CN114009444B - 一种多功能Janus型介孔二氧化硅纳米药肥的制备及应用 - Google Patents
一种多功能Janus型介孔二氧化硅纳米药肥的制备及应用 Download PDFInfo
- Publication number
- CN114009444B CN114009444B CN202111251723.5A CN202111251723A CN114009444B CN 114009444 B CN114009444 B CN 114009444B CN 202111251723 A CN202111251723 A CN 202111251723A CN 114009444 B CN114009444 B CN 114009444B
- Authority
- CN
- China
- Prior art keywords
- msns
- prochloraz
- pro
- nano
- mesoporous silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003814 drug Substances 0.000 title claims abstract description 29
- 229940079593 drug Drugs 0.000 title claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003337 fertilizer Substances 0.000 title claims abstract description 12
- 239000005820 Prochloraz Substances 0.000 claims abstract description 49
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 32
- 229940033123 tannic acid Drugs 0.000 claims abstract description 32
- 229920002258 tannic acid Polymers 0.000 claims abstract description 32
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 29
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 29
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 29
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 29
- 239000000575 pesticide Substances 0.000 claims abstract description 27
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 5
- 230000001954 sterilising effect Effects 0.000 claims abstract description 5
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000008055 phosphate buffer solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000000844 anti-bacterial effect Effects 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007792 addition Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002114 nanocomposite Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000002609 medium Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003899 bactericide agent Substances 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 3
- 239000001963 growth medium Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 244000052616 bacterial pathogen Species 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 27
- 238000011068 loading method Methods 0.000 abstract description 11
- 230000008021 deposition Effects 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract description 3
