CN108375574B - Ferroferric oxide supported nickel-loaded carbonized layer nanotube and preparation method and application thereof - Google Patents
Ferroferric oxide supported nickel-loaded carbonized layer nanotube and preparation method and application thereof Download PDFInfo
- Publication number
- CN108375574B CN108375574B CN201810102269.9A CN201810102269A CN108375574B CN 108375574 B CN108375574 B CN 108375574B CN 201810102269 A CN201810102269 A CN 201810102269A CN 108375574 B CN108375574 B CN 108375574B
- Authority
- CN
- China
- Prior art keywords
- nanotube
- loaded
- hydrogen peroxide
- ferroferric oxide
- nickel
- 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
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002071 nanotube Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 173
- 229910052759 nickel Inorganic materials 0.000 title claims description 55
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 106
- 238000001514 detection method Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001868 water Inorganic materials 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000000975 bioactive effect Effects 0.000 claims abstract description 18
- 102000003992 Peroxidases Human genes 0.000 claims abstract description 9
- 108040007629 peroxidase activity proteins Proteins 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 53
- 239000002073 nanorod Substances 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 39
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims description 21
- 150000004706 metal oxides Chemical class 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000862 absorption spectrum Methods 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 15
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims description 14
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- 229910001453 nickel ion Inorganic materials 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000523 sample Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 102000004316 Oxidoreductases Human genes 0.000 claims description 5
- 108090000854 Oxidoreductases Proteins 0.000 claims description 5
- -1 hydroxyl ferric oxide Chemical compound 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 108090000604 Hydrolases Proteins 0.000 claims description 2
- 102000004157 Hydrolases Human genes 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000012472 biological sample Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229940088623 biologically active substance Drugs 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 10
- 238000006479 redox reaction Methods 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 2
- 230000000007 visual effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 94
- 235000012000 cholesterol Nutrition 0.000 description 43
- 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 18
- 229910002588 FeOOH Inorganic materials 0.000 description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 14
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 14
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 13
- 239000007974 sodium acetate buffer Substances 0.000 description 10
- 102000004190 Enzymes Human genes 0.000 description 9
- 108090000790 Enzymes Proteins 0.000 description 9
- 108010089254 Cholesterol oxidase Proteins 0.000 description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000008103 glucose Substances 0.000 description 8
- 239000004471 Glycine Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229960005070 ascorbic acid Drugs 0.000 description 7
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 7
- 230000003278 mimic effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 210000002966 serum Anatomy 0.000 description 6
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 5
- 239000011668 ascorbic acid Substances 0.000 description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 4
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 4
- LCPUDZUWZDSKMX-UHFFFAOYSA-K azane;hydrogen sulfate;iron(3+);sulfate;dodecahydrate Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCPUDZUWZDSKMX-UHFFFAOYSA-K 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 235000001727 glucose Nutrition 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000000370 acceptor Substances 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 229960003638 dopamine Drugs 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PKYCWFICOKSIHZ-UHFFFAOYSA-N 1-(3,7-dihydroxyphenoxazin-10-yl)ethanone Chemical compound OC1=CC=C2N(C(=O)C)C3=CC=C(O)C=C3OC2=C1 PKYCWFICOKSIHZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 108010055297 Sterol Esterase Proteins 0.000 description 2
- 102000000019 Sterol Esterase Human genes 0.000 description 2
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QKUSRAKPUWQSJS-UHFFFAOYSA-N diazanium 3-ethyl-2H-1,3-benzothiazole-6-sulfonate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)C1=CC=C2N(CC)CSC2=C1.[O-]S(=O)(=O)C1=CC=C2N(CC)CSC2=C1 QKUSRAKPUWQSJS-UHFFFAOYSA-N 0.000 description 2
- CSVGEMRSDNSWRF-UHFFFAOYSA-L disodium;dihydrogen phosphate Chemical compound [Na+].[Na+].OP(O)([O-])=O.OP(O)([O-])=O CSVGEMRSDNSWRF-UHFFFAOYSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000003018 immunoassay Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LEAHFJQFYSDGGP-UHFFFAOYSA-K trisodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[Na+].OP(O)([O-])=O.OP([O-])([O-])=O LEAHFJQFYSDGGP-UHFFFAOYSA-K 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 241000152447 Hades Species 0.000 description 1
- 241000700721 Hepatitis B virus Species 0.000 description 1
- 108010001336 Horseradish Peroxidase Proteins 0.000 description 1
- 229910017626 NH4Fe(SO4)2 Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- UJGOCJFDDHOGRX-UHFFFAOYSA-M [Fe]O Chemical compound [Fe]O UJGOCJFDDHOGRX-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 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 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000002789 catalaselike Effects 0.000 description 1
- NYOXRYYXRWJDKP-GYKMGIIDSA-N cholest-4-en-3-one Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 NYOXRYYXRWJDKP-GYKMGIIDSA-N 0.000 description 1
- NYOXRYYXRWJDKP-UHFFFAOYSA-N cholestenone Natural products C1CC2=CC(=O)CCC2(C)C2C1C1CCC(C(C)CCCC(C)C)C1(C)CC2 NYOXRYYXRWJDKP-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003759 clinical diagnosis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009585 enzyme analysis Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
Images
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
- 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
- B01J23/755—Nickel
-
- 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
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- 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
- G01N2021/775—Indicator and selective membrane
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention belongs to a high-molecular material andthe field of biomedicine, and relates to a ferroferric oxide supported nickel-negative carbonized layer nanotube, a preparation method and application thereof, wherein the ferroferric oxide supported nickel-negative carbonized layer nanotube (Fe)3O4@ C-NT/Ni) is in a hollow tubular shape, has excellent electromagnetic property, catalytic activity, biocompatibility and water dispersibility, has peroxidase-like activity, and is used for detecting and analyzing hydrogen peroxide and bioactive substances. Fe3O4The preparation method of @ C-NT/Ni is simple, efficient, high in recovery rate, safe and environment-friendly. Fe3O4The catalytic activity of @ C-NT/Ni is similar to that of peroxidase, and the method is used for oxidation-reduction reaction of hydrogen peroxide as an electron acceptor, so that qualitative and quantitative determination of the hydrogen peroxide is realized; the method is also used for qualitative and quantitative detection of the bioactive substances with hydrogen peroxide as a constant proportion product, and compared with the prior art, the method is simple, fast, economic and environment-friendly, high in detection line width and sensitivity, good in selectivity and visual.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a ferroferric oxide-loaded nickel-carbon nanotube, and a preparation method and application thereof.
Background
The total cholesterol determination methods currently exceed 200, and can be divided into five major categories, namely chemical reagent colorimetry, enzyme analysis, fluorescence, gas phase and high performance liquid chromatography. The gas phase chromatography and the high performance liquid chromatography require special equipment, the detection time is long, and interference factors in a sample are many, so that the separation effect is poor; the operation steps of the chemical reagent colorimetric method are complicated, and particularly, the used reagents are more, the measurement result has deviation, and the calculation result is complex; the enzyme method has high technical content and strong specificity. At present, the price of a test strip used by a total cholesterol detection kit on the market is high, and the test strip is not economical and practical enough for daily life detection, so that the establishment of a rapid, efficient, simple, accurate, economical and practical cholesterol detection method is always a hotspot in recent years.
