NL2033192A - A Preparation Method of A Nanomaterial with bionic enzymes activity and An Application of the Nanomaterial in Glyphosate Detection - Google Patents
A Preparation Method of A Nanomaterial with bionic enzymes activity and An Application of the Nanomaterial in Glyphosate Detection Download PDFInfo
- Publication number
- NL2033192A NL2033192A NL2033192A NL2033192A NL2033192A NL 2033192 A NL2033192 A NL 2033192A NL 2033192 A NL2033192 A NL 2033192A NL 2033192 A NL2033192 A NL 2033192A NL 2033192 A NL2033192 A NL 2033192A
- Authority
- NL
- Netherlands
- Prior art keywords
- glyphosate
- nanomaterial
- activity
- prussian blue
- fe3o4
- Prior art date
Links
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 116
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 116
- 230000000694 effects Effects 0.000 title claims abstract description 54
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 29
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 26
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 26
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000001514 detection method Methods 0.000 title abstract description 37
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 132
- 229960003351 prussian blue Drugs 0.000 claims abstract description 131
- 239000013225 prussian blue Substances 0.000 claims abstract description 131
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 48
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 239000011258 core-shell material Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 102000003992 Peroxidases Human genes 0.000 claims description 27
- 108040007629 peroxidase activity proteins Proteins 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- 238000002835 absorbance Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 claims description 7
- 238000004042 decolorization Methods 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910018626 Al(OH) Inorganic materials 0.000 claims description 5
- ZTOJFFHGPLIVKC-CLFAGFIQSA-N abts Chemical group S/1C2=CC(S(O)(=O)=O)=CC=C2N(CC)C\1=N\N=C1/SC2=CC(S(O)(=O)=O)=CC=C2N1CC ZTOJFFHGPLIVKC-CLFAGFIQSA-N 0.000 claims description 5
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 5
- 238000004445 quantitative analysis Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 6
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 claims 1
- 241000208125 Nicotiana Species 0.000 abstract description 18
- 235000002637 Nicotiana tabacum Nutrition 0.000 abstract description 18
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 239000002356 single layer Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 229910001868 water Inorganic materials 0.000 description 32
- 239000000523 sample Substances 0.000 description 27
- ZTOJFFHGPLIVKC-YAFCTCPESA-N (2e)-3-ethyl-2-[(z)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound S\1C2=CC(S(O)(=O)=O)=CC=C2N(CC)C/1=N/N=C1/SC2=CC(S(O)(=O)=O)=CC=C2N1CC ZTOJFFHGPLIVKC-YAFCTCPESA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 9
- 238000000975 co-precipitation Methods 0.000 description 9
- 230000005764 inhibitory process Effects 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002055 nanoplate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000019505 tobacco product Nutrition 0.000 description 3
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 description 2
- UCDLBNQQNRQANR-UHFFFAOYSA-N 4-(4-amino-3-methylphenyl)-2,6,6-trimethylcyclohexa-2,4-dien-1-amine Chemical compound CC1(C)C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 UCDLBNQQNRQANR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229910020820 NaAc-HAc Inorganic materials 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910019931 (NH4)2Fe(SO4)2 Inorganic materials 0.000 description 1
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005978 Flumetralin Substances 0.000 description 1
- RXCPQSJAVKGONC-UHFFFAOYSA-N Flumetsulam Chemical compound N1=C2N=C(C)C=CN2N=C1S(=O)(=O)NC1=C(F)C=CC=C1F RXCPQSJAVKGONC-UHFFFAOYSA-N 0.000 description 1
- -1 H:0: (30% w/w) Chemical compound 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000005591 Pendimethalin Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000005940 Thiacloprid Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000005870 Ziram Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000012801 analytical assay Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003593 chromogenic compound Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000007398 colorimetric assay Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 238000010982 kinetic investigation Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000015205 orange juice Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical class [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/003—Catalysts comprising hydrides, coordination complexes or organic compounds containing enzymes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
- C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
- C12Q1/26—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving oxidoreductase
- C12Q1/28—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving oxidoreductase involving peroxidase
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
- H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
- H01F1/0054—Coated nanoparticles, e.g. nanoparticles coated with organic surfactant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Immunology (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Pathology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Biotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Genetics & Genomics (AREA)
- Composite Materials (AREA)
- General Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Plasma & Fusion (AREA)
- Microbiology (AREA)
- Biophysics (AREA)
- Biomedical Technology (AREA)
- Power Engineering (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The present invention discloses a preparation method of a nanomaterial with bionic enzymes activity and an application of the nanomaterial in glyphosate detection, where the nanomaterial with bionic enzymes activity is prepared by decorating Fe3O4 nanoparticles with a heptanic acid and Prussian blue to obtain Fe3O4@C7/PB with a core-shell structure in which the core is Fe3O4 and the shell is composed of the heptanoic acid and the Prussian blue. The present invention has a beneficial effect that a nanozyme (Fe3O4@C7/PB) with peroxisase-like activity is synthesized from heptanoic acid and Prussian blue decorated Fe3O4 nanoparticles, which has higher peroxisase-like activity than Fe3O4@C7, and Fe3O4@C7/PB may be stabilized against agglomeration by a monolayer of PB. We establish an anti-interference smartphone-assisted nanosensing platform based on the peroxise-like activity of the heptanoic acid and Prussian blue (PB) decorated Fe3O4 nanoparticles (Fe3O4@C7/PB) for the determination of glyphosate content in tobacco, where a limit of detection of the platform is 0.1ug mL'l.
Description
A Preparation Method of A Nanomaterial with bionic enzymes activity and An Application of the Nanomaterial in Glyphosate Detection
TECHNICAL FIELD The present invention relates to the technical field of chemical analysis and detection, in particular to a preparation method of a nanomaterial with bionic enzymes activity and an application of the nanomaterial in glyphosate detection.