- 230000000536 complexating effect Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000013270 controlled release Methods 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- 241000813090 Rhizoctonia solani Species 0.000 description 5
- 241000227653 Lycopersicon Species 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000008363 phosphate buffer Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 239000002539 nanocarrier Substances 0.000 description 3
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 244000053095 fungal pathogen Species 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000001863 plant nutrition Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 229940002612 prodrug Drugs 0.000 description 1
- 239000000651 prodrug Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LRBQNJMCXXYXIU-YIILYMKVSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)C(OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-YIILYMKVSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues 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
- 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
- A01N25/08—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 containing solids as carriers or diluents
-
- 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
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Toxicology (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
一种新型多功能Janus型介孔二氧化硅纳米药肥的制备及应用,属于纳米材料农学领域。通过在二氧化硅框架中引入Fe3+形成酸性条件下易断裂的‑Fe‑O‑键,将咪鲜胺和单宁酸分别通过与孔道内和载体表面的Fe3+配位结合。借助Fe‑MSN表面的Fe3+与单宁酸的络合,再凭借氢键、分子间作用力和π‑π堆积作用调节单宁酸层的厚度,实现客体分子咪鲜胺的封装与缓控释放,同时提高农药在目标植物上的沉积效率。在酸性条件下,由于H+浓度增加,配位键断开,载体Fe‑MSNs框架自发降解的同时释放农药咪鲜胺和Fe元素,达到持续杀菌和提供铁肥的功效,而在中性或碱性条件下药物装载稳定。
Description
技术领域
本发明属于纳米材料农学领域。本发明涉及一种pH响应、金属掺杂的可降解Janus型介孔二氧化硅包载咪鲜胺亲水性纳米复合体系的制备及应用。
技术背景
农药在防治作物病虫草害、保障粮食生产与安全方面发挥了重要的作用。传统农药制剂粒径粗大,有效利用率低,对生态环境造成了严重的危害。近年来,随着纳米学科的兴起,利用纳米技术开发智能缓释载药体系可以提高农药有效利用率,降低施药频率,减少农业投入成本,改善环境问题,为可持续绿色农业的发展提供了保障。介孔二氧化硅纳米颗粒(MSN)由于具有大表面积、良好的生物相容性、可调控的孔径以及高装载能力,在农药控释应用方面得到了广泛的应用。然而,传统介孔二氧化硅不可控的降解性、长期在靶标或非靶标生物中的滞留会导致严重的不可预测的潜在风险,而且二氧化硅纳米载体表面的功能化位点单一及后修饰过程繁琐复杂,极大的限制了它在农药控释中的使用。