The research group of biophysical institute Hades and Stachyn sieboldii of Chinese academy of sciences discovers that the ferroferric oxide nanoparticles have peroxidase-like catalytic activity, and two immunoassay methods are designed by utilizing the characteristic, so that the detection of the hepatitis B virus surface antigen and the troponin is realized. Subsequently, Wanerkang et al utilize the characteristics of ferroferric oxide nanoparticle peroxidase to realize the detection of hydrogen peroxide and glucose. In addition, various inorganic nano systems also show more stable catalytic properties than horseradish peroxidase, and are novel mimic enzymes. However, the artificial mimic enzyme based on nanomaterial still has many defects in biocatalysis application, such as small synthesis amount, complex synthesis process, inaccurate physical and chemical properties, etc., and therefore, the structure of the nanoenzyme needs to be optimally adjusted to make the performance of the nanoenzyme more stable.
The tubular magnetic material (Fe) with the ferroferric oxide supported with the nickel-loaded carbonized layer prepared by the invention3O4@ C-NT/Ni), simple preparation process, economy and environmental protection, and has excellent catalytic activity, electromagnetic property, biocompatibility and good dispersibility in water compared with other nano mimic enzymes with single peroxidase-like activity. Fe prepared by the invention3O4The method for colorimetric detection of cholesterol by @ C-NT/Ni has the advantages of no need of labeling, simple operation, rapidness, high efficiency, visualization, high sensitivity and selectivity, can still efficiently detect cholesterol even when the concentration of an interfering substance is 25 times of that of cholesterol, and has a wide linear range for detection of cholesterol.
Disclosure of Invention
The invention provides a ferroferric oxide supported nickel-loaded carbon nano tube, which is used as a mimic enzyme, has peroxidase activity, catalyzes oxidation-reduction reaction, is used for qualitative and quantitative determination of hydrogen peroxide, cholesterol, glucose, ascorbic acid, glycine or histidine and the like, does not need to be marked, and is simple to operate, rapid, efficient, visual, high in sensitivity and selectivity.
The invention also provides a preparation method and application of the ferroferric oxide supported nickel-loaded carbonized layer nanotube. The preparation method is simple, economic and environment-friendly; the obtained ferroferric oxide supported nickel-loaded carbon-based layer nanotube has high catalytic activity, good electromagnetic property, excellent biocompatibility and good dispersibility in water.
The technical scheme of the invention is as follows: the ferroferric oxide supported nickel-loaded carbonized layer nanotube comprises a ferroferric oxide nanotube and a nickel particle-loaded carbon nanotube coated on the outer wall of the ferroferric oxide nanotube, wherein the length of the carbon nanotube is 1-10 mu m, and the preferred length is 1-5 mu m; the inner diameter is 50-300 nm, preferably 80-220 nm, more preferably, the average inner diameter is 90-120 nm, and more preferably 100 nm; the thickness of the ferroferric oxide nanotube is 30-80 nm, preferably 50-75 nm; the thickness of the carbon nano tube loaded with the nickel particles is 3-10 nm, preferably 3-8 nm, and more preferably 5 nm; the particle size of the nickel particles is 2-6 nm, preferably 3-4 nm, and more preferably 3.5 nm.
The preparation method of the ferroferric oxide supported nickel-loaded carbonized layer nanotube comprises the following steps: (1) preparing a metal oxide supported iron oxyhydroxide nanorod: in an alcohol-water solution, reacting the metal oxide nanorod with ferric salt at 60-90 ℃ to generate a metal oxide supported hydroxyl ferric oxide nanorod;
(2) preparing a hydroxyl ferric oxide supported nickel ion/carbonized precursor nanotube: dispersing the metal oxide supported iron oxyhydroxide nanorods prepared in the step (1) in an alkali-containing aqueous solution or an alcohol aqueous solution, adding a carbonization precursor organic matter and a nickel salt for reaction, removing the metal oxide nanorods and reacting on the surface of the iron oxyhydroxide to generate a nickel ion-loaded carbonization precursor layer, thereby obtaining the iron oxyhydroxide nanotube supported nickel ion/carbonization precursor nanotube; preferably, the reaction time is 10-24 h; or adding a carbonization precursor organic matter and nickel salt under an alkaline condition, reacting on the surface of the iron oxyhydroxide to generate a carbonization precursor layer loaded with nickel ions, washing, drying, and removing the metal oxide nanorods by using acid, preferably, the reaction time is 10-24 h; washing, drying, and removing the metal oxide nanorod by using acid to generate a hydroxyl ferric oxide supported nickel ion/carbonized precursor nanotube;
(3) preparing a ferroferric oxide supported nickel-loaded carbonized layer nanotube: and (3) carbonizing the hydroxyl iron oxide supported nickel ion/carbonized precursor nanotube prepared in the step (2) at high temperature in a nitrogen atmosphere or an inert gas atmosphere to generate a ferroferric oxide supported nickel-loaded carbonized layer nanotube.
In the step (1), the length of the metal oxide nanorod is 1-10 μm, preferably 1-5 μm; the diameter is 50 to 300nm, preferably 70 to 300nm, more preferably, the average inner diameter is 90 to 120nm, and more preferably 100 nm.
In the step (1), the metal oxide nanorods include molybdenum trioxide nanorods, manganese dioxide nanorods, titanium dioxide nanorods, aluminum trioxide nanorods, zinc oxide nanorods, copper oxide nanorods, tin dioxide nanorods, or the like, and preferably are molybdenum trioxide nanorods.
In the step (1), the volume fraction of the ethanol in the alcohol-water solution is 3-15%, preferably 3-5%, and more preferably 3.3-3.5%; the molar ratio of the iron element to the molybdenum element is 2-3: 1, preferably 2.4-2.6: 1, and more preferably 2.5: 1; the molar concentration of the iron element is 3 multiplied by 10-2～5×10-2mol/L, preferably 4X 10-2～4.2×10-2mol/L。
In the step (1), firstly, dispersing the metal oxide in an alcohol-water solution, then dropwise adding an iron salt water solution, and reacting at constant temperature to obtain the metal oxide supported iron oxyhydroxide nanorod.
In the step (1), the reaction temperature is preferably 60-80 ℃, and more preferably 70 ℃; the reaction time is 2 to 12 hours, preferably 3 to 8 hours, and more preferably 4 hours.
In the step (1), the metal oxide and the ferric salt react under the stirring condition.
In the step (1), the preparation method of the molybdenum trioxide nanorod comprises the following steps: carrying out hydrothermal reaction on ammonium molybdate tetrahydrate in an acid-containing aqueous solution to generate the molybdenum trioxide nano-rod. The acid is an inorganic acid, typically nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and the like, preferably nitric acid.