BACKGROUND Glyphosate is a high-efficiency and broad-spectrum non-selective sterilant herbicide, which has been widely used in many fields, especially agriculture, due to its high conductivity, cost-effectiveness, and systemic killing efficiency. Glyphosate has become one of the world's top-ranked herbicides and its usage is still on increase. Although there are controversies about glyphosate toxicity at present, large amounts of glyphosate residues are easy to produce potential toxicity to animals and humans through the food chain, and it is reported that there are still cases of poisoning. China, U.S. Environmental Protection Agency, and the European Union have all set limits for glyphosate residues. Glyphosate is an amino acid herbicide with strong polarity, insoluble in general organic solvents, lacks chromogenic and fluorescent groups, and has a strong binding ability with organic compounds in plants, which makes it difficult to directly analyze. Up to now, traditional analytical techniques have been developed for glyphosate detection, including mass spectrometry, electrochemistry, ion chromatography, and fluorescent spectrometry, with various derivation methods. Nanomaterials with bionic enzymes activity (i.e. nanozymes) are generally mass-produced, low in cost, and stable compared to natural enzymes and are promising candidates for the detection of pesticides. Colorimetric sensing based on the catalytic oxidation of chromogenic substrates even trace amounts of targets by nanozymes is reported. About colorimetric nanozymes for pesticides detection, most are based on the inhibition of nanozymes activity. Luo et al. proposed a facile colorimetric nanozyme sheet for the rapid detection of glyphosate in agricultural products based on inhibiting peroxidase-like catalytic activity of porous Co30: nanoplates. Liu et al. developed a system composed of polyethylenimine-capped upconversion nanoparticles, copper (II), hydrogenperoxide and 3,3',5,5 -tetramethylbenzidine for colorimetric and fluorometric determination of glyphosate. Yan et al. established a colorimetric assay for the detection of organophosphorous pesticides by use of peroxidase (POD)-mimicking FesOq nanoparticles. Since the first report of Fe;O4 nanoparticles in 2007, the research scope has rapidly expanded to a large variety of nanomaterials, and the Fe304 nanoparticles also are decorated with various functional groups to improve the enzymes activity. Similar to Fe;O4, Prussian blue (PB) also consists of mixed valence states of Fe with a high POD-like activity. Therefore, colorimetric and fluorometric sensing platforms have terrific application prospects. Although current methods for detecting glyphosate have high sensitivity, the sample preparation is more complicated for complex samples and these methods are not applicable for rapid and onsite detection. Moreover, the catalytic activity of nanomaterials is also easily affected by the surrounding conditions for complex samples. To address these problems, some analytical techniques have been developed like pretreatment technology and smartphone-assisted sensing platform. A smartphone with a high-resolution camera working as a color shooter has developed into a comprehensive tool for receiving, processing, and displaying data for biochemical or chemical substances detection.
SUMMARY For overcoming the shortcomings of the prior art, the present invention provides a preparation method of a nanomaterial with bionic enzymes activity and an application of the nanomaterial in glyphosate detection.
The purpose of the present invention is achieved by the following technical solution: A preparation method of a nanomaterial with bionic enzymes activity is provided, where the nanomaterial is of a core-shell structure, and prepared by decorating Fe;O4 nanoparticles with a heptanic acid and Prussian blue to obtain Fe304@C7/PB with a core-shell structure in which the core is Fe3O4 and the shell is composed of the heptanoic acid and the Prussian blue.
Preferably, in a N; atmosphere, a heptanoic acid, ammonia, and Prussian blue are added into a liquid mixture of ammonium ferrous sulfate and ferric trichloride to react and then obtain a precipitate containing the nanomaterial Fe30:@C7/PB with bionic enzymes activity.
Preferably, the reaction time is 0.5-2 h, and the reaction temperature is 60-90°C.
Preferably, the molar ratio of the ammonium ferrous sulfate to the ferric trichloride, the heptanoic acid, the ammonia and the Prussian blue in reaction solution is 1:1-1.4:0.16-0.19:0.003-0.004:4-5.
Preferably, the precipitate is magnetically separated and cleaned to obtain Fe;04@C+/PB.
A method for detecting glyphosate by use of the nanomaterial with bionic enzymes activity includes determination of glyphosate in samples: a sample to be detected is added into a FesOu@C+/PB+H:0;+peroxidase substrate system, and quantitative analysis of glyphosate is performed by monitoring the color or absorbance changes of the system.
Preferably, the method also includes standard curve drawing: color images of the Fe30:(@C7/PB+H20:+peroxidase substrate system with different glyphosate concentrations are taken, RGB values of the color images are acquired and converted to gray values, and a linear relationship between different glyphosate concentrations and gray values is established; alternatively, the absorbance of the Fe30:4@C7/PB+H:O:+peroxidase substrate system with different glyphosate concentrations is determined, and a linear relationship between different glyphosate concentrations and absorbance is established.
Preferably, the method also includes sample pretreatment, the sample pretreatment comprises extraction and decolorization, and the decolorization step is implemented by adding Al(OH); solution and NaOH solution into extracting solution, and supernatant is taken for determination of glyphosate.
Preferably, the peroxidase substrate is 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) or 3,3',5,5 -tetramethylbenzidine.
Preferably, the pH value of the Fe30:@C7/PB+H20:+peroxidase substrate system is
1.9-2.2, where the H»O: concentration is 1.5-2.5 mM, the peroxidase substrate concentration is 0.15-0.25 mM, and the Fe;04(@C+/PB concentration is 11-14 pg mL".
Preferably, the samples include tea, tobacco, soil and environmental water samples.