通过方法向二氧化硅框架中引入Fe3+形成酸性条件下易断裂的-Fe-O-键,构建生物降解介孔二氧化硅载体Fe-MSNs。将铁元素螯合于MSN内部,由于铁元素大小较载体中其他元素相对较大,导致整体框架结构呈现Janus型,与传统MSN相比,这种创新结构MSN具有特殊的优势,可以解决传统二氧化硅作为农药载体的部分缺陷,增加载药率,促进药物的缓释。Fe-MSNs孔道中的Fe3+能与大多数农药分子配位结合,提高载药量的同时提供药物的pH响应控释。此外,Fe是植物进行光合作用的必需微量元素,当Fe-MSNs框架降解释放铁离子时能够促进植物生长。由此可见,Fe-MSNs作为农药输送和植物营养补充的多功能载体在农药控释方面有着相当大的应用前景。
单宁酸是一种广泛分布在自然界各类植物中的多酚,具有丰富的儿茶酚基团,可与多种物质或基团以共价键、氢键、配位键、分子间作用力和π-π堆积等方式发生物理或化学作用,被广泛用于具有粘附性和自我修复性的仿生材料中。但借助单宁酸与纳米载体中金属离子的络合作用对客体分子(农药)控释的研究还未见报道。
本发明将纳米技术与受仿生启发相结合,以广谱、高效、低毒但水分散性较差的杀菌剂咪鲜胺为模式农药,基于Fe-MSNs作为可降解的控释载体,接枝单宁酸,制备一种适合植物叶面喷施的pH响应性的多功能纳米药肥。制备工程如图1所示。通过在二氧化硅框架中引入Fe3+形成酸性条件下易断裂的-Fe-O-键,将咪鲜胺和单宁酸分别通过与孔道内和载体表面的Fe3+配位结合。借助Fe-MSN表面的Fe3+与单宁酸的络合,再凭借氢键、分子间作用力和π-π堆积作用调节单宁酸层的厚度,实现客体分子封装与缓控释放的同时提高纳米农药在目标植物上的沉积效率。在酸性条件下,由于H+浓度的增加,配位键被断开药物释放,而在中性或碱性条件下稳定装载药物。由于铁离子掺杂在介孔二氧化硅框架中,赋予了该载体优异的生物降解性,使该多功能载体在农业环境中降解并释放助植物生长的铁元素。此外,单宁酸层除了具有优异的黏附特性,提高了咪鲜胺在植物叶片上的沉积效率,还可以减缓农药突释,有效地促进了咪鲜胺的缓控释放。
发明内容
本发明的目的是进一步降低农药突释,控制咪鲜胺的缓释,从而提供一种pH响应、金属掺杂的可降解Janus型介孔二氧化硅包载咪鲜胺亲水性纳米复合体系的构建制备方法,步骤包括:
(1)Fe-MSNs的制备
将十六烷基三甲基溴化铵(CTAB)溶解于氨水中,加热并持续搅拌至表面活性剂完全溶解,缓慢加入乙醇稀释的正硅酸乙酯(TEOs)搅拌至少4小时,随后缓慢加入硝酸铁和再次加入乙醇稀释正硅酸乙酯并持续搅拌至少1小时;随后,将反应后的溶液置于反应釜内40℃下老化16小时,并收集纳米颗粒;最后,使用硝酸铵的异丙醇溶液于80℃下过夜回流纳米颗粒除去CTAB模板;
CTAB:TEOs(第一次添加)的摩尔比为0.1-10:1;硝酸铁和TEOs(第二次加入)体系中Si/Fe的摩尔比为15-150:1;两次加入TEOs摩尔比n(第一次):n(第二次)为0.21:0.5-5,优选0.21:1;
(2)金属介孔二氧化硅负载咪鲜胺纳米体系(Pro@Fe-MSNs)的制备
将杀菌剂咪鲜胺(Pro)分散到正己烷溶剂中,咪鲜胺在正己烷的浓度优选为1-20mg/mL,最优浓度为5mg/mL;称取Fe-MSNs于反应器中,加入咪鲜胺的正己烷溶液,室温下磁力中速搅拌14小时后离心,并用正己烷洗涤2-3次,真空干燥得到介孔硅负载咪鲜胺纳米体系,即Pro@Fe-MSNs Nps;咪鲜胺与Fe-MSNs的质量比为(0.5-2):1,优选为1:1。
(3)亲水性金属介孔硅负载咪鲜胺纳米体系(Pro@Fe-MSNs/TA)的制备
称取Pro@Fe-MSNs Nps分散于磷酸缓冲盐溶液中(PBS,pH=7.4),向其中滴加单宁酸的磷酸缓冲盐溶液,室温下持续搅拌1小时,离心,并用PBS缓冲液洗涤三次,真空干燥,得到金属介孔硅—单宁酸负载咪鲜胺纳米复合体系,即Pro@Fe-MSNs/TA Nps。
Pro@Fe-MSNs:TA的质量比为100:0.15-1500,最优比为100:15。
进一步称取100mg Pro@Fe-MSNs Nps分散于1-100mL(最优体积10ml)磷酸缓冲盐溶液中(PBS,pH=7.4),向其中滴加0.5 -50mL浓度0.3-30mg/mL(最优体积5mL最优浓度3mg/mL)单宁酸的磷酸缓冲盐溶液,进行搅拌反应。
本发明的有益效果是:本发明利用Fe3+与介孔二氧化硅及单宁酸的配位键合作用,构成具有pH响应的亲水性可降解Janus型农药载体。由于靶标致病菌如立枯丝核菌等真菌在培养过程中会酸化培养基增加自身定植,纳米粒子在酸性环境下自身发生pH响应,在载体降解的同时缓控释放咪鲜胺,达到持续杀菌的效果。通过有效的控制药物的缓释,提高了农药的使用效率,增强了农药的药效,减少了农药及载体过度累积对环境可能造成的污染。
附图说明
图1.纳米粒子Pro@Fe-MSNs/TA合成和释放示意图;
图2(a)Fe-MSNs,(b)Pro@Fe-MSNs/TA纳米粒子透射电镜及对应EDS分析图图3Fe-MSNs,Pro@Fe-MSNs及Pro@Fe-MSNs/TA纳米粒子Zeta电位图图4Fe-MSNs,Pro@Fe-MSNs及Pro@Fe-MSNs/TA纳米粒子X射线衍射图谱图5Fe-MSNs,Pro@Fe-MSNs及Pro@Fe-MSNs/TA纳米粒子傅里叶红外图谱图6不同的纳米粒子在番茄叶片表面接触角及图像;
图7Pro@Fe-MSNs(a)及Pro@Fe-MSNs/TA(b)纳米粒子不同pH条件下累积释放曲线
图8Fe-MSNs(a),Pro@Fe-MSNs(b)及Pro@Fe-MSNs/TA(c)纳米粒子中Fe元素XPS能谱图;