In the hydrothermal reaction system, the molar concentration of ammonium molybdate tetrahydrate is 2X 10-2～10×10-2mol/L, preferably 2X 10-2～5×10-2mol/L, more preferably 2.5X 10-2～3×10-2mol/L; the molar concentration ratio of ammonium molybdate tetrahydrate to acid is 1: 80-95, preferably 1: 85-90, and more preferably 1: 89.
In the step (2), the dosage ratio of the metal oxide supported iron oxyhydroxide nanorod to carbon element in the carbonization precursor is 1 g: (1.5X 10)-2～15×10-2) moL, preferably 1 g: (3X 10)-2～10×10-2) moL, more preferably 1 g: (3X 10)-2～5×10-2) mols; the molar ratio of the carbon element to the nickel element in the carbonization precursor is 1: 0.1-1, preferably 1: 0.1-0.5, and more preferably 1: 0.2.
In the step (2), the volume fraction of ethanol in the alcohol-water solution is 35% to 75%, preferably 40% to 60%, and more preferably 50%.
In the step (2), the concentration of the alkali is 0.1-1.0 mol/L, preferably 0.5-0.8 mol/L, and more preferably 0.5-0.6 mol/L; the base is an inorganic base, and generally includes ammonia water, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, and the like, and preferably ammonia water. The acid is inorganic acid, generally hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid and the like, and preferably, when the metal oxide nanorods are removed by the acid, the reaction time is 1-6 h. For example, the molybdenum trioxide nano-rods can be dissolved by ammonia water, and the manganese dioxide nano-rods can be dissolved by hydrochloric acid.
In the step (2), the carbonization precursor organic matter is dopamine, aniline or phenolic resin.
In the step (3), the hydroxyl iron oxide-supported nickel ion/carbonization precursor nanotube prepared in the step (2) is firstly dried at low temperature and then carbonized at high temperature to generate a ferroferric oxide-supported nickel-loaded carbonization nanotube.
The low-temperature drying temperature is 50-95 ℃, and preferably 60-80 ℃; the time is 5 to 10 hours, preferably 7 to 9 hours.
The high-temperature carbonization temperature is 350-700 ℃, preferably 400-600 ℃, and more preferably 500 ℃; the time is 3 to 8 hours, preferably 4 to 6 hours, and more preferably 5 hours.
The ferroferric oxide supported nickel-loaded carbonized layer nanotube prepared by the method has catalytic activity similar to that of peroxidase. The ferroferric oxide supported nickel-loaded carbon-based layer nanotube is used as a mimic enzyme for catalyzing redox reaction, particularly for catalyzing redox reaction of peroxide as an electron acceptor substrate, and can be used for preparing a peroxidase-like catalyst and a peroxidase mimic.
Based on the similar redox activity of the ferroferric oxide supported nickel-loaded carbonized layer nanotube and peroxidase, hydrogen peroxide can be catalyzed to accept electrons to be reduced, and the catalytic color indicator loses electrons to be oxidized and developed, so that the ferroferric oxide supported nickel-loaded carbonized layer nanotube can be used for constant-proportion redox reaction of hydrogen peroxide as an electron acceptor substrate, and qualitative and quantitative determination of the hydrogen peroxide is realized. For example, a color indicator 3,3',5,5' -Tetramethylbenzidine (TMB) is oxidized by hydrogen peroxide to generate a constant proportion of blue oxidation products (oxTMB, TMBox) under the catalytic action of a ferroferric oxide supported nickel carbide layer nanotube, and an ultraviolet absorption spectrum of the blue oxidation products at a wavelength of 652nm is measured to realize qualitative and quantitative detection of hydrogen peroxide, wherein the oxidation-reduction reaction route is shown as follows:
many intermediate products of biochemical reaction relate to the generation of hydrogen peroxide, and the ferroferric oxide supported nickel-loaded carbon nano tube can also be used for qualitative and quantitative detection of a bioactive substance taking hydrogen peroxide as a constant proportion product. The biological active substance, such as cholesterol, glucose, ascorbic acid, glycine or histidine, is subjected to oxidation reaction with oxygen under the catalysis of oxidase to generate constant proportion hydrogen peroxide, is subjected to constant proportion redox reaction with a color indicator under the catalysis of the ferroferric oxide supported nickel carbide layer nanotube, and the qualitative and quantitative determination of the hydrogen peroxide is realized.
Specifically, cholesterol is oxidized to generate hydrogen peroxide with a constant proportion by using cholesterol oxidase (CHOx) as a catalyst in the presence of oxygen, and the hydrogen peroxide is quantitatively measured according to the constant proportion oxidation-reduction reaction between the hydrogen peroxide and a color indicator, so that the content of the cholesterol is further determined, wherein the reaction route is as follows:
when detecting hydrogen peroxide, the method comprises the following steps: uniformly mixing a sample containing hydrogen peroxide, a ferroferric oxide supported nickel-loaded carbon-based layer nanotube, a color indicator and a buffer solution, and reacting for 5-30 minutes at the pH of 2-10 and at the temperature of 25-60 ℃; separating the ferroferric oxide supported nickel-loaded carbon-coated nanotube, detecting the absorption spectrum of the reaction solution, and performing qualitative or quantitative determination on the hydrogen peroxide.
Preferably, the pH is 2-6; more preferably, the pH is 3 to 5, and still more preferably 4; the buffer solution is acetic acid-sodium acetate, phosphoric acid-sodium phosphate, phosphoric acid-sodium hydrogen phosphate and the like, and preferably acetic acid-sodium acetate.
The color indicator comprises 3,3',5,5' -Tetramethylbenzidine (TMB), o-phenylenediamine (OPD), 2' -diaza-bis (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt (ABTS), luminous ammonia and a fluorescent reagent Amplex Red, and is preferably 3,3',5,5' -tetramethylbenzidine. The content of the color indicator in the detection system is 1-600 mu mol/L, preferably 1-100 mu mol/L, and more preferably 50 mu mol/L.
The content of the ferroferric oxide supported nickel-loaded carbonized layer nanotube in a detection system is 5-100 mu g/mL, preferably 5-40 mu g/mL, and more preferably 20 mu g/mL.
The reaction temperature is preferably 45 ℃ to 55 ℃, more preferably 50 ℃.
In a preferred embodiment of the invention, 0.2mol/L of an acetic acid-sodium acetate buffer solution with pH 4 is used, a color indicator is 3,3',5,5' -tetramethylbenzidine, the detection wavelength of an absorption spectrum is 652nm, the content of the 3,3',5,5' -tetramethylbenzidine in the detection system is 50 μmol/L, and the content of the ferroferric oxide supported nickel-loaded carbide layer nanotube is 20 μ g/mL.
The hydrogen peroxide detection method determines the linear response concentration range of hydrogen peroxide in a detection systemIs 1 × 10-6～2×10-3mol/L, the detection limit of hydrogen peroxide is 1.00 multiplied by 10-6mol/L, the detection method has good selectivity, high accuracy and sensitivity, simple and convenient and quick operation, economy and environmental protection.