The present invention has the following advantages: a nanozyme (Fe:O4@C+/PB) with peroxisase-like activity is synthesized from heptanoic acid and Prussian blue decorated Fe;Os nanoparticles, which has higher peroxisase-like activity than Fe30:@C7, and Fe;04@C+/PB may be stabilized against agglomeration by a monolayer of PB. For glyphosate assays in tobacco products, a potential problem is false-negative results caused by the complex matrix. Herein, we establish an anti-interference smartphone-assisted nanosensing platform based on the peroxidase-like activity of heptanoic acid and Prussian blue (PB) decorated Fe30: nanoparticles (Fe304@C7/PB) for glyphosate assays in tobacco, where the limit of detection of the platform is 0.1 pg mL! | and three characteristic absorption peaks are observed at 416 nm, 647 nm and 730 nm. As-synthesized Fe:04(@C7/PB exhibits excellent peroxidase-like activity compared to Fe;0u, which is evaluated using 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as a substrate in the presence of HO». Furthermore, the catalytic activity of Fe;O4(@C-/PB is inhibited even by trace amounts of glyphosate. Glyphosate molecules may occupy active sites on the surfaces of porous Fe;04@C+/PB nanoparticles, which can block the conversion of HO: to OH, leading to the delicate color change of ABTS. By monitoring the color change of ABTS, the glyphosate concentration can be detected within 10 min. According to the color changes, a colorimetric quantitative method is developed and employed for glyphosate quantitation by combining the RGB color mode with the smartphone technology. Due to its simple operation, low cost, and fast response, the method has a great potential for on-site evaluation of glyphosate.
BRIEF DESCRIPTION OF THE FIGURES FIG. 1 shows a TEM image of the prepared Fe;04@C7 (A); a TEM image of the prepared Fe30:4@C7/PB (B), XRD patterns of Fe;04@C7 and Fe304(@C7/PB (C); FTIR spectra of Fe;04@C7 and Fe304@C7/PB (D); survey XPS spectra of Fe;04@C7 and Fe;04(@C+/PB (E); and a core-level spectrum of Fe 2p in a Fe;s04@C+/PB composite (F). FIG. 2 shows UV-Vis absorption spectra of the catalytic activity of Fe;04@C+/PB to TMB and ABTS (A); the inhibition of glyphosate on different systems (B); the catalytic activity of three different materials (Fe:O4, Fe;04@C7 and Fe;04(@C7/PB) on TMB (C); and UV absorption spectra of the oxidation of TMB in the presence of Fe304, Fe304@C: and Fe;04@C+/PB (D).
FIG. 3 shows steady-state kinetic analysis of Fe:O4@C7 and Fe:0:@C+/PB Peroxidase mimetics. Fe304(@C:: (A) Curve of velocity against the TMB concentration in the presence of H;0:; (C) Curve of velocity against the H>O; concentration in the presence of TMB; and (B, D) Double-reciprocal plots of (A, C). Fe;04@C+/PB: (E) 5 Curve of velocity against the TMB concentration in the presence of H:0:; (G) Curve of velocity against the H>O: concentration in the presence of TMB; and (F, H) Double-reciprocal plots of (A, C).
FIG. 4 shows the fluorescence spectra for the interaction of TA with different systems (A); and the elution effect of different eluents on FesOu@C-/PB-adsorbed glyphosate (B), 1: blank; 2: water; 3: 1% NaOH aqueous solution; 4: Ethanol; 5: 1% NaOH ethanol solution; and Raman spectra of the different systems (C).
FIG. 5 shows an purification effect of a co-precipitation method on tobacco samples (A); and UV-Vis absorption spectra of a tobacco sample before and after purification (B).
FIG. 6 shows the colorimetric signal change of a Fe30:@C7/PB+H:0,+ABTS system with different glyphosate concentrations. Inset: the color change of the nanozyme catalytic system (A), and a linear relationship between glyphosate concentration and absorbance (B).
FIG. 7 shows specificity of a color sensing platform for glyphosate detection (A); the interference of three kinds of phosphates (B); the effect of IP, CaCl, and IP+CaCl: on the color sensing platform (C); and UV—Vis absorption spectra of the color sensing platform with IP, CaCl: and IP+CaCly, respectively (D). Inset: the color changes of the color sensing platform with IP, CaCl, and IP+CaCl:.
FIG. 8 shows a linear relationship between smartphone readout gray values and glyphosate concentrations (A); and a linear relationship between smartphone readout gray value and glyphosate concentration (B).
FIG. 9 shows a schematic diagram of colorimetric sensors for glyphosate detection.
DESCRIPTION OF THE INVENTION To illustrate the purpose, technical solutions and advantages of the embodiments of the present invention more clearly, the following clearly and completely describes the technical solutions in the embodiments of the present invention with reference to the accompanying figures in the embodiments of the present invention. Apparently, the described embodiments are merely a part rather than all of the embodiments of the present invention. The units of the embodiments of the present invention commonly described and shown in the accompanying figures here may be laid out and designed in various configurations.
Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying figures is not intended to limit the scope of the present invention for which protection is claimed, but merely to indicate the selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
It is to be appreciated that the embodiments and the features in the embodiments of the present invention may be combined with each other in the absence of conflicts.
It should be noted that similar labels and letters indicate similar terms in the following accompanying figures, so once an item is defined in one accompanying figure, it does not need to be further defined and explained in subsequent accompanying figures.
The present application provides a preparation method of a nanomaterial with bionic enzymes activity, where the nanomaterial is of a core-shell structure, and prepared by decorating Fes;Os nanoparticles with a heptanic acid and Prussian blue to obtain Fe:0:@C7/PB with a core-shell structure in which the core is FesOs and the shell is composed of the heptanoic acid and the Prussian blue, specifically, in a N» atmosphere, a heptanoic acid, ammonia, and Prussian blue are added into a liquid mixture of ammonium ferrous sulfate and ferric trichloride to react and then obtain a precipitate containing the nanomaterial Fe:0:@C7/PB with bionic enzymes activity, and the precipitate is magnetically separated and cleaned to obtain Fe;O0:4@C+/PB; where the reaction time is 0.5-2 h, and the reaction temperature is 60-90°C.
