- 230000012010 growth Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000003337 fertilizer Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000001963 growth medium Substances 0.000 description 5
- 239000005740 Boscalid Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 206010048259 Zinc deficiency Diseases 0.000 description 4
- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 description 4
- 229940118790 boscalid Drugs 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229920001542 oligosaccharide Polymers 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 102000003846 Carbonic anhydrases Human genes 0.000 description 2
- 108090000209 Carbonic anhydrases Proteins 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
- 238000010672 photosynthesis Methods 0.000 description 2
- 239000013641 positive control Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000004562 water dispersible granule Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229930192334 Auxin Natural products 0.000 description 1
- 235000000832 Ayote Nutrition 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 241001478240 Coccus Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 235000009854 Cucurbita moschata Nutrition 0.000 description 1
- 235000009804 Cucurbita pepo subsp pepo Nutrition 0.000 description 1
- 208000035240 Disease Resistance Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000006137 Luria-Bertani broth Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000001866 Vernicia fordii Species 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 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 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000002363 auxin Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- 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 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005078 fruit development Effects 0.000 description 1
- 238000009963 fulling Methods 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 244000039328 opportunistic pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 235000015136 pumpkin Nutrition 0.000 description 1
- 230000002786 root growth Effects 0.000 description 1
- 238000011218 seed culture Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008223 sterile water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H23/00—Compounds containing boron, silicon or a metal, e.g. chelates or vitamin B12
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Pest Control & Pesticides (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Agronomy & Crop Science (AREA)
- Medicinal Chemistry (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to control of plant disease application fields.Specifically, the present invention relates to a kind of chitosan oligosaccharide chelates of zinc and its preparation method and application.The present invention adds appropriate organic acid and obtains chitosan oligosaccharide chelates of zinc using chitosan oligosaccharide and zinc oxide as raw material.The mass ratio of chitosan oligosaccharide and zinc oxide is 10:1~5:1；The average molecular weight of chitosan oligosaccharide is 1000~3500Da, deacetylation >=85%.Chitosan oligosaccharide chelates of zinc appearance of the present invention is the light yellow supernatant liquid to claret, is had no irritating odor, and pH value is 4.0~6.0.Chitosan oligosaccharide chelates of zinc of the present invention is under its effective concentration, the multiple pathogenic microorganisms such as pathogenic bacteria are withered with good antibacterial, bactericidal effect to Escherichia coli, staphylococcus aureus and rice banded sclerotial blight pathogenic bacteria, apple decay pathogenic bacteria and cotton, have to the viroses of plant and prevent and treat effect well, while there is significant facilitation to plant growth.
Description
Technical field
The invention belongs to control of plant disease application fields.Specifically, the present invention relates to a kind of chitosan oligosaccharide chelates of zinc
And its preparation method and application.
Background technique
Chitosan oligosaccharide also known as amino-oligosaccharide are the product after chitosan hydrolyzate, good water solubility, by 2-20 Glucosamine
It is formed with β -1,4 glucosides key connection.Studies have shown that chitosan oligosaccharide have unique physiological function, at present for, it is most important to answer
With being agriculturally.As biological pesticide, chitosan oligosaccharide is free from environmental pollution to person poultry harmless, can inhibit multiple pathogenic microorganisms
Growth, dosage is low and price is close with chemical pesticide；Moreover, chitosan oligosaccharide can effectively be degraded, soil can be promoted to have
The growth of beneficial microorganism and plant, be known as " be not the pesticide of pesticide, be not chemical fertilizer chemical fertilizer ".Chitosan oligosaccharide is agriculturally
It applies while chemical fertilizer amount of application is effectively reduced, to China's soil environment is improved, produces nuisanceless green grain, melon
Fruit, flowers etc. promote China's agricultural sustainable development to have great economic value and social benefit.But due to chitosan oligosaccharide
The unstable of itself, quick-acting are poor, to limit it in the extensive use in agriculture field.Therefore, to chitosan oligosaccharide carry out into
The modification of one step, preparing, there is higher active chitosan oligosaccharide derivative to become the key for solving its application limitation.