When detecting the bioactive substances, the method comprises the following steps: a. mixing a sample containing bioactive substances with oxidase or hydrolase and oxidase corresponding to the bioactive substances to enable the bioactive substances in the sample to generate oxidation reaction with oxygen to generate hydrogen peroxide; b. adding ferroferric oxide supported nickel-loaded carbon-coated nanotube, a color indicator and a buffer solution, uniformly mixing, and reacting for 5-30 minutes at 25-60 ℃ under the condition that the pH value is 2-10; c. removing the ferroferric oxide supported nickel-loaded carbon nano tube, measuring the absorption spectrum of the reaction solution, and carrying out qualitative or quantitative detection.
The bioactive substances include saccharides, lipids, protein polypeptides, sterols, vitamins, etc., which can be oxidized to generate hydrogen peroxide, such as total cholesterol, glucose, ascorbic acid, glycine or histidine, etc.
In the step b, preferably, the pH is 3-8, more preferably 3-5, and still more preferably 4; the buffer solution is acetic acid-sodium acetate, phosphoric acid-sodium phosphate, phosphoric acid-sodium hydrogen phosphate and the like, and preferably acetic acid-sodium acetate.
In the step b, the color indicator comprises 3,3',5,5' -Tetramethylbenzidine (TMB), o-phenylenediamine (OPD), 2' -diaza-bis (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt (ABTS), luminol and a fluorescent reagent Amplex Red, and is preferably 3,3',5,5' -tetramethylbenzidine. The content of the color indicator in the detection system is 0-600 mu mol/L, preferably 1-100 mu mol/L, and more preferably 50 mu mol/L.
In the step b, the content of the ferroferric oxide supported nickel-loaded carbonized layer nanotube in a detection system is 5-100 mug/mL, preferably 5-40 mug/mL, and more preferably 20 mug/mL.
In the step b, the reaction temperature is preferably 45 to 55 ℃, more preferably 50 ℃.
In a preferred embodiment of the invention, the bioactive substance is cholesterol or total cholesterol, 0.2mol/L of acetic acid-sodium acetate buffer solution with pH 4 is used, the chromogenic indicator is 3,3',5,5' -tetramethylbenzidine, the detection wavelength of the absorption spectrum is 652nm, the content of the 3,3',5,5' -tetramethylbenzidine in the detection system is 50 μmol/L, and the content of the ferroferric oxide supported nickel carbide layer nanotube is 20 μ g/mL;
when the bioactive substance is cholesterol, adding cholesterol oxidase in the step a; when the bioactive substance is total cholesterol, adding cholesterol esterase and cholesterol oxidase in the step a.
Detecting cholesterol or total cholesterol by the above method, and determining the linear response concentration range of cholesterol to be 5 × 10-6～1×10-3mol/L, limit of cholesterol detection is 5X 10-6And when the concentration of the interfering substance is 25 times of that of the cholesterol, the method can still efficiently detect the cholesterol, and the detection method has the advantages of good selectivity, strong specificity, high accuracy and sensitivity, simple and quick operation, economy and environmental protection.
Based on the peroxidase-like catalytic activity of the ferroferric oxide supported nickel-carbide layer-loaded nanotube, the ferroferric oxide supported nickel-carbide layer-loaded nanotube can also be used for preparing a reagent or a kit for detecting hydrogen peroxide, or a reagent or a kit for detecting bioactive substances in a biological sample.
In the present specification, the term "peroxidase-like enzyme" refers to a substance exhibiting peroxidase catalytic activity. Specifically, the peroxidase-like enzymes of the present invention catalyze redox reactions and oxidize substrates using peroxides as electron acceptors. The term "TMB" is the abbreviated name for the compound "3, 3',5,5' -tetramethylbenzidine", which are interchangeable.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides a high polymer material ferroferric oxide supported nickel-loaded carbon-coated nanotube which has excellent electromagnetic property, catalase-like activity, biocompatibility and water dispersibility, can catalyze the oxidation reaction of hydrogen peroxide as one of reaction substrates, and realizes qualitative and quantitative detection of the hydrogen peroxide; it can also be used for qualitative and quantitative detection of bioactive substances with hydrogen peroxide as product.
(2) The qualitative and quantitative detection method using the ferroferric oxide supported nickel-loaded carbon-loaded nanotube as the catalyst has the advantages of simple process, easy operation, high recovery rate, good selectivity, high accuracy and precision, environmental protection and high efficiency, and the ferroferric oxide supported nickel-loaded carbon-loaded nanotube has good magnetism and can be separated from the solution through an external magnetic field.
(3) The ferroferric oxide supported nickel-loaded carbonized layer nanotube has catalytic activity similar to that of peroxidase and can catalyze oxidation-reduction reaction; the ferroferric oxide supported nickel-loaded carbide layer nanotube is used as a novel mimic enzyme, can replace catalase and is widely used in the fields of biological detection, clinical diagnosis, immunoassay and the like.
Drawings
FIG. 1 shows MoO in example 1 of the present invention3Nanorods, MoO3@FeOOH、FeOOH@PDA-Ni2+And Fe3O4SEM and TEM images of @ C-NT/Ni; in FIG. 1, A is MoO3SEM picture of nano-rod, B is MoO3TEM image of nanorods; c is MoO3SEM picture of @ FeOOH, D is MoO3TEM image of @ FeOOH; e is FeOOH @ PDA-Ni2+In SEM picture of (1), F is FeOOH @ PDA-Ni2+A TEM image of (B); g is Fe3O4SEM picture of @ C-Ni, H is Fe3O4TEM image of @ C-Ni.
FIG. 2 shows Fe at different temperatures in example 2 of the present invention3O4Graph of catalytic effect of @ C-NT/Ni.
FIG. 3 shows Fe at different pH values in example 3 of the present invention3O4Graph of catalytic effect of @ C-NT/Ni.
FIG. 4 shows different Fe in example 4 of the present invention3O4Graph of catalytic effect at the dosage of @ C-NT/Ni.
FIG. 5 shows Fe at different amounts of TMB in example 5 of the present invention3O4Graph of catalytic effect of @ C-NT/Ni.
FIG. 6 is example 6Fe of the present invention3O4The @ C-NT/Ni colorimetric detection of the catalytic effect of the hydrogen peroxide is shown.
FIG. 7 is the present inventionMing example 7Fe3O4The catalysis effect graph of the colorimetric detection of cholesterol is formed at @ C-NT/Ni.
FIG. 8 is example 7Fe of the present invention3O4Standard curve diagram of colorimetric cholesterol determination of @ C-NT/Ni.
FIG. 9 shows example 8Fe of the present invention3O4Selective colorimetric detection of @ C-NT/Ni.
FIG. 10 is Fe3O4Schematic preparation of @ C-NT/Ni.
FIG. 11 is Fe3O4A schematic diagram of colorimetric detection of cholesterol at @ C-NT/Ni.
Detailed Description
The invention is described in detail below with reference to the drawings and specific examples.