The present application also provides a method for detecting glyphosate by use of the nanomaterial with bionic enzymes activity, which includes standard curve drawing, sample pretreatment and determination of glyphosate in samples, standard curve drawing: color images of the Fe3:0:@C7:/PB+H20O:+peroxidase substrate system with different glyphosate concentrations are taken, RGB values of the color images are acquired and converted to gray values, and a linear relationship between different glyphosate concentrations and gray values is established, alternatively, the absorbance of the Fe30:4@C7/PB+H:O:+peroxidase substrate system with different glyphosate concentrations are determined, and a linear relationship between different glyphosate concentrations and absorbance is established: sample pretreatment: the sample pretreatment includes extraction and decolorization, and the decolorization step is implemented by adding Al(OH); solution and NaOH solution into extracting solution, and supernatant is taken for determination of glyphosate; determination of glyphosate in samples: a sample to be detected is added into the Fe30:@C:/PB+H20:+peroxidase substrate system, and quantitative analysis of glyphosate is performed by monitoring the color or absorbance changes of the system; where the peroxidase substrate is 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) or 3,3 5,5-tetramethylbenzidine, and the pH value of the Fe:0:@C7/PB+H20:+peroxidase substrate system is 1.9-2.2, where the HzO» concentration is 1.5-2.5 mM, the peroxidase substrate concentration 1s 0.15-0.25 mM, and the Fe;04(@C+/PB concentration is 11-14 ug mL", and the samples may include tea, tobacco, soil and environmental water samples.
Embodiments:
1. Materials All reagents are commercially available, of analytical grade and used as received unless otherwise indicated. (NH:)2Fe(S0:)2:6H20, heptanoic acid, Prussian blue (PB), FeCl;:6H;0, NH; H:0 (25%w/w), 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), H:0: (30% w/w), glyphosate and other competitive organophosphorus pesticides (OPs) are supplied from Aladdin Industrial Corporation (Shanghai, China). Terephthalic acid (TA) is purchased from Shanghai Macklin Biochemical Co., Ltd. (Shanghai, China). Deionized water used in experiments is prepared by ultra-pure water equipment (18.23 MQ-cm, UPT-II, Ulupure, China).
2. Instrumentation The morphology and microstructure of Fe30:4@C7/PB are observed on a TecnaiG2 TF30 transmission electron microscope (TEM) with an accelerating voltage of 200 kV (FEL USA). UV-Vis absorption spectra are determined on a TU-1901 double beam UV-visible spectrophotometer from Beijing Persee General Analysis Instrument Co., Ltd (Persee, China).
3. Synthesis of Fe;O4@C+/PB nanoparticles A one-pot synthesis method is used for the preparation of Fe304@C7/PB. Initially,
3.38 g of (NH4)2Fe(SO4)2:6H20 and 2.82 g of FeCl3:6H20 are dispersed in 80 mL of deionized water. In a N; atmosphere, suspension is heated at 80°C with vigorous stirring. Then, 200 mg of a heptanoic acid (dissolved in 5 mL of acetone), 5 mL of NH; H:0 (28%, w/v) and 200 mg Prussian blue (PB) are added gradually into the solution, respectively. The obtained mixture is kept for 1 h at 80°C. After cooling down to room temperature, the obtained precipitate is magnetically separated and washed with deionized water followed by ethanol. The precipitate is lyophilized to turn it into powder. Finally, the obtained powder is redispersed in water, and the concentration of nanomaterials is set to 3.24 mg mL"! The usages of various reactants in this embodiment may fluctuate within a certain range, for example, the molar ratio of the ammonium ferrous sulfate to the ferric trichloride, the heptanoic acid, the ammonia and the Prussian blue is 1:1-1.4:0.16-0.19:0.003-0.004:4-5, and Fe30:4@C7PB nanoparticles may be obtained by magnetic separation once they can be generated in the reaction solution.
In this embodiment, with consideration of the reaction rate and the precipitation rate, the reaction temperature is set to 60-90°C. The precipitation rate is fast within 0.5 h of the reaction, and the precipitation can be completed in about 2 hours, however, with consideration of the reaction rate, the optimal reaction time, i.e., precipitation time, is 1 h.
4. Kinetic tests on Fe:0:@C7/PB Under optimal conditions, a kinetic investigation on the POD-like performance of Fe304(@C-7/BB is studied by varying TMB and H:0: concentrations. Firstly, an analysis is studied by using Fe30:@C7/PB (3.24 mg mL") with a fixed HO: concentration (50 mM) and varied TMB concentrations (0.0625, 0.125, 0.1875, 0.25, 0.3125, 0.375,
0.4375, 0.5, 0.5625, 0.625 mM). Then, with HO: as a substrate, a test is studied by using Fe30:@C7/PB (3.24 mg mL") with a fixed TMB concentration (0.25 mM) and varied H>O: concentrations (0.625, 1.25, 1.875, 2.5, 3.125, 3.75). Kinetic parameters are calculated according to the Michaelis-Menten equation:
i Vn f Lis where J refers to initial velocity, Vu. refers to maximal reaction velocity, [S] refers to substrate concentration, and K, refers to Michaelis constant. The K value and Va value of the POD-like activity of Fe:04@C7/PB, with TMB and H:0: as substrates, are calculated respectively.
5. Peroxidase-like catalytic activity of Fe;0:@C+/PB The peroxidase-like activity of Fe304@C+7/PB is investigated through employing it to catalyze some chromogenic reactions. Typically, 50 uL of S mM ABTS solution, 50 uL of (30%) H20: solution and 50 uL of 1 mg mL"! Fe;04@C+/PB solution are added into 2.5 mL of 0.1 M NaAc-HAc buffer (pH 2.0). The UV-Vis spectra and absorbance values are recorded at a fixed wavelength (416 nm) for analysis.
The buffer in this embodiment is to ensure the stability of the system and color development, those skilled in the art may choose other kinds of buffer according to the situations. The usage of each component in the system can also fluctuate within a certain range, but to ensure the sensitivity of glyphosate detection, an optimal usage is chosen in this embodiment.