图9Pro@Fe-MSNs/TA纳米粒子在pH=4时72h降解图
图10Pro@Fe-MSNs/TA纳米粒子对立枯丝核菌7天杀菌活性图及抑菌率图。
具体实施方式
下面结合实施例对本发明做进一步说明,但本发明并不限于以下实施例。
实施例1:
1、Fe-MSNs的制备
称取0.58g CTAB溶解于300mL 0.51mol/L的氨水中,加热至40℃并持续搅拌至表面活性剂完全溶解,缓慢加入稀释的正硅酸乙酯(0.2mol/L溶于5mL乙醇)搅拌5小时,随后缓慢加入硝酸铁和正硅酸乙酯(Si/Fe摩尔比为30:1;67.3mg九水合硝酸铁溶于5mL乙醇)并持续搅拌2小时。随后,将反应后的溶液置于反应釜内40℃下老化16小时,并收集纳米颗粒。最后,使用0.3g硝酸铵在50mL异丙醇中于80℃下过夜回流纳米颗粒除去CTAB模板。
2、金属介孔硅负载咪鲜胺纳米体系的制备
(1)将咪鲜胺分散到正己烷溶剂中,浓度为5mg/mL。
(2)称取100mg Fe-MSNs于圆底烧瓶中,加入咪鲜胺的正己烷溶液,室温下磁力中速搅拌14小时后6500rpm离心,并用正己烷洗涤2-3次,35℃下真空干燥8小时,得到介孔硅负载咪鲜胺纳米体系,即Pro@Fe-MSNs Nps。咪鲜胺与Fe-MSNs的质量比为1:1。
3、亲水性金属介孔硅负载咪鲜胺纳米体系的制备
称取100mg Pro@Fe-MSNs Nps分散于10mL磷酸缓冲盐溶液中(PBS,pH=7.4),向其中滴加5mL浓度3mg/mL单宁酸的磷酸缓冲盐溶液,室温下持续搅拌1小时,6000rpm离心,并用PBS缓冲液洗涤三次,35℃下真空干燥12小时,得到金属介孔硅—单宁酸负载咪鲜胺纳米复合体系,即Pro@Fe-MSNs/TA Nps。
使用投射电子显微镜(TEM)观察纳米粒子的形态并对纳米粒子进行元素分析(图2),TEM中可清洗观察到Fe-MSNs具有典型的Janus型结构,尺寸较小,表面较光滑,B中看出Pro@Fe-MSNs/TA仍保持其形貌,具有纳米级尺寸,但表面变为粗糙,说明载药及修饰单宁酸后并没有破坏Fe-MSNs的形貌及尺寸大小,且咪鲜胺成功装载及单宁酸成功接枝。EDS图表明Fe粒子成功装载。
图3为三种纳米颗粒Zeta电位图,表1为三种纳米颗粒粒度表,通过DLS测得纳米颗粒的水合粒径(396.9nm和525.9nm)远大于TEM拍摄得出的测量值,是由于纳米颗粒在水中发生聚沉导致。在水溶液中,受Fe-MSNs表面硅羟基影响,因此Fe-MSNs电荷为负,装载模型药物Pro后,由于Pro带正电荷,因此Zeta电位数值有所上升,接枝单宁酸后,由于丹宁酸中含有大量羟基,导致纳米粒子Zeta电位值下降。
图4为Pro@Fe-MSNs/TA等纳米粒子的X射线衍射图,从上往下分别为Fe-MSNs,Pro@Fe-MSNs和Pro@Fe-MSNs/TA的小角XRD图。从图可以看出,样品Fe-MSNs在(100)和(110)晶面出现了明显的布拉格衍射峰,该峰为Fe-MSNs的特征峰,说明其具有高度有序的介孔结构;装载药物Pro后,峰强度明显降低,说明药物模型Pro的成功吸附。加入单宁酸后,2θ=2°处的衍射角强度仍出现小幅度下降,说明单宁酸的成功接枝。
图5为Pro@Fe-MSNs/TA等纳米粒子的FT-IR光谱分析,其中约3460cm-1处的峰值可归因于Fe-MSNs表面羟基的O-H拉伸以及物理吸附的水分子,1086cm–1处为–Si–O–C–的不对称伸缩振动吸收峰,795cm–1处为–Si–O–Si–的对称伸缩振动吸收峰,说明目标产物Fe-MSNs制备成功。咪鲜胺在1720cm-1处具有特征吸收峰,装载咪鲜胺后,Pro@Fe-MSNs在1720cm-1处具有Pro特征吸收峰,说明药物咪鲜胺成功装载。
以咪鲜胺原药(5mg溶于50mL水,Pro(a))为阳性对照,将含有相同咪鲜胺活性浓度的纳米药物Pro@Fe-MSNs(c)和Pro@Fe-MSNs/TA(d)分别缓慢滴在番茄植物叶片上,空载体Fe-MSNs(b)为阴性对照(与样品中纳米载体浓度相同),采用动态接触角测试仪检测液滴1分钟的动态接触角(图6)。从室温下生长的番茄植物上摘取大小相似的叶片并用去离子水冲洗2-3次以去除叶表杂质,干燥后固定于载玻片上,用接触角仪器测量叶片上的纳米药滴的接触角。分别将2μl Pro,Fe-MSNs、Pro@Fe-MSNs和Pro@Fe-MSNs/TA纳米粒子的水分散液滴滴加到叶表面上,从刚滴落开始计时到滴落1分钟,捕获叶片表面液滴的图像并得到接触角度数。结果显示Pro@Fe-MSNs/TA相较于Fe-MSNs及Pro@Fe-MSNs接触角明显减小,在叶面的铺展性更好,说明了单宁酸提高了纳米药物在番茄叶面上的浸润性,增强了亲水性。
实施例2
对于Pro@Fe-MSNs/TA纳米粒子的载药率进行测定。称取10mg Pro@Fe-MSNs/TA于烧瓶中,加入30mL甲醇溶液,使用细胞破碎仪超声2h后,7000rpm离心8min后取上清,利用公式进行计算。通过高效液相色谱法(HPLC)进行检测,检测条件,流动相:乙腈:0.2%的乙酸水=70:30,进样体积V=10μL,波长220nm,柱温30℃,保留时间约9min。经计算,Pro@Fe-MSNs、Pro@Fe-MSNs/TA中Pro载药量均为27.1%。