Example 1 ferroferric oxide-supported nickel-negative carbonized layer nanotube (Fe)3O4Preparation of @ C-NT/Ni)
(1) Molybdenum trioxide (MoO)3) Preparation of nanorods
Weighing 1g ammonium molybdate tetrahydrate ((NH)4)6Mo7O24·4H2O) is dissolved in a mixed solution of 25mL of distilled water and 5mL of concentrated nitric acid (65%, 14.4 mol/L);
② after complete dissolution, the reaction solution was transferred to a 50mL Teflon lined stainless steel autoclave and heated at 180 ℃ for 20 hours in a preheated electric oven;
thirdly, centrifuging and drying to obtain MoO3The nano-rods have the length of 1-10 mu m and the average length of 5 mu m; the diameter is 50-150 nm, and the average diameter is 100 nm.
(2) Molybdenum trioxide supported iron oxyhydroxide nanorod (MoO)3@ FeOOH) preparation
Weighing 0.288g of MoO prepared in the step (1)3Nanorods dispersed in a mixture of 4mL absolute ethanol and 36mL water to form MoO3Suspension of nanorods;
② 80mL of ammonium ferric sulfate dodecahydrate (NH)4Fe(SO4)2·12H2O) aqueous solution drop addition to MoO3Stirring the nano-rod suspension for 4 hours at 70 ℃ to obtain MoO3@ FeOOH hybrid, NH4Fe(SO4)2·12H2NH in aqueous O solution4Fe(SO4)2·12H2The mass of O is 1.928 g;
thirdly, centrifuging, washing and drying to obtain reddish brown MoO3@FeOOH。
(3) Nickel ion/polydopamine nanotube (FeOOH @ PDA-Ni) supported by iron oxyhydroxide2+) Preparation of
Weighing 50mg of MoO prepared in the step (2)3@ FeOOH, 25mL of anhydrous EtOH, 25mL of H2O, performing ultrasonic treatment for 30min to uniformly disperse the particles;
② 2mL of ammonia water (NH)3·H2O, 28 percent and 14.8mol/L) is added into the first step dropwise and stirred for 5min at room temperature;
③ 30mg of Dopamine (DA) and 75.2mg of NiCl2·6H2O (0.32mmol) is added into the mixed solution and stirred for 16h at room temperature; obtaining FeOOH @ PDA-Ni2+。
(4) Ferroferric oxide supported nickel-loaded carbonized layer nanotube (Fe)3O4Preparation of @ C-NT/Ni)
Washing FeOOH @ PDA-Ni with deionized water and ethanol for multiple times2+And drying at 60 ℃ for 8 h;
② in nitrogen atmosphere, the obtained FeOOH @ PDA-Ni2+Carbonizing at 500 deg.C for 5h in a tube furnace to obtain Fe3O4@C-NT/Ni。
This example Fe3O4Production of @ C-NT/Ni As shown in FIG. 10, MoO produced in this example3Nanorods, MoO3@FeOOH、FeOOH@PDA-Ni2+And Fe3O4SEM and TEM images of @ C-NT/Ni are shown in FIG. 1. The ferroferric oxide supported nickel-loaded carbon-coated nanotube (Fe) prepared in this example3O4@ C-NT/Ni) is a hollow tubular structure, the length of which is 1-10 μm, and the average is 5 μm; the inner diameter is 50-150 nm, and the average diameter is 100 nm; the outer diameter is 180-315 nm, and the average diameter is 230 nm; the thickness of the ferroferric oxide nanotube is 50-75 nm, the thickness of the carbon nanotube is 3-10 nm, and the average thickness is 5 nm; the particle size of the nickel particles is 2-6 nm, and the average particle size is 3.5 nm.
Example 2 reaction temperature vs. Fe3O4Colorimetric detection of the Effect of Hydrogen peroxide in a @ C-NT/Ni solution
(1) The mixed solution was prepared in parallel as follows: 290 μ L of 0.2mol/L acetic acid-sodium acetate buffer solution with pH 4.00 are put into a centrifuge tube, and 6 μ LFe is added into the centrifuge tube in turn3O4@ C-NT/Ni (1mg/mL), 3. mu.L of aqueous hydrogen peroxide (0.1mol/L), 1. mu.L of 3,3',5,5' -tetramethylbenzidine (TMB, 20mmol/L), and mixed well;
(2) respectively placing the mixed solution prepared in step (1) in a water bath kettle with the temperature of 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃ for reaction for 10 min;
(3) by applying a magnetic field to Fe3O4Separating the @ C-NT/Ni from the reaction solution;
(4) the ultraviolet absorption spectrum of the reaction solution was measured by an ultraviolet-visible absorption spectrophotometer.
As shown in FIG. 2, it can be seen that the absorbance at 652nm increases and then decreases with the increase in temperature, in order to satisfy Fe3O4The optimum catalytic activity of @ C-NT/Ni is required, so that 50 ℃ is selected as the optimum reaction temperature.
Example 3 reaction pH vs. Fe3O4Colorimetric detection of the Effect of Hydrogen peroxide in a @ C-NT/Ni solution
(1) Respectively taking 290 mu L of 0.2mol/LpH ═ 2.00, 3.00, 4.00, 5.00, 6.00, 7.00, 8.00, 9.00 and 10.00 acetic acid-sodium acetate buffer solutions into different centrifuge tubes, and sequentially adding 3 mu L of Fe into each centrifuge tube3O4@ C-NT/Ni (1mg/mL), 3. mu.L of aqueous hydrogen peroxide (0.1mol/L), 3. mu.L of 3,3',5,5' -tetramethylbenzidine (TMB, 20mmol/L), and mixed well;
(2) reacting the mixed solution obtained in the step (1) in a water bath kettle at 50 ℃ for 10 min;
(3) by applying a magnetic field to Fe3O4Separating the @ C-NT/Ni from the reaction solution;
(4) the ultraviolet absorption spectrum of the reaction solution was measured by an ultraviolet-visible absorption spectrophotometer.
The result is shown in FIG. 3, where 652nm is shownThe absorbance of (A) is increased and then decreased with the increase of pH, in order to satisfy Fe3O4Since the optimum catalytic activity of @ C-NT/Ni is required, pH 4.00 is selected as the optimum reaction pH.
Example 4Fe3O4Detection of the Effect of the amount of @ C-NT/Ni on color
(1) 290. mu.L of 0.2mol/LpH ═ 4.00 acetic acid-sodium acetate buffer solution were placed in different centrifuge tubes, and 6. mu.L of Fe at different concentrations were added to each centrifuge tube in sequence3O4@ C-NT/Ni ( final concentration 0, 5, 10, 15, 20, 50, 100. mu.g/mL), 3. mu.L of aqueous hydrogen peroxide (0.1mol/L), 1. mu.L of 3,3',5,5' -tetramethylbenzidine (TMB, 20mmol/L), and mixed well;
(2) reacting the mixed solution obtained in the step (1) in a water bath kettle at 50 ℃ for 10 min;
(3) by applying a magnetic field to Fe3O4Separating the @ C-NT/Ni from the reaction solution;
(4) the ultraviolet absorption spectrum of the reaction solution was measured by an ultraviolet-visible absorption spectrophotometer.