6. Smartphone-based detection of glyphosate A detection experiment is carried out in an aqueous medium. Firstly, 50 uL of 5 mM ABTS solution, 50 pL of (30%) H.0; solution and 50 pL of 1 mg mL" Fe;04@C+/PB solution are added into a prepared sample. Then, a 0.1 M NaAc-HAc buffer (pH 2.0) is added to adjust the volume of the obtained liquid mixture to 2.5 mL. After the color changed, images are captured by the camera of the smartphone. The obtained color images corresponding to different glyphosate concentrations are instantaneously converted by an installed color picker APP into digital values regarding red (R), green (G), and blue (B) color channels for the onsite quantitative analysis of glyphosate. Finally, an inhibition efficiency (IE, %) is applied to assess the inhibitory effects and calculate the glyphosate content. Inhibition efficiency (%) is calculated by the following equation: IE (%) = (Ao-Ag) Ao *100, where As and Ao represent the absorbance of the Fe304@C7/PB-ABTS-H20: system at 416 nm in the presence and absence of glyphosate, respectively. The limit of detection (LOD) is determined by the 3c rule. All colorimetric glyphosate measurements are conducted with three replicates.
7. Sample pretreatment For colorless liquid samples, they may be directly added into the Fe304@C7/PB+H20:+peroxidase substrate system, and if a liquid sample is colored, which may affect the detection of glyphosate, it needs to be decolorized, and then added into the Fe:0:@C7/PB+H20:+peroxidase substrate system for determination. For solid samples, glyphosate must be extracted first. The sample pretreatment mode and the sample pretreatment method in this application may be selected by those skilled in the art according to the situations of samples. This embodiment provides an optimal sample pretreatment method.
With a tobacco sample as an example, 1 g of sample powder may be added into 30 mL of deionized water containing 1 mL of NaOH (1 M). After 15 minutes of ultrasound, the obtained yellow solution is centrifuged at 8000 rpm for 5 min. Supernatant is stored at 4°C for subsequent decolorization experiments.
The extract is decolorized by use of the co-precipitation method. Briefly, 300 pL of Al(OH): (0.33 M) is added into 2 mL of the extract. After mixing, 300 uL of NaOH (1 M) is added into the solution, and then the obtained mixture is subjected to vortex mixing for 30s. Then, the mixed solution is centrifuged at 6000 rpm for 5 min. The upper glyphosate extract is used for enzyme inhibition analysis.
To avoid the presence of glyphosate in a yellow precipitate, the study is conducted to reduce the loss of glyphosate through secondary precipitation. 1 mL of deionized water is added into the yellow precipitate. After stirring for 1 min, 300 pL of HCI (1 M) is adopted to dissolve the precipitate. Then, 300 uL of NaOH (1 M) is added for secondary precipitation. After centrifugation, the supernatant of the two extracting solution is combined and stored at 4 °C for subsequent analysis.
8. Results and discussion
8.1. Characterization of Fe:O0:@C7/PB The TEM images shown in FIG. 1A and B reveal the core-shell structures of Fe;04@C7 and Fe:04@C7/PB. After modification with PB, the particles tend to be slightly larger. This may be due to the modified PB on the surface of Fe304@C-.
However, the size increases only a little with increasing PB which may related to the surface decomposition of Fe:04@C7 in the reaction process. The prepared Fe304@C-/PB is stabilized against agglomeration by a monolayer of PB, in the preparation process of Fe:04@C7, the heptanoic acid needs to be added slowly to slow down the agglomeration. In the present application, the PB in this embodiment may be stabilized against agglomeration, so the rate of PB addition may not be controlled. The crystalline structure of Fe;O04@C+/PB is identified by XRD analysis (FIG. IC). The diffraction peaks with 28 of 17.5°, 24.8°, 39.7° and 51.0° are observed, corresponding to the diffraction planes of 200, 220, 400 and 440 respectively. The high-resolution XPS spectra of Fe 2p, C 1s (284 eV), and N Is (401.2 eV) are fitted to Fe30:4@C7/PB and templating organic moiety (FIG. 1E). The fine Fe 2p XPS (FIG. 1F) provides peaks that can be well assigned to Fe** 2pi2, Fe?" 2p12, Fe™ 2psp and Fe?” 2p3;, verifying the mixed valence states of Fe in the collected products. The FTIR spectra (FIG. ID) of AuNPs/CDs and Fe:0:@C+/PB show IR peaks at 2084 cm’! and 1412 cm’! assigning to the y(C=N) stretching mode of PB.
8.2. Peroxidase-like activity of Fe30:@C7/PB The catalytic performance of the prepared Fe304@C7/PB on the peroxidase substrates such as TMB and ABTS is evaluated. As shown in FIG. 2A, green (TMB) or steelblue (ABTS) color may be observed when the Fe:04@C+/PB reacts with H20; at room temperature. An obvious color response for TMB (from colorless to green) and ABTS (from colorless to steelblue) with a maximum absorption peak at 650 nm and 730 nm is observed. In acidic buffer, Fe304@C+/PB shows the highest activity on ABTS, about 5.0 times compared with TMB chromogen (FIG. 2A). Due to the excellent affinity and sensitivity of Fe304@C7/PB towards ABTS, we select ABTS as a chromogenic tool for peroxidase-mimic activity for further quantitative smartphone-based analytical assays. In the absence of H20», the characteristic peaks at 650 nm and 730 nm disappear (FIG. 2A), which illustrates that the Fe:0:@C7/PB shows peroxidase-like activity. As shown in FIG. 2B, if Fe:04@C+/PB is pretreated with SCN” before being introduced into the TMB/H:;0: solution, the PODs activity of the Fe30:@C7/PB will be unreversibly inhibited by SCN”, indicating that Fe-Cx moieties are main active sites to PODs. To further assess the peroxidase-mimicking catalytic efficiency of Fe;04@C+/PB, the enzyme kinetic constants (Km) and the maximum rate (Vmax) are obtained to measure the enzyme efficiency (FIG. 3). When H20: and TMB are taken as substrates, the Km of Fe30:@C7 and Fe304@C7/PB are
1.165 mM and 1.593mM for H20,, 2.104 mM and 1.413 mM for TMB, respectively, which are both clearly lower than that of HRP, suggesting that Fe304@C+/PB exhibits a higher affinity toward the substrates than to HRP. This may be owing to the existence of more “active sites” on the surface of the Fe;04@C+/PB. Table 1 Comparison of the apparent Michaelis Menten constant (X;:) and maximum reaction rate (max) of different NPs TMB H:0: TMB H20: Fe304@C 1.284 1.392 21.04 11.65 Fe304@C7/PB 0.344 0.683 14.13 15.93 HRP 0.434 3.702 10 8.710
8.3. Effect of glyphosate on peroxidase-like activity of Fe30:@C7/PB To investigate the effect of glyphosate on peroxidase-like activity of Fe30:4(@C-7/PB, the absorption spectra of different systems are measured (FIG. 2A and FIG. 2B ). After the addition of glyphosate, the absorption peak at 730 nm in Fe;04@C+/PB +H0.+ABTS+glyphosate is significantly reduced. There is no absorption peak in ABTS+glyphosate and H20:+ABTS+glyphosate systems, which reveals that glyphosate may not achieve the catalytic oxidation of ABTS discoloration and the peroxidase-like activity of Fe;O4@C-/PB may be inhibited by glyphosate. Therefore, the inhibition of Fe;O0s@C-/PB enzymes activity may be developed for glyphosate detection.