Zinc is a kind of mankind and the essential metallic element of animal and plant growth, primarily as the gold of enzyme in plant
Belong to activator.The zinc-containing metal enzyme found earliest is carbonic anhydrase, and this enzyme is distributed very extensively in plant, is primarily present in leaf
In green body.It is catalyzed the aquation of carbon dioxide, promotes the fixation of carbon dioxide in photosynthesis, and zinc-deficiency makes carbonic anhydrase
Activity reduces.Therefore, zinc is important the formation of carbohydrate.Zinc also participates in auxin (heteroauxin) in plant
Synthesis, when zinc-deficiency, the intracorporal growth cellulose content of plant decreases, and dead state occurs in growth and development, and stipes shortens, plant
Short and small, leaf expansion elongation is blocked, and forms leaflet, and is in leafage shape.Occur light green, yellow or white rust between vein
Spot, especially in old leaf.In field, it is seen that plant height is uneven, and the maturity period postpones, and fruit development is bad.It has been reported in China
The plant of zinc-deficiency has " shrunk rice seedling ", " runt seedling ", " root decline " of rice, " white bud " of corn, citrus etc. " little leaf " of fruit trees,
" bronzed disease " of tung oil tree etc..Crop zinc content is generally 20~100mg/kg, may zinc-deficiency when being lower than 20mg/kg.Studies have shown that
Zinc is not easy to be absorbed and used by plants in practical applications, and how to find a kind of form conducive to plant absorption is also to promote plant
The key point more preferably grown.
Some researches show that using amino-oligosaccharide as carrier, the new function fertilizer developed through high temperature chelating was produced in recent years
Product-oligosaccharides zinc and marine oligosaccharide zinc.It is remarkably improved the activity of enzyme in crop body after application, promotes carbohydrate conversion,
Promote full seed, enhance winter resistance and salt tolerance, improve chlorophyll content in leaf blades, crop photosynthesis and protein is promoted to close
At raising yield, improving quality enhances disease-resistant, the anti-adversity ability of crop.Have great importance to agricultural production.
Summary of the invention
In view of the above-mentioned problems, the chelate is at it the present invention provides a kind of chitosan oligosaccharide chelates of zinc and preparation method thereof
Have under effective concentration to plant disease and prevent and treat effect well, while also can be used as Plant leaf fertilizer application, to plant
Object growth has significant facilitation.
The mass ratio of chitosan oligosaccharide and zinc is 10:1-5:1 in chelate of the present invention；The average molecular weight of chitosan oligosaccharide is
1000-3500Da, deacetylation >=85%.The molecular weight of chitosan oligosaccharide is different, different from the complexing effect of zinc.For the present invention
It says, the complexing effect of chitosan oligosaccharide and zinc in the molecular weight ranges is best, obtained product yield highest.
The chelate appearance is in the light yellow supernatant liquid to claret, pH value 4-6.
Its specific preparation step are as follows: after mixing zinc oxide with water, organic acid is added, chitosan oligosaccharide aqueous solution is added, in 40-
60 DEG C are stirred to react 1-6h, and end of reaction is post-treated, obtains chitosan oligosaccharide chelates of zinc.In order to guarantee fully reacting and final
The stabilization of product, the present invention is in 40-60 DEG C of reaction 1-6h.
In specific preparation process, the mass ratio of zinc oxide and water is 1-3:100.
Chitosan oligosaccharide aqueous solution is the aqueous solution of mass fraction 6-20%.
In terms of pure material, the mass ratio of chitosan oligosaccharide and zinc oxide is 10:1-5:1.
Post-processing of the present invention is filtration treatment, removes impurity.
The invention also discloses chitosan oligosaccharide chelates of zinc as fungicide prevention and treatment phytosis pathogenic microorganism purposes,
The growth of Escherichia coli, staphylococcus aureus can be completely inhibited under effective concentration (mass fraction) 0.06%-0.2%.
Purposes the invention also discloses chitosan oligosaccharide chelates of zinc as fungicide in terms of preventing and treating fungal plant disease,
It is withered to rice banded sclerotial blight pathogenic bacteria, apple decay pathogenic bacteria and cotton in effective concentration (mass fraction) range (1%-5%)
Pathogenic bacteria have the activity of complete antibacterial growth.
Application the invention also discloses chitosan oligosaccharide chelates of zinc as foliar fertilizer in terms of promoting plant growth, effective
In concentration (mass fraction) range (20-100ppm), there is significantly growth-promoting to crops such as tomato, cucurbita pepo, cucumber and muskmelons
Long effect, and the viroses of plant can be prevented and treated.
The present invention makes chitosan oligosaccharide and zinc form stable chelate by chelatropic reaction, can give full play to the excellent of the two
Point.Plant growth can not only be effectively promoted using chitosan oligosaccharide-chelates of zinc that chitosan oligosaccharide is prepared as raw material, and is able to maintain simultaneously
Even increase the induction plant disease-resistant ability of chitosan oligosaccharide, can quickly, enduringly controlling plant diseases, use low concentration, that is, table
Reveal preferable function and effect, this provides a new way to efficiently use and playing the advantage of chitosan oligosaccharide and zinc.Institute of the present invention
The preparation process stated is easy；Reaction condition is mild.
Detailed description of the invention
Fig. 1 is chitosan oligosaccharide infrared spectrogram；
Fig. 2 is chitosan oligosaccharide chelates of zinc infrared spectrogram；
Fig. 3 is the XPS spectrum figure of the Zn2p of chitosan oligosaccharide zinc；
Fig. 4 is the UV spectrogram of chitosan oligosaccharide and chitosan oligosaccharide zinc solution；
Fig. 5 is the FTIR spectrogram of chitosan oligosaccharide and chitosan oligosaccharide zinc.
Specific embodiment
Embodiment 1
A kind of chitosan oligosaccharide chelates of zinc, the mass ratio of chitosan oligosaccharide and zinc is 5:1 in the chelate；The mean molecule of chitosan oligosaccharide
Amount is 1000-3500Da, deacetylation >=90%.The chelate appearance is in light yellow liquid, pH value 6.
Its specific preparation step are as follows: after mixing zinc oxide with water, sulfamic acid is added, chitosan oligosaccharide aqueous solution is added, mixes
After closing uniformly, in 60 DEG C of reaction 1h, after completion of the reaction, filtering and impurity removing is to get chitosan oligosaccharide chelates of zinc solution.
The mass ratio of the zinc oxide and water is 3:100
Chitosan oligosaccharide aqueous solution mass fraction is 20%.
Zinc oxide: organic acid=1:1
In terms of pure material, the mass ratio of chitosan oligosaccharide and zinc oxide is 5:1.
Embodiment 2
A kind of chitosan oligosaccharide chelates of zinc, the mass ratio of chitosan oligosaccharide and zinc is 8:1 in the chelate；The mean molecule of chitosan oligosaccharide
Amount is 1000-3500Da, deacetylation >=90%.The chelate appearance is in claret liquid, pH value 5.5.
Its specific preparation step are as follows: after mixing zinc oxide with water, citric acid is added, chitosan oligosaccharide aqueous solution, mixing is added
After uniformly, after mixing, in 50 DEG C of reaction 6h, after completion of the reaction, filtering and impurity removing is to get chitosan oligosaccharide chelates of zinc solution.
The mass ratio of the zinc oxide and water is 2:100
Chitosan oligosaccharide aqueous solution mass fraction is 13%.
Zinc oxide: organic acid=2:1
In terms of pure material, the mass ratio of chitosan oligosaccharide and zinc oxide is 8:1.
Embodiment 3
A kind of chitosan oligosaccharide chelates of zinc, the mass ratio of chitosan oligosaccharide and zinc is 10:1 in the chelate；The average mark of chitosan oligosaccharide
Son amount is 1000-3500Da, deacetylation >=90%.The chelate appearance is in light yellow liquid, pH value 5.
Its specific preparation step are as follows: after mixing zinc oxide with water, malic acid is added, chitosan oligosaccharide aqueous solution, mixing is added
After uniformly, after mixing, in 60 DEG C of reaction 4h, after completion of the reaction, filtering and impurity removing is to get chitosan oligosaccharide chelates of zinc solution.
The mass ratio of the zinc oxide and water is 1:100
Chitosan oligosaccharide aqueous solution mass fraction is 6%.
Zinc oxide: organic acid=3:1
In terms of pure material, the mass ratio of chitosan oligosaccharide and zinc oxide is 10:1.
Embodiment 4
Verifying to phytopathogen effect is carried out for chitosan oligosaccharide chelates of zinc obtained by the present invention, the results are shown in Table 1 and table
2。
It is withered to choose Escherichia coli, staphylococcus aureus and rice banded sclerotial blight pathogenic bacteria, apple decay pathogenic bacteria and cotton
The pathogenic bacteria that wither are antibacterial object, verify the fungistatic effect of chitosan oligosaccharide chelates of zinc, and with chitosan oligosaccharide, sterilization ling and Boscalid water
Dispersible granule is as control.
The measurement of bacterium minimal inhibitory concentration
Bacterium activation: 250ml triangular flask fills 50ml LB seed culture medium, and one environmental protection of inoculation is stored in 4 DEG C of bacterium inclined-plane
Seed, 160r/min, 37 DEG C of overnight incubations.
Minimal inhibitory concentration MIC (minimum inhibitory concentration), refers to and incubates in certain circumstances
After educating 24 hours, it can inhibit certain microorganism and the lowest concentration of drug to rise appreciably i.e. minimal inhibitory concentration occur.
Minimum bactericidal concentration MBC (minimum bactericidal concentration) kills 99.9% confession
Try the lowest concentration of drug that Institute of Micro-biology needs.
Selection two kinds of bacteriums of Escherichia coli and staphylococcus aureus are antibacterial object, and the activated bacterium solution of 1ml is taken to be added
Into 9ml sterile water, 6 gradients are successively diluted, the 100 μ l of bacterium solution after taking dilution is spread evenly across the plate of solid LB media
On, overnight incubation at 37 DEG C finds out the optimum concentration as strain bacteriostatic experiment according to flat-plate bacterial colony number.
The LB solid medium for preparing various concentration sample respectively, after fulling shake uniformly, inverted plate, and mark.
The LB culture medium of any sample is not added as blank control, the LB culture medium containing various concentration sterilization ling is positive control.
Two kinds of bacterium solutions, the 100 μ l of debita spissitudo is taken to be spread evenly across on plate, three repetitions of each processing are cultivated at 37 DEG C, and culture is for 24 hours
And 48h, it counts respectively.
Table 1
The result shows that for the inhibitory effect of bacterium: chitosan oligosaccharide-chelates of zinc is to the minimal inhibitory concentration of Escherichia coli
0.05%, minimum bactericidal concentration 0.2%, for staphylococcus aureus, the chitosan oligosaccharide chelates of zinc that concentration is 0.1% is just right
Staphylococcus aureus has good bactericidal effect；And chitosan oligosaccharide is 0.2% to the minimal inhibitory concentration of Escherichia coli, it is minimum
Bacteriocidal concentration is 0.4%, and to staphylococcus aureus, the minimal inhibitory concentration of chitosan oligosaccharide is 0.1%, and minimum bactericidal concentration is
0.2%；Sterilization ling is 0.4% to the minimal inhibitory concentration of Escherichia coli, minimum bactericidal concentration 0.5%, to golden yellow grape
Coccus, the minimal inhibitory concentration of chitosan oligosaccharide are 0.5%, minimum bactericidal concentration 0.6%.
The measurement of fungi minimal inhibitory concentration
Fungi activation: the fungi seed on the picking inclined-plane appropriate for being stored in 4 DEG C is transferred in the PDA plate of cooled and solidified
In, it is cultivated 6 days in 28 DEG C of constant incubators.
Organic filter membrane (0.45um) filtration treatment carried out to fluid sample, solid irradiation-sterilize 30min in the UV lamp.
The PDA solid medium for preparing various concentration sample respectively, is formulated as inverted plate after various concentration gradient respectively.
Each bacterial strain colony edge cultivated 6 days from PDA beats the bacteria cake for taking diameter 6mm, and mycelia downwards, is inoculated in
The PDA culture medium center of solidification, is placed in 28 DEG C of constant incubators, cultivates 5 days, measures colony diameter with crossing method, often
3 repetitions of a processing.The PDA culture medium of any sample is not added as blank control, Boscalid is positive control.
The calculating of inhibiting rate: inhibiting rate=(control medium colony diameter-processing culture medium colony diameter)/control culture
Base colony diameter × 100%
Table 2
| Apple decay pathogenic bacteria | Cotton withers pathogenic bacteria | Rice banded sclerotial blight pathogenic bacteria | |
| Minimal inhibitory concentration | Minimal inhibitory concentration | Minimal inhibitory concentration | |
| The present invention | 0.8% | 1.4% | 1.4% |
| Chitosan oligosaccharide | 4% | 6.5% | 4% |
| Boscalid | 4% | 3% | 3% |
For the inhibitory effect of fungi: liquid chitosan oligosaccharide-chelates of zinc is withered pathogenic to apple decay pathogenic bacteria, cotton
Bacterium, three kinds of fungies of rice banded sclerotial blight pathogenic bacteria minimum inhibitory concentration be respectively 0.8%, 1.4%, 1.4%；And chitosan oligosaccharide is to apple
Fruit rot pathogenic bacteria minimum inhibitory concentration be 4%, to cotton wither pathogenic bacteria minimum inhibitory concentration be 6.5%, rice line
The minimum inhibitory concentration of withered pathogenic bacteria is 4%；Minimum inhibitory concentration of the Boscalid water dispersible granules to apple decay pathogenic bacteria
It is 4%, is 3% to the wither minimum inhibitory concentration of pathogenic bacteria of cotton, the minimum inhibitory concentrations of rice banded sclerotial blight pathogenic bacteria is 3%.
The result shows that the chitosan oligosaccharide chelates of zinc of low concentration of the present invention can effectively inhibit and kill phytopathy
Opportunistic pathogen, effect is preferable, and is substantially better than control.