The results are shown in FIG. 4, from which it is clear that Fe is present3O4The addition of @ C-NT/Ni is in linear relation with the absorbance at the wavelength of 652nm, and according to experience, 20 mug/mL is selected as Fe3O4The optimum concentration of the @ C-NT/Ni solution.
Example 5 concentration of TMB solution versus Fe3O4Colorimetric detection of Hydrogen peroxide Effect of @ C-NT/Ni
(1) 290. mu.L of 0.2mol/LpH ═ 4.00 acetic acid-sodium acetate buffer solution were placed in separate centrifuge tubes, and 6. mu.L of Fe was added to each centrifuge tube in sequence3O4@ C-NT/Ni (1mg/mL), 3. mu.L of aqueous hydrogen peroxide (0.01mol/L), 1. mu.L of 3,3',5,5' -Tetramethylbenzidine (TMB) at various concentrations, and mixing the above solutions uniformly; in the reaction system, the concentrations of TMB were 0, 1, 25, 50, 100, 200, 300. mu. mol/L, hydrogen peroxide 100. mu. mol/L, Fe3O4@C-NTs20μg/mL；
(2) Reacting the mixed solution obtained in the step (1) in a water bath kettle at 50 ℃ for 10 min;
(3) by applying a magnetic field to Fe3O4Separating the @ C-NT/Ni from the reaction solution;
(4) the ultraviolet absorption spectrum of the reaction solution was measured by an ultraviolet-visible absorption spectrophotometer.
As shown in FIG. 5, it can be seen that the amount of TMB added is linear with the absorbance at the wavelength of 652nm, and that 50. mu. mol/L was empirically selected as the optimum concentration of the TMB solution.
Example 6Fe3O4Colorimetric determination of hydrogen peroxide in @ C-NT/Ni solution
According to the optimum experimental conditions searched for in examples 2 to 5, Fe was used3O4The method for colorimetric determination of hydrogen peroxide by @ C-NT/Ni comprises the following steps:
(1) respectively putting 290 mu L of 0.2mol/L acetic acid-sodium acetate buffer solution with pH of 4.0 into different centrifuge tubes, and sequentially adding 6 mu L of Fe into the centrifuge tubes3O4@ C-NT/Ni (1mg/mL), 2.5. mu.L of aqueous hydrogen peroxide solutions of various concentrations ( final concentration 0, 1, 5, 10, 20, 50, 100, 200, 500, 1000, 2000. mu. mol/L), 1.5. mu.L of 3,3',5,5' -tetramethylbenzidine (TMB, 10mmol/L), and the above solutions were mixed well;
(2) reacting the mixed solution obtained in the step 1 in a water bath kettle at 50 ℃ for 10 min;
(3) by applying a magnetic field to Fe3O4Separating the @ C-NT/Ni from the reaction solution;
(4) the ultraviolet absorption spectrum of the reaction solution was measured by an ultraviolet-visible absorption spectrophotometer.
The results are shown in FIG. 6, where it can be seen that Fe is 652nm in wavelength3O4The linear range of the detection of the @ C-NT/Ni to the hydrogen peroxide is 1 x 10-6～2×10-3mol/L。
Example 7Fe3O4Colorimetric detection of cholesterol by @ C-NT/Ni
According to the optimum experimental conditions searched for in examples 2 to 5, Fe was used3O4The principle of colorimetric determination of cholesterol with @ C-NT/Ni is shown in figure 11, cholesterol oxidase oxidizes cholesterol into cholest-4-en-3-one and generates hydrogen peroxide; adding Fe3O4Catalytic peroxidation of @ C-NT/NiHydrogen decomposition, oxidation of TMB to blue oxide oxTMB; and detecting the contents of hydrogen peroxide and cholesterol by a colorimetric method. The method comprises the following steps:
(1) respectively adding 90 mu L of cholesterol with different concentrations to be detected and 10 mu L of 10mg/mL cholesterol oxidase into each centrifuge tube, uniformly mixing, wherein the final concentration of the cholesterol in the system is respectively 0, 5, 10, 20, 50, 100, 150, 200, 400, 600, 800 and 1000 mu mol/L, and placing the mixed solution in a water bath kettle at 37 ℃ for reaction for 10 min;
(2) 385 mu L of 0.2mol/L acetic acid-sodium acetate buffer solution with pH of 4.0 is added into the reaction solution obtained in the step (1), and then 10 mu L of Fe is added in sequence3O4@ C-NT/Ni (1mg/mL, final concentration 20. mu.g/mL), 5. mu.L of 3,3',5,5' -tetramethylbenzidine (TMB, 5mmol/L), and mixed well;
(3) reacting the mixed solution obtained in the step 2 in a water bath kettle at 50 ℃ for 10 min;
(4) by applying a magnetic field to Fe3O4Separating the @ C-NT/Ni from the reaction solution;
(5) the ultraviolet absorption spectrum of the reaction solution was measured by an ultraviolet-visible absorption spectrophotometer.
The results are shown in FIGS. 7 and 8, in which Fe is observed3O4The detection limit of cholesterol is 1.00 multiplied by 10 under the catalysis of @ C-NT/Ni-6mol/L, linear range of detection is 5X 10-6～1×10-3mol/L. The linear correlation between the cholesterol concentration and the absorbance (A) is high (R)20.99865), the linear regression equation is a 0.0326+0.0010CCholesterol。
Example 8Fe3O4Selectivity of @ C-NT/Ni colorimetric detection of cholesterol, glucose, ascorbic acid, glycine and histidine
(1) Respectively adding 90 mu L of 1mmol/L cholesterol, 25mmol/L glucose, 25mmol/L ascorbic acid, 25mmol/L glycine, 25mmol/L histidine and 10 mu L of 10mg/mL cholesterol oxidase to be detected into a centrifuge tube, uniformly mixing, and placing the mixed solution into a water bath kettle at 37 ℃ for reaction for 10 min;
(2) adding 385 mu L of 0.2mol/L acetic acid-sodium acetate buffer solution with pH value of 4.00 into the reaction solution obtained in the step (1)Liquid, then 10. mu.L of Fe was added in sequence3O4@ C-NT/Ni (1mg/mL), 5. mu.L of 3,3',5,5' -tetramethylbenzidine (TMB, 5mmol/L), and mixed well;
(3) reacting the mixed solution obtained in the step 2 in a water bath kettle at 50 ℃ for 10 min;
(4) by applying a magnetic field to Fe3O4Separating the @ C-NT/Ni from the reaction solution;
(5) the ultraviolet absorption spectrum of the reaction solution was measured by an ultraviolet-visible absorption spectrophotometer, and the absorbance a0 of the blank sample was used as a control.
As shown in the bar chart of FIG. 9, the absorbance values of 1mmol/L cholesterol, 25mmol/L glucose, 25mmol/L ascorbic acid, 25mmol/L glycine and 25mmol/L histidine are shown in the bar chart from left to right, and the absorbance values corresponding to cholesterol are much higher than those of other control substances, thus proving that the method of the present invention has high selectivity and good specificity for detecting cholesterol, and can still efficiently detect cholesterol even if the concentration of interfering substances such as glucose, ascorbic acid, glycine and histidine is 25 times the concentration of cholesterol.