8.4. Inhibition mechanism of glyphosate on enzymes activity The Fe:04@C+/PB nanozyme can promote the ‘OH generation by decomposing H>0:, resulting in the oxidation of the substrate ABTS. In the presence of glyphosate, the conversion of H20: to ‘OH may be interrupted through occupying the active sites on the surface of Fes04@C+/PB. To further investigate the inhibition mechanism of glyphosate on catalytic activity of Fe;O4@C+/PB nanozymes, a fluorescence experiment is applied for tracking OH in a Fe304@C+/PB +H:0:2 system. A terephthalic acid (TA) is adopted to captureOH because it can become 2-hydroxyterephthalic acid, a fluorescent agent with peak around 430 nm. As shown in FIG. 4A, the intensity of fluorescence in the Fe;04@C+/PB +H20:+glyphosate system is lower than that of the Fe:0:4@C7/PB +H20: system, indicating that glyphosate may effectively inhibit the production of ‘OH. In addition, no fluorescence is observed when the TA is incubated with Fe;O04@C- nanoplates, suggesting clearly the absence of ‘OH. The generated ‘OH also may be directly detected by an electron paramagnetic resonance (EPR) spectroscopy (FIG. 4B). The Fe30:@C+7/PB +H20: system has a higher signal peak than the Fe30:@C7/PB+H20:+glyphosate system, showing the better catalytic activity of Fe3O4@C7. These results confirm that the peroxidase activity of Fe30:@C7/PB may be inhibited by glyphosate.
The absorbance of the Fe30:@C7/PB+ABTS+H20: system decreases (FIG. 2B) when glyphosate is added into the Fe:0:@C:/PB+ABTS+H20: system. When glyphosate adsorbed on Fe30:@C7/PB is eluted with different eluents (deionized water, 1% NaOH deionized water, ethanol and 1% NaOH ethanol), the absorbance of the Fe:30:@C7/PB-ABTS-H20: system eluted with the 1% NaOH deionized water is best, indicating that the glyphosate adsorbed on Fe;O0:@C+/PB is eluted (FIG. 4B). This phenomenon proves our speculation that the active sites of Fe;04@C+/PB nanozymes are blocked by glyphosate. Surface-enhanced Raman spectroscopy (SERS) is applied to reveal how the active sites are blocked by glyphosate. Au NPs are synthesized according to a reported literature Au NPsfH.l.a.Z.Z. Mingming Han, Fast and Low-Cost Surface-Enhanced Raman Scattering (SERS) Method for On-Site Detection of Flumetsulam in Wheat, Molecules, 25 (2020) 4662]. The SERS spectra show a much stronger Raman signal intensity of Fe304@C7/PB+glyphosatetAu NPs (437, 1344 cm-1) than Au NPs and Fe:0:@C7/PB-Au NPs, and two new signals are observed at 797 and 905 cm’! (FIG. 3C). As can be seen in FIG. 3, the peaks at 437 and 797 cm’! are formed mainly due to the stretching vibration of glyphosate molecules (Gaussian 09 programs, density functional theory at the B3LYP/6-31G(d) level). The results show that a chemical bond may be formed between the surface of Fe;04@C-/PB and the glyphosate.
8.5. Purification and method optimization A color interference of tobacco extract has a great influence on colorimetric results. To improve the accuracy and stability of the proposed on-site test sensing platform, a co-precipitation technology is used to pretreat tobacco samples. As shown in FIG. SA, when Al(OH); and NaOH are added, the color interference is eliminated. To test whether glyphosate may be precipitated by the co-precipitation technology, spiked water and tobacco samples are used to evaluate the co-precipitation purification technology. The glyphosate in the precipitate is also analyzed after being dissolved by use of 1 mL of HCI (1M). As shown in Table 2, the precipitation efficiency of glyphosate is 1.87-3.23%, and relative standard deviations (RSDs) are within the range of 2.14-4.38%. This result indicates that the effect of the co-precipitation technology on glyphosate detection is almost negligible. After a sample is purified by use of the co-precipitation method, the absorption peak at 250 nm in the tobacco sample is significantly reduced (FIG. 5B). Meanwhile, the background absorbance of the tobacco sample also declines significantly, which indicates that co-precipitation technology can eliminate background interference well. FIG. 2 Precipitation efficiency of glyphosate by the co-precipitation method © Sample Spiked Amountof Glyphosate Precipitation Relative Standard (ng ml”) Efficiency (%) Deviation Tobacco sample 1 12 sl > Tobacco sample 2 12 a i Warm 2 Hf EE Water sample 2 2 oo pt The parameters, including Fe;04@C+/PB concentration, pH, reaction time and HO; and ABTS substrate concentrations, are optimized for the ideal analytical performance of the Fe30:@C7/PB+ABTS+H20:2 system. Glyphosate has an inhibitory effect on the Fe:04@C7/PB peroxidase-mimicking activity, which is caused by that glyphosate molecules occupy the active sites on the surfaces of porous Fe:0:@C7/PB nanoparticles. Hence, the Fe;O04@C7/PB concentration plays an important role in a color probe of a detection system. When the Fe;04@C7/PB concentration is 12.5 ug mL, the chromatic aberration of system colors may easily be identified by the eyes at different glyphosate concentrations. Therefore, the Fe;04@C7 concentration is 12.5 pg mL! in follow-up experiment. Then, to obtain optimal experimental results, the pH, the reaction time, the ABTS and H20: substrate concentrations are optimized, 10 min of reaction time, pH=2, 2 mM of H;0: concentration and 0.2 mM of ABTS are selected for the ensuing experiments.