对具有相同载药率的Pro@Fe-MSNs和Pro@Fe-MSNs/TA两种纳米粒子的累计释放率进行测定(见图7中的a和b),分别称量3组5mg Pro@Fe-MSNs/TA均匀混悬于2mL pH值分别为4.0、7.0、10.0的含有0.1%吐温-80的去离子水中,将悬浮液转移至透析袋中,将透析袋密封于50mL以含有0.1%吐温-80的去离子水作为释放介质的石英烧杯(100mL,19.6cm2)中,模拟酸性、中性及碱性环境下的释放,将烧杯置于100rpm的摇床中。图7中可看出接枝单宁酸前,药物在12h内大量突释,在酸性条件下释放量大于中性及碱性,由于Fe-MSNs框架不稳定,酸性条件下容易被H+破坏,导致药物突释,接枝单宁酸后由于单宁酸与Fe-MSNs表面铁离子的相互作用及沉积率增加,导致单宁酸对Fe-MSNs框架的具有一定的稳固作用,咪鲜胺突释显著降低(图7中b)。
为了进一步验证单宁酸与Fe-MSNs表面铁离子发生相互作用,利用X射线光电子能谱(XPS)分析了铁元素的能量变化。如图8中a所示,能谱中出现了Fe元素对应的峰值发生偏移,图8中b、c中Fe2p1的电子能在Pro的装载后,由725.89eV偏移至725.22eV,,接枝单宁酸后又偏移至725.57eV,Fe2p3的电子能在装载Pro后,由712.29eV偏移至711.62eV,接枝单宁酸后又偏移至711.97eV,表明Pro及单宁酸均可能分别与Fe-MSNs孔内部及表面的Fe元素发生相互作用。
为验证Pro@Fe-MSNs/TA纳米体系的可降解性,利用透射电镜(TEM)图像直接监测了Pro@Fe-MSNs/TA在pH为4.0时不同时间下生物降解过程中的结构演变和形态变化,Pro@Fe-MSNs/TA纳米体系在12小时时结构依然保持稳定,但在24小时、48小时及72小时Pro@Fe-MSNs/TA的结构已发生明显变形,见图9;在酸性条件下,Pro@Fe-MSNs/TA骨架中螯合的Fe3+的配位键被H+破坏导致了纳米结构的崩解和Pro释放。
图10为装载咪鲜胺的单宁酸封端Fe-MSNs的杀菌活性,图10第一行为Pro@Fe-MSNs/TA对立枯丝核菌7七天的杀菌效果,第二行为咪鲜胺原药对立枯丝核菌7天的杀菌效果作为对照,与对照组相比,当活性成分Pro含量为0.05mg/L时,其抑制率在7d时增加了18.4%,这是由于纳米系统中Pro的持续释放。数据表明,该体系对真菌的生长抑制率优于Pro,可能原因是该体系粒径较小,水分散性提高,与菌丝的接触机会增多,更容易渗透到菌丝中起到杀菌效果。纳米粒子Pro@Fe-MSNs/TA对Pro具有保护性和pH响应性,能在初始阶段有效保护咪鲜胺活性成分,不被真菌过早降解。而立枯丝核菌等致病性真菌在培养过程中由于分泌代谢产物会酸化培养基增加自身定植,纳米粒子在酸性环境下自身发生pH响应,在载体降解的同时缓控释放咪鲜胺,达到持续杀菌的效果。此外,由于单宁酸的包被,对Fe-MSNs框架的具有一定的稳固作用,使咪鲜胺突释显著降低,促进了药物的缓控释放,使药物能够维持在一定浓度水平,因此,与原药对照相比,表现出较好的抑制效果。
表1
Claims (7)
1.一种多功能Janus型介孔二氧化硅纳米药肥的制备方法,其特征在于,包括以下步骤:
(1)Fe-MSNs的制备
将十六烷基三甲基溴化铵CTAB溶解于氨水中,加热并持续搅拌至表面活性剂完全溶解,缓慢加入乙醇稀释的正硅酸乙酯TEOs搅拌至少4小时,随后缓慢加入硝酸铁和再次加入乙醇稀释正硅酸乙酯并持续搅拌至少1小时;随后,将反应后的溶液置于反应釜内40℃下老化16小时,并收集纳米颗粒;最后,使用硝酸铵的异丙醇溶液于80℃下过夜回流纳米颗粒除去CTAB模板;
CTAB:第一次添加TEOs的摩尔比为0.1-10:1;硝酸铁和第二次加入TEOs体系中Si/Fe的摩尔比为15-150:1;两次加入TEOs摩尔比第一次n:第二次n为0.21:0.5-5;
(2)金属介孔二氧化硅负载咪鲜胺纳米体系(Pro@Fe-MSNs)的制备
将杀菌剂咪鲜胺Pro分散到正己烷溶剂中,咪鲜胺在正己烷的浓度为1-20mg/mL;称取Fe-MSNs于反应器中,加入咪鲜胺的正己烷溶液,室温下磁力中速搅拌14小时后离心,并用正己烷洗涤2-3次,真空干燥得到介孔硅负载咪鲜胺纳米体系,即Pro@Fe-MSNs Nps;咪鲜胺与Fe-MSNs的质量比为(0.5-2):1;
(3)亲水性金属介孔硅负载咪鲜胺纳米体系Pro@Fe-MSNs/TA的制备
称取Pro@Fe-MSNs Nps分散于pH=7.4的磷酸缓冲盐溶液PBS中,向其中滴加单宁酸的磷酸缓冲盐溶液,室温下持续搅拌1小时,离心,并用PBS缓冲液洗涤三次,真空干燥,得到金属介孔硅—单宁酸负载咪鲜胺纳米复合体系,即Pro@Fe-MSNs/TA Nps;
Pro@Fe-MSNs:TA的质量比为100:0.15-1500。
2.按照权利要求1所述的一种多功能Janus型介孔二氧化硅纳米药肥的制备方法,其特征在于,步骤(1)中两次加入TEOs摩尔比第一次n:第二次n为0.21:1。
3.按照权利要求1所述的一种多功能Janus型介孔二氧化硅纳米药肥的制备方法,其特征在于,步骤(2)中咪鲜胺在正己烷的浓度为5mg/mL;咪鲜胺与Fe-MSNs的质量比为1:1。
4.按照权利要求1所述的一种多功能Janus型介孔二氧化硅纳米药肥的制备方法,其特征在于,步骤(3)中Pro@Fe-MSNs:TA的质量比为100:15。