Example 9Fe3O4Colorimetric detection of serum total cholesterol at @ C-NT/Ni
According to the optimum experimental conditions searched for in examples 2 to 5, Fe was used3O4The method for colorimetric determination of serum total cholesterol comprises the following steps:
(1) adding four cholesterol standard solutions with different concentrations into each serum sample respectively;
(2) respectively and sequentially adding 80 mu L of the labeled serum samples with different cholesterol concentrations prepared in the step (1), 10 mu L of 10mg/mL cholesterol oxidase and 10 mu L of 10mg/mL cholesterol esterase into each centrifuge tube, and reacting for 10min in a water bath kettle at 37 ℃;
(3) 385 μ L of 0.2mol/LpH ═ 4.00 acetic acid-sodium acetate buffer solution, 2 μ L Fe3O4@ C-NT/Ni (5mg/mL), 12.5. mu.L of 3,3',5,5' -tetramethylbenzidine (TMB, 2mmol/L) were added to the above reaction solution and mixed well;
(4) reacting the mixed solution in a water bath at 50 ℃ for 10 min;
(5) by applying a magnetic field to Fe3O4Separating the @ C-NT/Ni from the reaction solution;
(6) the ultraviolet absorption spectrum of the reaction solution was measured by an ultraviolet-visible absorption spectrophotometer. And finally, calculating the content of the serum total cholesterol according to a standard curve of the cholesterol colorimetric detection.
TABLE 1 results of colorimetric determination of serum Total Cholesterol
The foregoing description of the embodiments is provided to enable any person skilled in the art to make or use the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of inventive faculty. Therefore, the present invention is not limited to the above-mentioned embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. The application of the ferroferric oxide-supported nickel-loaded carbonized layer nanotube in preparation of a peroxidase-like catalyst or a peroxidase simulant is characterized in that the ferroferric oxide-supported nickel-loaded carbonized layer nanotube comprises a ferroferric oxide nanotube and a nickel particle-loaded carbon nanotube coated on the outer wall of the ferroferric oxide nanotube, the length of the nickel particle-loaded carbon nanotube is 1-10 mu m, the inner diameter of the nickel particle-loaded carbon nanotube is 50-300 nm, the thickness of the ferroferric oxide nanotube is 30-80 nm, the thickness of the nickel particle-loaded carbon nanotube is 3-10 nm, and the particle size of the nickel particle is 2-6 nm.
2. The application of the ferroferric oxide supported nickel-loaded carbide layer nanotube according to claim 1, wherein the preparation method comprises the following steps:
(1) preparing a metal oxide supported iron oxyhydroxide nanorod: in an alcohol-water solution, reacting the metal oxide nanorod with ferric salt at 60-90 ℃ to generate a metal oxide supported hydroxyl ferric oxide nanorod;
(2) preparing a hydroxyl ferric oxide nanotube-supported nickel ion/carbonized precursor nanotube: dispersing the metal oxide supported iron oxyhydroxide nanorods prepared in the step (1) in an alkali-containing aqueous solution or an alcohol aqueous solution, adding a carbonization precursor organic matter and a nickel salt for reaction, removing the metal oxide nanorods and reacting on the surface of the iron oxyhydroxide to generate a nickel ion-loaded carbonization precursor layer, thereby obtaining the iron oxyhydroxide nanotube supported nickel ion/carbonization precursor nanotube;
(3) preparing a ferroferric oxide supported nickel-loaded carbonized layer nanotube: and (3) carbonizing the hydroxyl iron oxide supported nickel ion/carbonized precursor nanotube prepared in the step (2) at high temperature in a nitrogen atmosphere or an inert gas atmosphere to generate a ferroferric oxide supported nickel-loaded carbonized layer nanotube.
3. The application of claim 2, wherein in the step (1), the metal oxide nanorods have a length of 1-10 μm and a diameter of 50-300 nm, and comprise molybdenum trioxide nanorods, manganese dioxide nanorods, titanium dioxide nanorods, aluminum oxide nanorods, zinc oxide nanorods, copper oxide nanorods or tin dioxide nanorods;
the volume fraction of ethanol in the alcohol-water solution is 3% -15%, the molar ratio of the iron element to the molybdenum element is 2-3: 1, and the molar concentration of the iron element is 3 multiplied by 10-2～5×10-2mol/L。
4. The use according to claim 2, wherein in the step (2), the ratio of the amount of the iron oxyhydroxide nanorods supported on the metal oxide to the amount of the carbon element in the carbonized precursor is 1 g: (1.5X 10)-2～15×10-2) moL, wherein the molar ratio of carbon element to nickel element in the carbonization precursor is 1: 0.1-1; in the alcohol-water solution, the volume fraction of the ethanol is 35-75%, and the concentration of the alkali is 0.5-1.0 mol/L.
5. The ferroferric oxide supported nickel-loaded carbonized layer nanotube according to claim 1 is used for qualitatively or quantitatively detecting hydrogen peroxide or bioactive substances capable of generating hydrogen peroxide.
6. A method for detecting hydrogen peroxide is characterized in that a sample containing hydrogen peroxide, the ferroferric oxide supported nickel-loaded carbonized layer nanotube according to claim 1, a color indicator and a buffer solution are uniformly mixed and react for 5-30 minutes under the conditions that the pH is = 2-10 and the temperature is 25-60 ℃; separating the ferroferric oxide supported nickel-loaded carbon-coated nanotube, detecting the absorption spectrum of the reaction solution, and performing qualitative or quantitative determination on the hydrogen peroxide.
7. A method for detecting a biologically active substance, comprising the steps of:
a. mixing a sample containing bioactive substances with oxidase or hydrolase and oxidase corresponding to the bioactive substances to oxidize the bioactive substances in the sample with oxygen to generate hydrogen peroxide;
b. then adding the ferroferric oxide supported nickel-loaded carbon-coated nanotube, the color indicator and the buffer solution according to claim 1, uniformly mixing, and reacting for 5-30 minutes at the pH = 2-10 and the temperature of 25-65 ℃;
c. removing the ferroferric oxide supported nickel-loaded carbon nano tube, measuring the absorption spectrum of the reaction solution, and carrying out qualitative or quantitative detection.
8. The ferroferric oxide-supported nickel-carbide-layer nanotube according to claim 1, which is used for preparing a reagent or a kit for detecting hydrogen peroxide, or a reagent or a kit for detecting a bioactive substance capable of generating hydrogen peroxide in a biological sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810102269.9A CN108375574B (en) | 2018-02-01 | 2018-02-01 | Ferroferric oxide supported nickel-loaded carbonized layer nanotube and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810102269.9A CN108375574B (en) | 2018-02-01 | 2018-02-01 | Ferroferric oxide supported nickel-loaded carbonized layer nanotube and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108375574A CN108375574A (en) | 2018-08-07 |
| CN108375574B true CN108375574B (en) | 2020-11-20 |
Family
ID=63017105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810102269.9A Active CN108375574B (en) | 2018-02-01 | 2018-02-01 | Ferroferric oxide supported nickel-loaded carbonized layer nanotube and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108375574B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499616B (en) * | 2018-11-23 | 2021-08-24 | 杭州电子科技大学 | Preparation and application of ferroferric oxide composite metal chelate mimic enzyme |
| CN109342532B (en) * | 2018-12-07 | 2021-07-02 | 上海工程技术大学 | Core-shell nanorod coated with ferroferric oxide by nickel-negative carbonization layer and preparation method and application thereof |
| CN109879327B (en) * | 2019-01-25 | 2021-09-10 | 重庆科技学院 | Preparation of Fe by using metal oxide as catalyst3O4Method (2) |
| CN110208233A (en) * | 2019-06-09 | 2019-09-06 | 福建医科大学 | The method of nano cupric oxide enhancing fluoremetry ascorbic acid |
| CN110479241B (en) * | 2019-08-02 | 2021-09-28 | 电子科技大学 | Treatment method for improving peroxidase-like activity of nano-enzyme and product |
| CN110690446A (en) * | 2019-09-29 | 2020-01-14 | 蔚蓝(广东)新能源科技有限公司 | Preparation method of carbon-coated ferroferric oxide for iron-nickel battery |
| CN111001410B (en) * | 2019-12-25 | 2022-07-26 | 扬州大学 | Preparation of semiconductor bismuth vanadate-iron oxyhydroxide nanoenzyme and method for detecting hydrogen peroxide |
| CN111001423B (en) * | 2019-12-25 | 2022-07-01 | 扬州大学 | Preparation of semiconductor bismuth ferrite-titanium dioxide-nickel phosphide nanoenzyme and method for detecting hydrogen peroxide |
| CN113492012B (en) * | 2020-04-03 | 2024-06-11 | 中国石油化工股份有限公司 | Non-noble metal Ni-based catalyst, preparation method thereof and method for preparing cyclopentane by cyclopentadiene hydrogenation |
| CN114797889B (en) * | 2022-04-12 | 2023-10-17 | 上海工程技术大学 | Fe (Fe) 3 O 4 @MnO 2 -CeO 2 Nanometer material and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101387606A (en) * | 2008-08-01 | 2009-03-18 | 中国科学院长春应用化学研究所 | Method for detecting hydrogen peroxide or glucose based on enzyme simulation by ferroferric oxide magnetic nanometer particle |
| CN101832937A (en) * | 2010-04-23 | 2010-09-15 | 中国科学院上海应用物理研究所 | Method for detecting glucose based on nanometer materials |
| CN105129863B (en) * | 2015-08-11 | 2016-06-29 | 甘肃省科学院传感技术研究所 | Ferriferrous oxide nano cluster analogue enztme and preparation method and the method quickly detecting lactic acid with it |
| CN107242996B (en) * | 2017-05-08 | 2019-11-05 | 同济大学 | A kind of gel rubber material and preparation method thereof for oncotherapy |
-
2018
- 2018-02-01 CN CN201810102269.9A patent/CN108375574B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108375574A (en) | 2018-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108375574B (en) | Ferroferric oxide supported nickel-loaded carbonized layer nanotube and preparation method and application thereof | |
| Zhao et al. | Recent improvements in enzyme-linked immunosorbent assays based on nanomaterials | |
| CN108387545B (en) | Triiron tetraoxide-based composite carbon nanotube mimic enzyme and preparation method and application thereof | |
| Jiang et al. | Electrochemiluminescence of luminol enhanced by the synergetic catalysis of hemin and silver nanoparticles for sensitive protein detection | |
| Zeng et al. | Magnetic bead-based photoelectrochemical immunoassay for sensitive detection of carcinoembryonic antigen using hollow cadmium sulfide | |
| Luo et al. | Ultrasensitive fluorometric determination of hydrogen peroxide and glucose by using multiferroic BiFeO3 nanoparticles as a catalyst | |
| Rossini et al. | Green synthesis of fluorescent carbon dots for determination of glucose in biofluids using a paper platform | |
| CN109777412B (en) | Double-emission fluorescent carbon dot and preparation method and application thereof | |
| CN111517360A (en) | Nanocomposite based on phosphorus-molybdenum-containing polyoxometallate and preparation method thereof, aptamer sensor and electrode thereof | |
| Feng et al. | Sweetsop-like α-Fe 2 O 3@ CoNi catalyst with superior peroxidase-like activity for sensitive and selective detection of hydroquinone | |
| Gao et al. | Synthesis of core-shell structured Au@ Bi2S3 nanorod and its application as DNA immobilization matrix for electrochemical biosensor construction | |
| Gao et al. | Turn-on fluorescent sensor for the detection of glucose using manganese dioxide− phenol formaldehyde resin nanocomposite | |
| Luo et al. | Bimetallic Fe-Co nanoalloy confined in porous carbon skeleton with enhanced peroxidase mimetic activity for multiple biomarkers monitoring | |
| CN114487395A (en) | Construction method and use of nano antibody photoelectrochemical immunosensor for detecting SARS-CoV-2S protein | |
| Ren et al. | A multi-scenario dip-stick immunoassay of 17β-estradiol based on multifunctional and non-composite nanoparticles with colorimetric-nanozyme-magnetic properties | |
| CN110006722B (en) | Preparation method and application of ferroferric oxide/gold structure nanoparticles | |
| Yu et al. | Magnetically induced self-assembly DNAzyme electrochemical biosensor based on gold-modified α-Fe2O3/Fe3O4 heterogeneous nanoparticles for sensitive detection of Ni2+ | |
| Ma et al. | A cascade-triggered ratiometric fluorescent sensor based on nanocomposite for lactate determination | |
| Li et al. | Colorimetric strategy for ascorbic acid detection based on the oxidase‐like activity of silver nanoparticle single‐walled carbon nanotube composites | |
| Luo et al. | Pt/Ti3C2Tx nanozyme-amplified colorimetric lateral flow biosensor for dual-readout detection of HIV-DNA | |
| Guan et al. | Electrochemical Enhanced Detection of Uric Acid Based on Peroxidase‐like Activity of Fe3O4@ Au | |
| Chen et al. | Fluorescent biosensor based on magnetic cross-linking enzyme aggregates/CdTe quantum dots for the detection of H 2 O 2-bioprecursors | |
| CN111829993B (en) | Method for detecting hydrogen peroxide and related targets by CaS nano fluorescent probe | |
| Zhang et al. | A fluorimetric and colorimetric dual-signal sensor for hydrogen peroxide and glucose based on the intrinsic peroxidase-like activity of cobalt and nitrogen co-doped carbon dots and inner filter effect | |
| Gong et al. | Double-Amplified Electrochemiluminescence Immunoassay Sensor for Highly Sensitive Detection of CA19-9 Using a Ternary Semiconductor CdSSe |
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 |