8.6 Assay performance toward glyphosate The peroxidase-like activity of Fe30:@C7/PB may promote the decomposition of H:0: into hydroxyl radicals (OH), which directly oxidize ABTS to form steelblue products with three characteristic absorption peaks in 416 nm, 647 nm and 730 nm. With an increase in the glyphosate concentration (FIGS. 6A and 6B), the absorbance at 416 nm, 647 nm and 730 nm gradually decreases, and are proportional to the glyphosate concentration, indicating that a linear relationship in the range of 0.125-15 ug mL is good, a correlation coefficient R is greater than 0.99, and the limit of detection is 0.1 ug mL". Specificity and anti-interference capability are crucial indices to estimate the detection capacity of the peroxidase-like nanozyme-based sensor. Other common pesticides (a-glyphosate, b-ilubendiamide, c-imiprothrin, d-thiacloprid, e-atrazine, t-triphenyl phosphate, g-flumetralin, h-butralin, i-pendimethalin, j-parathion-methyl, k-flucythrinate and l-ziram) and phosphate (PO, HPO4* and HoPO..) are chosen to assess the interference effect. As shown in FIG. 7, only glyphosate causes an induced remarkable response in the system, while other pesticides with the same concentration (10.0 mg L"!) have no significant effect (FIGS. 7A and 7B). But phosphate (IP) can also cause the absorbance to decrease in Fe30:4@C7/PB-ABTS-H20: system, revealing that the phosphate has an interference with the detection system. To clear up the interference of phosphate, we add calcium chloride (CaCl:) to form insoluble compounds between phosphate and Ca?” to eliminate interference (FIGS. 7C and 7D).
8.7. Smartphone color sensing platform Due to the significance of on-site testing, portable devices and detection should be also taken into consideration. We design a portable smartphone for the on-site detection of glyphosate based on the inhibition of glyphosate on peroxidase activity, as shown in FIG. 9. By utilizing the system to photograph the colors of reaction solution with various glyphosate concentrations and further analyzing through a color recognizer APP installed in the smartphone, the color changes are transformed into RGB values. Because the acquired images' brightness of the probe solution is in negative connection with glyphosate concentrations, in combination with Adobe photoshop CC 2015.5 software, a linear relationship between the smartphone readout gray values and different glyphosate concentrations (in the range of 5-125 ug mL) (R?=0.9973) is shown in FIGS. 8A and 8B. The performance of the developed smartphone-assisted sensing platform is compared with other methods in literature. As summarized in Table 3, the detection sensitivity of the method proposed in the present invention is not as low as the electrochemical sensor, but they have great advantages in on-site testing and detection time. Table 3 Comparison with earlier reported sensing platforms for glyphosate detection. Analysis Strategy Materials Sample mt of an,
‘abb: v 0.175 Smartphone color sensing Porous Co304 nanoplates Cabbage, snow 0.17 me 10 pea, orange kg Colorimetric sensor Copper doped poly(vinyl Water 0.1 He <1 alcohol) mL Fluorescent and Rhodamine derivatives Agricultural 4.1 aM 2 colorimetric chemosensor products Colorimetric method Peroxidase like activity of - I uM 40 Electrochemical sensor Molecularly imprinted Orange juice, rice 1.94 ng 60 polypyrrole nanotubes beverages mL Smartphone color sensing Fe3O4ia;C1 Tobacco samples Oo EE 10
8.8. Assay of glyphosate in actual samples Considering that the substrates of tobacco samples are more complicated than those of general agricultural products, different tobacco products are selected to evaluate the application of the smartphone color sensing platform. As listed in Table 4, the average recoveries of glyphosate from spiked actual samples are between 89.44 and 97.10%, and the relative standard deviations are in the range of 1.89-5.38%. Furthermore, the spiked recoveries obtained by the smartphone color sensing platform are very similar to those obtained by GC-MS (China National Standard GB/T 23750-2009). These results reveal that the smartphone color sensing platform has excellent accuracy and repeatability, which has great practical application in the field of rapid detection of glyphosate in tobacco products. Table 4 Determination of glyphosate in spiked tobacco samples (n=6). oo Smartphone Color Sensing Platform GC-MS Spiked AOP SEE RE wee eee Tobacco Detection Detection Samples Amount Value (ug Recovery RSD (%) Value (ug Recovery RSD g -1 c 0 - 0/5 0, (ng mL”) mL (%0) mL) (Yo) (Yo) 0 0 - - 0 - - 1 12.5 11.18 89.44 3.53 11.65 93.2 3.23 50 48.55 97.1 4.67 48.54 97.08 432 0 0 - - 0 - - 2 12.5 11.57 92.56 1.89 11.64 93.12 2.65 50 48.34 96.68 434 47.87 95.74 5.21 0 0 - - 0 - - 3 12.5 11.83 94.64 5.38 11.03 88.24 3.59 50 46.56 93.12 3.53 48.32 96.64 4.07 Although the present invention is described in detail with reference to the foregoing embodiments, those skilled in the art still could amend the technical solutions recorded in the foregoing embodiments, or carry out equivalent replacement on some of technical features therein, any amendments, equivalent replacement and improvement and the like based on the spirit and the principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210962449.0A CN115266702A (en) | 2022-08-11 | 2022-08-11 | Preparation method of nano material with bionic enzyme activity and application of nano material in glyphosate detection |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NL2033192A true NL2033192A (en) | 2023-01-17 |
| NL2033192B1 NL2033192B1 (en) | 2023-06-14 |
Family
ID=83750775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL2033192A NL2033192B1 (en) | 2022-08-11 | 2022-09-30 | A Preparation Method of A Nanomaterial with bionic enzymes activity and An Application of the Nanomaterial in Glyphosate Detection |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115266702A (en) |
| NL (1) | NL2033192B1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115266702A (en) * | 2022-08-11 | 2022-11-01 | 云南省烟草质量监督检测站 | Preparation method of nano material with bionic enzyme activity and application of nano material in glyphosate detection |
| CN115888811A (en) * | 2022-12-29 | 2023-04-04 | 云南省烟草质量监督检测站 | Nano enzyme material, preparation method and application thereof, and Pb 2+ Ion detection method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113406068A (en) * | 2021-07-08 | 2021-09-17 | 云南伦扬科技有限公司 | Method for rapidly detecting glyphosate based on smart phone |
| CN115266702A (en) * | 2022-08-11 | 2022-11-01 | 云南省烟草质量监督检测站 | Preparation method of nano material with bionic enzyme activity and application of nano material in glyphosate detection |
-
2022
- 2022-08-11 CN CN202210962449.0A patent/CN115266702A/en active Pending
- 2022-09-30 NL NL2033192A patent/NL2033192B1/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113406068A (en) * | 2021-07-08 | 2021-09-17 | 云南伦扬科技有限公司 | Method for rapidly detecting glyphosate based on smart phone |
| CN115266702A (en) * | 2022-08-11 | 2022-11-01 | 云南省烟草质量监督检测站 | Preparation method of nano material with bionic enzyme activity and application of nano material in glyphosate detection |
Non-Patent Citations (4)
Also Published As
| Publication number | Publication date |
|---|---|
| CN115266702A (en) | 2022-11-01 |
| NL2033192B1 (en) | 2023-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| NL2033192B1 (en) | A Preparation Method of A Nanomaterial with bionic enzymes activity and An Application of the Nanomaterial in Glyphosate Detection | |
| Su et al. | Biosensors based on fluorescence carbon nanomaterials for detection of pesticides | |
| Weerathunge et al. | Dynamic interactions between peroxidase-mimic silver NanoZymes and chlorpyrifos-specific aptamers enable highly-specific pesticide sensing in river water | |
| Chen et al. | Highly sensitive detection of chromium (III) ions by resonance Rayleigh scattering enhanced by gold nanoparticles | |
| Yan et al. | Fluorometric and colorimetric analysis of carbamate pesticide via enzyme-triggered decomposition of Gold nanoclusters-anchored MnO2 nanocomposite | |
| Hayat et al. | Colorimetric cholesterol sensor based on peroxidase like activity of zinc oxide nanoparticles incorporated carbon nanotubes | |
| Han et al. | Peroxidase-like activity of acetylcholine-based colorimetric detection of acetylcholinesterase activity and an organophosphorus inhibitor | |
| Yao et al. | A new coumarin-based chemosensor for Fe3+ in water | |
| Luo et al. | A versatile platform for colorimetric, fluorescence and photothermal multi-mode glyphosate sensing by carbon dots anchoring ferrocene metal-organic framework nanosheet | |
| Wang et al. | Etching of single-MnO2-coated gold nanoparticles for the colorimetric detection of organophosphorus pesticides | |
| Qi et al. | A convenient chemiluminescence detection for bisphenol A in E-waste dismantling site based on surface charge change of cationic gold nanoparticles | |
| Chen et al. | Fluorescent and colorimetric dual-response sensor based on copper (II)-decorated graphitic carbon nitride nanosheets for detection of toxic organophosphorus | |
| Guo et al. | Determination of trace copper ions with ultrahigh sensitivity and selectivity utilizing CdTe quantum dots coupled with enzyme inhibition | |
| Zhang et al. | A convenient label free colorimetric assay for pyrophosphatase activity based on a pyrophosphate-inhibited Cu 2+–ABTS–H 2 O 2 reaction | |
| Su et al. | Direct colorimetric detection of hydrogen peroxide using 4-nitrophenyl boronic acid or its pinacol ester | |
| Nangare et al. | Structural design of nanosize-metal–organic framework-based sensors for detection of organophosphorus pesticides in food and water samples: current challenges and future prospects | |
| Zhao et al. | Nanozyme-based biosensor for organophosphorus pesticide monitoring: Functional design, biosensing strategy, and detection application | |
| Wang et al. | Coupling diazotization with oxidase-mimetic catalysis to realize dual-mode double-ratiometric colorimetric and electrochemical sensing of nitrite | |
| Li et al. | Dual colorimetric and ratiometric fluorescent responses for the determination of glutathione based on fluorescence quenching and oxidase-like activity of MnO2 nanosheets | |
| Liu et al. | A dual-mode sensing platform based on metal–organic framework for colorimetric and ratiometric fluorescent detection of organophosphorus pesticide | |
| Zhang et al. | Photothermal and colorimetric dual-readout silver ions determination utilizing the oxidase-mimicking activity of MnO2 nanosheets | |
| Liu et al. | Bimodal ratiometric fluorescence and colorimetric sensing of paraoxon based on trifunctional Ce, Tb co-coordinated polymers | |
| Kim et al. | Nano‐Conjugate Fluorescence Probe for the Discrimination of Phosphate and Pyrophosphate | |
| Jayeoye et al. | Creatinine assembled on dithiobis (succinimidylpropionate) modified gold nanoparticles as a sensitive and selective colorimetric nanoprobe for silver ion detection | |
| Chen et al. | Sensitive and reversible perylene derivative-based fluorescent probe for acetylcholinesterase activity monitoring and its inhibitor |