5.按照权利要求1所述的一种多功能Janus型介孔二氧化硅纳米药肥的制备方法,其特征在于,步骤(3)的具体步骤:称取100mg Pro@Fe-MSNs Nps分散于1-100mL、pH=7.4的磷酸缓冲盐溶液PBS中,向其中滴加0.5-50mL浓度0.3-30mg/mL单宁酸的磷酸缓冲盐溶液,进行搅拌反应。
6.按照权利要求1-5任一项所述的方法制备得到的一种多功能Janus型介孔二氧化硅纳米药肥。
7.按照权利要求1-5任一项所述的方法制备得到的一种多功能Janus型介孔二氧化硅纳米药肥的应用,分散于水中,由于靶标致病菌在培养过程中会酸化培养基增加自身定植,纳米粒子在此酸性环境下自身发生pH响应,在载体降解的同时缓控释放咪鲜胺,达到持续杀菌的效果。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111251723.5A CN114009444B (zh) | 2021-10-26 | 2021-10-26 | 一种多功能Janus型介孔二氧化硅纳米药肥的制备及应用 |
LU502502A LU502502B1 (en) | 2021-10-26 | 2022-07-13 | Preparation method and characteristic of novel multifunctional janus-type mesoporous silica nano-pesticide fertilizer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111251723.5A CN114009444B (zh) | 2021-10-26 | 2021-10-26 | 一种多功能Janus型介孔二氧化硅纳米药肥的制备及应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114009444A CN114009444A (zh) | 2022-02-08 |
CN114009444B true CN114009444B (zh) | 2023-04-25 |
Family
ID=80057804
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111251723.5A Active CN114009444B (zh) | 2021-10-26 | 2021-10-26 | 一种多功能Janus型介孔二氧化硅纳米药肥的制备及应用 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN114009444B (zh) |
LU (1) | LU502502B1 (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114806544A (zh) * | 2022-05-28 | 2022-07-29 | 南昌大学 | 一种基于活化炔点击反应的发光纳米粒子及其制备方法 |
CN115836679B (zh) * | 2022-10-20 | 2024-05-24 | 江苏艾津作物科技集团有限公司 | 一种对叶片具有粘附性及pH响应性的农药及其制备方法 |
CN116730770B (zh) * | 2023-04-23 | 2024-02-02 | 北京工业大学 | 一种智能化可降解型硅基纳米药肥及其制备方法和应用 |
CN117247302B (zh) * | 2023-09-22 | 2024-05-14 | 锦州硕丰农药集团有限公司 | 一种新型缓控释多元农药肥料混合肥及其制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112262850A (zh) * | 2020-10-27 | 2021-01-26 | 扬州大学 | 一种pH响应吡唑醚菌酯控释剂及其制备方法和应用 |
-
2021
- 2021-10-26 CN CN202111251723.5A patent/CN114009444B/zh active Active
-
2022
- 2022-07-13 LU LU502502A patent/LU502502B1/en active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
CN114009444A (zh) | 2022-02-08 |
LU502502B1 (en) | 2023-01-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN114009444B (zh) | 一种多功能Janus型介孔二氧化硅纳米药肥的制备及应用 | |
Xu et al. | Copper ions chelated mesoporous silica nanoparticles via dopamine chemistry for controlled pesticide release regulated by coordination bonding | |