Embodiment 7
Research to plant growth promotion effect and disease resistance is carried out for chitosan oligosaccharide chelates of zinc obtained by the present invention:
Using spraying insecticide-applying way, chitosan oligosaccharide chelates of zinc is diluted to a certain concentration (20-100ppm), is used per acre
Amount is 50-70L, carries out even spraying to tomato and Pumpkin Seedlings plant, each processing is 20 plants spraying, marks, and compares
The chitosan oligosaccharide of equivalent is sprayed, blank sprays equivalent clear water.Observe the growing state of plant.
The result shows that: 1, Summer squash virus plant is twice sprayed, application 2 days, 5 days after observe as a result,
Comparison discovery: compared with clear water blank control, chitosan oligosaccharide-zinc and chitosan oligosaccharide have inhibiting effect to the extension of virosis, specifically
Show as the mitigation of young leaves shrinkage degree, the yellowish green alternate ratio of leaf color is reduced.Through Comprehensive Comparison, chitosan oligosaccharide-zinc effect is most
It is good.
2, foliage-spray and irrigation experiment have been carried out to tomato seedling, it is intended to investigate chitosan oligosaccharide-chelates of zinc and promote to tomato
Growth, the effect for preventing and treating disease, promoting root growth.The plant height and stem thickness of spray front and back tomato plant are surveyed
Amount, the results showed that compared with chitosan oligosaccharide control, chitosan oligosaccharide-zinc has certain promotion to make plant height, the stem thickness of tomato plant
With.Meanwhile compared with blank control, virosis occurs less in experimental plants, illustrates that chitosan oligosaccharide-zinc is not only raw to tomato plant
It is long that there is facilitation, but also there is certain disease resisting effect.
Claims (10)
1. a kind of chitosan oligosaccharide chelates of zinc, it is characterised in that: the chelate using chitosan oligosaccharide and zinc oxide as raw material to be made, the chela
It closes object beyond the region of objective existence and sees the light yellow supernatant liquid to claret of presentation, have no irritating odor, pH value is 4.0~6.0.
And add appropriate organic acid.The mass ratio of chitosan oligosaccharide and zinc oxide is 10:1~5:1；The average molecular weight of chitosan oligosaccharide is
1000~3500Da, deacetylation >=85%.
2. the method for preparing chitosan oligosaccharide chelates of zinc described in claim 1, it is characterised in that: the specific steps are that: it will aoxidize
After zinc is mixed with water, organic acid is added, chitosan oligosaccharide aqueous solution is added, 1-6h, end of reaction, after are stirred to react in 40-60 DEG C
Processing, obtains chitosan oligosaccharide chelates of zinc.
3. the preparation method of chitosan oligosaccharide chelates of zinc according to claim 2, it is characterised in that: in terms of pure material, shell is few
The mass ratio of sugar and zinc oxide is 10:1~5:1.
4. the preparation method of chitosan oligosaccharide chelates of zinc according to claim 2, it is characterised in that: the chitosan oligosaccharide is averaged
Molecular weight is 1000~3500Da, deacetylation >=85%.
5. the preparation method of chitosan oligosaccharide chelates of zinc according to claim 2, it is characterised in that: the organic acid of addition is ammonia
Base sulfonic acid or citric acid or malic acid or its mixture, in terms of the mass ratio of pure material, zinc oxide: organic acid=3:1-
1:1。
6. the preparation method of chitosan oligosaccharide chelates of zinc according to claim 2, it is characterised in that: the chitosan oligosaccharide aqueous solution
Mass fraction is 6-20%.
7. the preparation method of chitosan oligosaccharide chelates of zinc according to claim 2, it is characterised in that: the post-processing approach
To filter or being centrifuged.
8. application of the chitosan oligosaccharide chelates of zinc described in claim 1 in terms of preventing and treating phytosis pathogenic microorganism, the bacterium
Venereal disease pathogenic microorganism is Gram-negative bacteria and gram-positive bacteria.
9. purposes of the chitosan oligosaccharide chelates of zinc described in claim 1 in terms of preventing and treating fungal plant disease, the fungoid
Phytopathogen is rice banded sclerotial blight pathogenic bacteria or apple decay pathogenic bacteria or the withered pathogenic bacteria of cotton or wheat bar shaped handle rest fungus or ash
Grape born of the same parents bacterium or cucumber monofilament shell powdery mildew.
10. application of the chitosan oligosaccharide chelates of zinc described in claim 1 in terms of promoting plant growth and viral diseases, the plant
Object is tomato or cucurbita pepo or muskmelon or watermelon or cucumber or wheat or corn.
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