Zhang et al. | Hydrothermal synthesis of Ag nanoparticles on the nanocellulose and their antibacterial study | |
Xiang et al. | Efficient synthesis of starch-regulated porous calcium carbonate microspheres as a carrier for slow-release herbicide | |
Olad et al. | Synthesis, characterization, and fertilizer release study of the salt and pH-sensitive NaAlg-g-poly (AA-co-AAm)/RHA superabsorbent nanocomposite | |
He et al. | Preparation and characterization of double-shelled avermectin microcapsules based on copolymer matrix of silica–glutaraldehyde–chitosan | |
El-Sherif et al. | Hydrogels as template nanoreactors for silver nanoparticles formation and their antimicrobial activities | |
CN110292041B (zh) | 一种纳米农药制剂及其制备方法 | |
El‐Sherbiny et al. | Green synthesis of metallic nanoparticles using biopolymers and plant extracts | |
CN116730770B (zh) | 一种智能化可降解型硅基纳米药肥及其制备方法和应用 | |
Budi et al. | Size-controlled chitosan nanoparticles prepared using ionotropic gelation. | |
CN110746225A (zh) | 一种纳米控释肥及其制备方法 | |
Zhang et al. | An eco-friendly photo-responsive hyaluronic acid-based supramolecular polysaccharide hybrid hydrogels for plant growth regulation and heavy metal ions adsorption | |
CN107828032A (zh) | 一种超支化星状聚离子液体及其制备方法和应用 | |
CN113735175B (zh) | 一种纳米拟酶、制备方法及包含其的种子浸泡剂 | |
Akbari et al. | Controlled delivery of tetracycline with TiO2@ Chitosan@ ZIF-8 nanocomposite and evaluation of their antimicrobial activities | |
CN104843715A (zh) | 二氧化硅不对称修饰磁性胶体颗粒的制备方法 | |
CN113615706A (zh) | 一种水溶性复合缓释剂及其制备方法 | |
WO2023227145A1 (zh) | 一种铂纳米粒的制备方法及其制备的铂纳米粒和铂纳米粒的应用 | |
Hao et al. | Antibacterial Microfibrillated Cellulose as Stimuli-Responsive Carriers with Enhanced UV Stability for Sustained Release of Essential Oils and Pesticides | |
CN116584480A (zh) | 金属有机框架纳米农药控释剂的制备方法及其应用 | |
Zuo et al. | An enzyme-responsive core-double shell structured nano pesticide delivery system for improving the UV stability of emamectin benzoate (EB) | |
CN109512800A (zh) | 一种载药氧化锌二氧化硅复合纳米粒的制备方法 | |
Sipponen et al. | Advances in Preparation and Applications of Lignin Nanoparticles | |
Xu et al. | Rotenone nanoparticles based on mesoporous silica to improve the stability, translocation and insecticidal activity of rotenone |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |