CN113457741B - Preparation method and application of multi-enzyme active three-layer FeOx @ ZnMnFeOy @ Fe-Mn bimetal organogel - Google Patents
Preparation method and application of multi-enzyme active three-layer FeOx @ ZnMnFeOy @ Fe-Mn bimetal organogel Download PDFInfo
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- 229910002551 Fe-Mn Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910015189 FeOx Inorganic materials 0.000 title 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 174
- 238000001514 detection method Methods 0.000 claims abstract description 76
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 72
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229960001180 norfloxacin Drugs 0.000 claims abstract description 53
- 229940074391 gallic acid Drugs 0.000 claims abstract description 36
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 36
- 230000000694 effects Effects 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- 238000011088 calibration curve Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 238000005303 weighing Methods 0.000 claims description 20
- 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 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
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- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 7
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 7
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 7
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 7
- 235000018417 cysteine Nutrition 0.000 claims description 7
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims 1
- 229960004106 citric acid Drugs 0.000 abstract description 49
- 230000002194 synthesizing effect Effects 0.000 abstract 3
- 239000011572 manganese Substances 0.000 description 30
- 239000011701 zinc Substances 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 238000004737 colorimetric analysis Methods 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 230000007423 decrease Effects 0.000 description 4
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 3
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- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 description 2
- 238000011481 absorbance measurement Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
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- 235000009569 green tea Nutrition 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000273 veterinary drug Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-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 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- 206010061825 Duodenal neoplasm Diseases 0.000 description 1
- 208000013038 Hypocalcemia Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000204031 Mycoplasma Species 0.000 description 1
- 208000028389 Nerve injury Diseases 0.000 description 1
- KYGZCKSPAKDVKC-UHFFFAOYSA-N Oxolinic acid Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC2=C1OCO2 KYGZCKSPAKDVKC-UHFFFAOYSA-N 0.000 description 1
- 206010062237 Renal impairment Diseases 0.000 description 1
- 206010054184 Small intestine carcinoma Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
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- 201000000312 duodenum cancer Diseases 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
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- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 230000000705 hypocalcaemia Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000002405 nuclear magnetic resonance imaging agent Substances 0.000 description 1
- 239000003306 quinoline derived antiinfective agent Substances 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- 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
-
- 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
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- 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
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Abstract
The invention relates to a three-layer FeO with multienzyme activity x @ZnMnFeO y The preparation method of the @ Fe-Mn bimetal organogel comprises the following steps: s1: synthesizing Fe-Mn bimetallic organogel; s2: zn 0.5 Mn 0.5 Fe 2 O 4 Synthesizing; s3: znMnFeO y Preparing a nanoparticle-cysteine mixture; s4: three layers of FeO x @ZnMnFeO y And (3) synthesizing the @ Fe-Mn bimetallic organogel. The prepared catalyst is FeO x @ZnMnFeO y Modified Fe-Mn bimetallic organogel-based nanoenzymes having the properties of a three-enzyme mimetic. Meanwhile, a three-layer FeO with multi-enzyme activity is provided x @ZnMnFeO y Application of @ Fe-Mn bimetallic organogel to establish H 2 O 2 And a colorimetric detection method of citric acid, norfloxacin and gallic acid.
Description
Technical Field
The invention relates to a chemical substance preparation and determination technology, in particular to a multi-enzyme active three-layer FeO x @ZnMnFeO y A preparation method and application of @ Fe-Mn bimetal organogel.
Background
Citric Acid (CA) is used in food as an antioxidant and sour agent. Excessive CA intake can lead to hypocalcemia, duodenal cancer, and nerve damage. The implementation of CA detection is crucial in food products.
Norfloxacin is a quinolone antibiotic and veterinary drug. Is mainly used for urinary tract infection and gastrointestinal tract infection caused by sensitive bacteria. Children are prohibited from taking the drug because of cartilage development, renal impairment, and joint closure. The veterinary drug is mainly used for treating various infectious diseases caused by sensitive bacteria and mycoplasma in animals.
Nanoenzymes, a novel natural enzyme mimetic, have been studied extensively for decades. Due to its high tolerance, high catalytic efficiency and low cost, nanoenzymes are widely used in many fields, such as biosensing, biomedical applications, antibacterial and pollutant detection. In recent years, manganese zinc ferrite has received much attention due to its activity, magnetic and dielectric properties of various enzymes. Zinc-doped manganese ferrites having a spinel structure are of technical significance due to their use in information storage, electronics, magnetic resonance imaging contrast agents, medical diagnostics, drug delivery. Metal organogels are 3D porous metal nano-networks with high specific surface area and porosity. The manganese-zinc ferrite nanoenzyme with simple structure and multienzyme simulation property and the iron-manganese bimetallic organogel with large specific surface area can have the potential of detecting antibiotics, food pollutants, antibiotics and biomolecules.
The main limitations of the current detection technology are: long time consumption, destructive analysis, qualified personnel, use of chemical reagents and low sensitivity. Therefore, developing a simple, rapid and sensitive analysis method remains one of the research hotspots and a technical problem to be solved in the art.
Disclosure of Invention
To solve the above problems of the prior art, the present invention provides three layers
FeO x @ZnMnFeO y Method for preparing @ Fe-Mn bimetal organogel (FO @ ZMFO @ FM-MOG), and catalyst prepared by the method is FeO x @ZnMnFeO y (abbreviated as FO @ ZMFO) modified Fe-Mn bimetallic organogel (FM-MOG) based core-shell structured nanoenzymes having the properties of a three-enzyme mimetic including peroxidase-like, catalase-like and oxidase-like. The oxidase-like catalytic mechanism originates from oxygen vacancies and superoxide radicals (. O) 2 - ) Whereas peroxidase-like activity results from electron transport capability and hydroxyl radical (. OH). Simultaneously, the application of the FO @ ZMFO @ FM-MOG core-shell structure on the intelligent terminal platform is provided, namely, the H @ ZMFO @ FM-MOG nano composite material based on the multi-enzyme activity of the FO @ ZMFO @ FM-MOG nano composite material is established 2 O 2 A colorimetric method of citric acid, norfloxacin and gallic acid, a simple four-functional colorimetric sensing platform for detecting H 2 O 2 Citric acid, norfloxacin and gallic acid.
In order to achieve the purpose, the invention adopts the main technical scheme that:
according to a first aspect of the invention: three-layer FeO with multi-enzyme activity x @ZnMnFeO y The preparation method of the @ Fe-Mn bimetal organogel comprises the following steps:
s1: synthesis of Fe-Mn bimetal organogel
Weighing Mn (NO) 3 ) 2 ·4H 2 O and Fe (NO) 3 ) 3 ·9H 2 Dissolving O in ethanol, weighing trimesic acid, dissolving in ethanol, adding triethylamine, standing, washing with ethanol for three times, and freeze-drying to obtain Fe-Mn bimetallic organogel;
S2：Zn 0.5 Mn 0.5 Fe 2 O 4 synthesis of (2)
Weighing polyvinylpyrrolidone, dissolving in ultrapure waterAnd stirred, then Mn (NO) is added 3 ) 2 ·4H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 Continuously stirring after O, drying the mixture in an oven overnight to obtain dry powder, and calcining the dry powder in a muffle furnace to obtain Zn 0.5 Mn 0.5 Fe 2 O 4 Nanoparticles;
S3：ZnMnFeO y preparation of nanoparticle-cysteine mixture
Weighing Zn 0.5 Mn 0.5 Fe 2 O 4 Dissolving the nano particles and the cysteine in ethanol, stirring and dissolving, washing with ethanol, centrifuging and drying to obtain ZnMnFeO y Storing the nanoparticle-cysteine mixture at room temperature;
s4: three layers of FeO x @ZnMnFeO y Synthesis of @ Fe-Mn bimetal organogel
Weighing ZnMnFeO y Dissolving the nanoparticle-cysteine mixture in 2- (N-morpholine) ethanesulfonic acid containing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, stirring, adding Fe-Mn bimetallic organogel, stirring, washing with ethanol for three times, centrifuging, and freeze-drying to obtain three-layer FeO x @ZnMnFeO y @ Fe-Mn bimetallic organogels.
Further, in step S1:
the Mn (NO) 3 ) 2 ·4H 2 O and Fe (NO) 3 ) 3 ·9H 2 The dosage ratio of O is a molar ratio, and the molar ratio is 2-3:1;
the mol dosage of the trimesic acid is Fe (NO) 3 ) 3 ·9H 2 1.5-2 times of O;
the standing time is 3.5-5h.
Further, in step S2:
the Mn (NO) 3 ) 2 ·4H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The dosage ratio of O is a molar ratio, and the molar ratio is 1:1:2-4;
the stirring time is 1-2h;
the calcining temperature is 550-560 ℃, and the calcining time is 3-4h.
Further, in step S3:
said Zn 0.5 Mn 0.5 Fe 2 O 4 The dosage ratio of the nano particles to the cysteine is a mass ratio, and the mass ratio is 10:1;
the stirring time is at least 12h;
in step S4:
the dosage ratio of the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 2- (N-morpholine) ethanesulfonic acid of the N-hydroxysuccinimide is a mass ratio of (5-6): 4;
the stirring time for adding the Fe-Mn bimetallic organogel is not less than 48h.
According to a second aspect of the invention, three layers of FeO are produced x @ZnMnFeO y Application of @ Fe-Mn bimetallic organogel to H 2 O 2 Detection of (2):
adding three layers of FeO with concentration of 12.5 μ g/mL into 0.2M acetic acid buffer with pH =3.5 x @ZnMnFeO y The method comprises the steps of @ Fe-Mn bimetallic organogel and 3,3',5,5' -tetramethylbenzidine, and then adding H with different concentrations 2 O 2 Incubating at 50 ℃ for 10min, and recording the absorbance at 652nm by using an ultraviolet spectrophotometer;
wherein:
said H 2 O 2 The linear detection concentration range of (1) is 37-337 muM;
the calibration curve is y =1.92521x +0.41151 2 =0.997,x is H 2 O 2 The concentration of (c).
According to a third aspect of the invention, three layers of FeO are produced x @ZnMnFeO y The application of @ Fe-Mn bimetal organogel in the detection of citric acid:
citric acid with different concentrations, three layers of FeO with the volume of 100 mu L and the concentration of 1mg/mL x @ZnMnFeO y @ Fe-Mn bimetallic organogel and 5mM 3,3',5,5-Tetramethylbenzidine was added to acetate buffer pH =3.5, and H was added in a volume of 100. Mu.L at 50 ℃ and at a concentration of 10mM 2 O 2 After adding the mixture for 10min, recording the ultraviolet absorption spectrum;
the linear detection concentration of the citric acid is 0.415-6.21 mu M, and the lower detection limit is 79nM;
the calibration curve is y = -0.2289x +1.79865 2 =0.99133, x is the concentration of citric acid.
Further, an intelligent terminal platform APP is established, colorimetric photos and colorimetric signals are collected through an intelligent terminal, citric acid with different concentrations is added into a reaction system, then a photo specific area is selected through the intelligent terminal platform APP, a recording mode is carried out, and an automatically generated fitting equation is displayed on a screen of the intelligent terminal;
wherein the mode is one of G/B-C, R/B-C, R/G-C, R-C, G-C, B-C, gray-C and S/V-C;
wherein, under the mode Gray-C, the fitting equation is Y =15.2236+2.5257X 2 =0.9942, x is the concentration of citric acid.
According to the fourth aspect of the invention, three layers of FeO are produced x @ZnMnFeO y The application of @ Fe-Mn bimetallic organogel in detecting norfloxacin:
adding 12 μm citric acid solution and norfloxacin at different concentrations in acetate buffer with concentration of 0.2M, pH =3.5, incubating at 50 deg.C for 10min, adding 3,3',5,5' -tetramethylbenzidine at concentration of 5mM and three layers of FeO at concentration of 1mg/mL x @ZnMnFeO y @ Fe-Mn bimetallic organogel, and then, measuring the absorbance of the reaction solution at 625nm by an ultraviolet-visible spectrophotometer;
the linear detection concentration of the norfloxacin is 0.409 mu M-4.706 mu M, and the lower detection limit is 0.52nM;
the calibration curve is y =0.1429x +0.28305 2 =0.99224,x is the concentration of norfloxacin.
Further, an intelligent terminal platform APP is established, colorimetric photos and colorimetric signals are collected through an intelligent terminal, norfloxacin with different concentrations is added into the reaction system, then, a photo specific area is selected through the intelligent terminal platform APP, a recording mode is carried out, and an automatically generated fitting equation is displayed on a screen of the intelligent terminal;
wherein the mode is one of a G/BC mode and an HC mode;
wherein, in the G/BC mode, the fitting equation is Y =0.9357+0.0041X 2 =0.9942,x is the concentration of norfloxacin;
in HC mode, the fitting equation is Y =183.9125-0.2488X, R 2 =0.9936,x is the concentration of norfloxacin.
According to a fifth aspect of the invention, three layers of FeO are produced x @ZnMnFeO y The application of @ Fe-Mn bimetallic organogel to the detection of gallic acid:
1mg/mL of three-layer FeO was added to an acetate buffer solution having a concentration of 0.2M, a volume of 2.2mL and a pH =3.5 x @ZnMnFeO y A @ Fe-Mn bimetallic organogel catalyst, 5mM 3,3',5,5' -tetramethylbenzidine solution and gallic acid with different concentrations were incubated at 37 ℃ for 30min, and the UV absorption spectrum at 652nm wavelength was recorded;
the linear detection concentration of the gallic acid is 0.4762-5.2632 muM, and the lower detection limit is 0.079 muM;
the calibration curve is y = -0.0615x +0.76644 2 =0.9979,x is the concentration of gallic acid.
The beneficial effects of the invention are:
(1) Synthesizes and constructs a new compound with FeO x @ZnMnFeO y (FO @ ZMFO) modified Fe-Mn bimetallic organogel (FM-MOG) based nanoenzymes with properties of a three-enzyme mimetic including peroxidase-like, catalase-like and oxidase-like. The oxidase-like catalytic mechanism originates from oxygen vacancies and superoxide radicals (. O) 2 - ) Whereas peroxidase-like activity results from electron transport capability and hydroxyl radical (. OH).
(2) The peroxidase-like activity of FO @ ZMFO @ FM-MOG was utilized to establish H 2 O 2 Colorimetric sensorThe linear range is 37 μ M to 337 μ M.
(3) A colorimetric sensor and an intelligent terminal detection platform of citric acid are established by using peroxidase-like activity of FO @ ZMFO @ FM-MOG, the linear range of the colorimetric sensor and the intelligent terminal detection platform is 0.415 mu M to 6.21 mu M, and the lower limit of detection (LOD) is 79nM. An intuitive and convenient field detection method for the concentration of the citric acid can be established without using expensive equipment. The established sensor requires little expensive reagents and instruments and provides a convenient and rapid quantitative citric acid detection route.
(4) A colorimetric sensor and an intelligent terminal detection platform of norfloxacin are established by utilizing peroxidase-like activity of FO @ ZMFO @ FM-MOG, the linear range of the colorimetric sensor and the intelligent terminal detection platform is 0.409 mu M to 4.706 mu M, and the lower limit of detection (LOD) is 52nM. The established intelligent terminal detection platform integrates colorimetric signals and can realize intuitive norfloxacin detection. Compared with other methods for monitoring norfloxacin by simulating enzyme, the colorimetric sensor disclosed by the invention is more sensitive than most of sensors based on other nano-enzyme.
(5) A colorimetric sensor of gallic acid is established by utilizing similar oxidase-like activity of FO @ ZMFO @ FM-MOG, the linear range of the colorimetric sensor is 0.4762 mu M to 5.2632 mu M, and the lower limit of detection (LOD) is 0.079 mu M. Compared with the prior art, the FO @ ZMFO @ FM-MOG nanoenzyme is an effective candidate for constructing a gallic acid colorimetric sensor.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of FM-MOG.
FIG. 2 is a Transmission Electron Microscope (TEM) image of ZMFO.
FIG. 3 is a Transmission Electron Microscope (TEM) image of FO @ ZMFO @ FM-MOG.
In fig. 4: (A) Detection of H for FO @ ZMFO @ FM-MOG 2 O 2 Ultraviolet spectrogram of (A) and (B) for detecting H 2 O 2 The calibration curve of (1).
In fig. 5: (A) is the ultraviolet spectrogram that FO @ ZMFO @ FM-MOG detects citric acid, (B) is the calibration curve that detects citric acid and (C) is the Gray-C mode fitting curve that intelligent terminal platform APP detected citric acid.
In fig. 6: the method comprises the following steps of (A) detecting an ultraviolet spectrogram of norfloxacin for FO @ ZMFO @ FM-MOG, (B) detecting a calibration curve of norfloxacin, (C) detecting a G/BC mode fitting curve of norfloxacin for an intelligent terminal platform APP, and (D) detecting an HC mode fitting curve of norfloxacin for the intelligent terminal platform APP.
In fig. 7: (A) The UV spectrogram of gallic acid detected by FO @ ZMFO @ FM-MOG and (B) the calibration curve of gallic acid detection.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The technical scheme of the invention is summarized as follows: the invention provides three layers of FeO x @ZnMnFeO y Preparation method of @ Fe-Mn bimetallic organogel (FO @ ZMFO @ FM-MOG for short), and prepared catalyst is FeO x @ZnMnFeO y (abbreviated as FO @ ZMFO) modified Fe-Mn bimetallic organogel (abbreviated as FM-MOG) based core-shell structured nanoenzymes having the characteristics of a three-enzyme mimetic including peroxidase-like, catalase-like and oxidase-like. The oxidase-like catalytic mechanism originates from oxygen vacancies and superoxide radicals (. O) 2 - ) Whereas peroxidase-like activity results from electron transport capability and hydroxyl radical (. OH). Simultaneously, the application of the FO @ ZMFO @ FM-MOG core-shell structure on the intelligent terminal platform is provided, namely, the H @ ZMFO @ FM-MOG nano composite material based on the multi-enzyme activity of the FO @ ZMFO @ FM-MOG nano composite material is established 2 O 2 A colorimetric method of citric acid, norfloxacin and gallic acid, a simple four-functional colorimetric sensing platform for detecting H 2 O 2 Citric acid, norfloxacin and gallic acid.
To illustrate the solution and technical advancement of the present invention, the technical solution and technical application designed now are as follows:
three-layer FeO with multi-enzyme activity x @ZnMnFeO y The preparation method of the @ Fe-Mn bimetal organogel comprises the following steps:
s1: synthesis of Fe-Mn bimetallic organogel
Weighing Mn (NO) 3 ) 2 ·4H 2 O and Fe (NO) 3 ) 3 ·9H 2 Dissolving O in ethanol, weighing trimesic acid, dissolving in ethanol, adding triethylamine, standing, washing with ethanol for three times, and freeze-drying to obtain Fe-Mn bimetallic organogel;
S2：Zn 0.5 Mn 0.5 Fe 2 O 4 synthesis of (2)
Weighing polyvinylpyrrolidone, dissolving in ultrapure water, stirring, and adding Mn (NO) 3 ) 2 ·4H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 Continuously stirring after O, drying the mixture in an oven overnight to obtain dry powder, and calcining the dry powder in a muffle furnace to obtain Zn 0.5 Mn 0.5 Fe 2 O 4 Nanoparticles;
S3：ZnMnFeO y preparation of nanoparticle-cysteine mixture
Weighing Zn 0.5 Mn 0.5 Fe 2 O 4 Dissolving the nano particles and the cysteine in ethanol, stirring and dissolving, washing with ethanol, centrifuging and drying to obtain ZnMnFeO y Storing the nanoparticle-cysteine mixture at room temperature;
s4: three layers of FeO x @ZnMnFeO y Synthesis of @ Fe-Mn bimetal organogel
Weighing ZnMnFeO y Dissolving the nanoparticle-cysteine mixture in 2- (N-morpholine) ethanesulfonic acid containing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, stirring, adding Fe-Mn bimetallic organogel, stirring, washing with ethanol for three times, centrifuging, and freeze-drying to obtain three layers of FeO x @ZnMnFeO y @ Fe-Mn bimetallic organogel.
In step S1: mn (NO) 3 ) 2 ·4H 2 O and Fe (NO) 3 ) 3 ·9H 2 The dosage ratio of O is a molar ratio, and the molar ratio is 2-3:1; the mol dosage of the trimesic acid is Fe (NO) 3 ) 3 ·9H 2 1.5-2 times of O; the standing time is 3.5-5h.
In step S2: mn (NO) 3 ) 2 ·4H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The dosage ratio of O is a molar ratio, and the molar ratio is 1:1:2-4; the stirring time is 1-2h; the calcining temperature is 550-560 ℃, and the calcining time is 3-4h.
In step S3: zn 0.5 Mn 0.5 Fe 2 O 4 The dosage ratio of the nano particles to the cysteine is mass ratio, and the mass ratio is 1:1; the stirring time is at least 12h;
in step S4: the dosage ratio of the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 2- (N-morpholine) ethanesulfonic acid of the N-hydroxysuccinimide is the mass ratio of 5-6:4; the stirring time for adding the Fe-Mn bimetal organogel is not less than 48h.
Applying the prepared FO @ ZMFO @ FM-MOG to H 2 O 2 Detection of (2):
to 0.2M acetic acid buffer at pH =3.5 was added FO @ ZMFO @ FM-MOG and 3,3',5,5' -tetramethylbenzidine at a concentration of 12.5. Mu.g/mL, followed by different concentrations of H 2 O 2 Incubating at 50 ℃ for 10min, and recording the absorbance at 652nm by using an ultraviolet spectrophotometer;
wherein:
H 2 O 2 the linear detection concentration range of (1) is 37-337 muM;
the calibration curve is y =1.92521x +0.41151 2 =0.997,x is H 2 O 2 The concentration of (c).
The prepared FO @ ZMFO @ FM-MOG is applied to the detection of citric acid:
citric acid at various concentrations, FO @ ZMFO @ FM-MOG at a concentration of 1mg/mL in a volume of 100. Mu.L and 5mM in a volume of 3,3',5,5' -tetramethylbenzidine were added to acetate buffer pH =3.5, and H at a concentration of 10mM in a volume of 100. Mu.L at 50 ℃ was added 2 O 2 After adding the mixture for 10min, recording the ultraviolet absorption spectrum;
the linear detection concentration of the citric acid is 0.415-6.21 mu M, and the lower detection limit is 79nM;
the calibration curve is y = -0.2289x +1.79865，R 2 =0.99133, x is the concentration of citric acid.
An intelligent terminal platform APP is further established, colorimetric photos and colorimetric signals are collected through an intelligent terminal, citric acid with different concentrations is added into a reaction system, then, a photo specific area is selected through the intelligent terminal platform APP, a recording mode is carried out, and an automatically generated fitting equation is displayed on a screen of the intelligent terminal;
wherein the mode is one of G/B-C, R/B-C, R/G-C, R-C, G-C, B-C, gray-C and S/V-C;
wherein, under the mode Gray-C, the fitting equation is Y =15.2236+2.5257X 2 =0.9942,x is the concentration of citric acid.
The prepared FO @ ZMFO @ FM-MOG is applied to the detection of norfloxacin:
to acetate buffer at a concentration of 0.2M, pH =3.5 was added a 12 μm citric acid solution and various concentrations of norfloxacin, after incubation at 50 ℃ for 10min, 3,3',5,5' -tetramethylbenzidine at a concentration of 5mM and fo @ zmfo @ fm-MOG at a concentration of 1mg/mL were added. Then, absorbance measurement of the reaction solution was performed at 625nm by an ultraviolet-visible spectrophotometer;
the linear detection concentration of norfloxacin is 0.409 mu M-4.706 mu M, and the lower limit of detection is 0.52nM;
the calibration curve is y =0.1429x +0.28305 2 =0.99224,x is the concentration of norfloxacin.
Further establishing an intelligent terminal platform APP, collecting colorimetric photos and colorimetric signals through an intelligent terminal, adding citric acid with different concentrations into a reaction system, then selecting a photo specific area through the intelligent terminal platform APP, recording a mode, and displaying an automatically generated fitting equation on a screen of the intelligent terminal;
wherein the mode is one of a G/BC mode and an HC mode;
wherein, in the G/BC mode, the fitting equation is Y =0.9357+0.0041X 2 =0.9942,x is the concentration of norfloxacin;
in HC mode, the fitting equation is Y =183.9125-0.2488X 2 =0.9936,x is the concentration of norfloxacin.
The prepared FO @ ZMFO @ FM-MOG is applied to detection of gallic acid:
adding 1mg/mL Zn to an acetate buffer solution with a concentration of 0.2M, a volume of 2.2mL and a pH =3.5 0.5 Mn 0.5 Fe 2 O 4 @ FeMn-MOG catalyst and 5mM 3,3',5,5' -tetramethylbenzidine solution and different concentrations of gallic acid, incubating the reaction mixture at 37 ℃ for 30min, and recording the UV absorption spectrum at 652nm wavelength;
the linear detection concentration of the gallic acid is 0.4762-5.2632 muM, and the lower detection limit is 0.079 muM;
the calibration curve is y = -0.0615x +0.76644 2 =0.9979,x is the concentration of gallic acid.
Example (b):
preparation of (mono) FO @ ZMFO @ FM-MOG
S1: synthesis of Fe-Mn bimetallic organogel (FM-MOG)
The molar ratio of the raw materials is 2:1 weighing 0.7553g of Mn (NO) 3 ) 2 ·4H 2 O (manganese nitrate) and 0.6g of Fe (NO) 3 ) 3 ·9H 2 Dissolving O (ferric nitrate) in 10mL of ethanol, weighing 0.5g of trimesic acid to dissolve in 10mL of ethanol, adding 0.5mL of triethylamine, standing for 4 hours, washing with ethanol for three times after standing, and freeze-drying to obtain Fe-Mn bimetal organogel (FM-MOG);
S2：Zn 0.5 Mn 0.5 Fe 2 O 4 synthesis of (2)
Weighing 3g of polyvinylpyrrolidone, dissolving in 100mL of ultrapure water, stirring for 2h, and then mixing according to a molar ratio of 1:1:2 weighing Mn (NO) added with 0.01255g 3 ) 2 ·4H 2 O (manganese nitrate), 0.0149g of Zn (NO) 3 ) 2 ·6H 2 O (Zinc nitrate) and 0.0404g of Fe (NO) 3 ) 3 ·9H 2 Continuously stirring for 1h after O (ferric nitrate), drying in an oven overnight to obtain dry powder, and calcining the dry powder in a muffle furnace at 550 ℃ for 3h to obtain Zn 0.5 Mn 0.5 Fe 2 O 4 Nanoparticles;
S3：ZnMnFeO y preparation of nanoparticle-cysteine mixture
0.03g of Zn was weighed 0.5 Mn 0.5 Fe 2 O 4 Dissolving the nano particles and 0.3g of cysteine in 100mL of ethanol, stirring for 12h for dissolving, washing with ethanol, centrifuging and drying to obtain ZnMnFeO y Storing the nanoparticle-cysteine mixture at room temperature;
s4: three layers of FeO x @ZnMnFeO y Synthesis of @ Fe-Mn bimetallic organogel (FO @ ZMFO @ FM-MOG)
Weighing ZnMnFeO y The nanoparticle-cysteine mixture was dissolved in 2- (N-morpholine) ethanesulfonic acid containing 0.25g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.2g of N-hydroxysuccinimide and stirred for 1.5h, then FM-MOG was added and stirred for 48h, then washed three times with ethanol, centrifuged and freeze dried to give three layers of FeO x @ZnMnFeO y @ Fe-Mn bimetallic organogels (FO @ ZMFO @ FM-MOG).
As shown in FIGS. 1 to 3, FO @ ZMFO @ FM-MOG was prepared by the 4-step method described above, in which TEM showed that FM-MOG is one nanorod (FIG. 1), ZMFO is a nanoparticle (FIG. 2), and ZMFO was supported on the surface of FM-MOG, demonstrating the successful preparation of FO @ ZMFO @ FM-MOG composite (FIG. 3).
Table 1 shows inductively coupled plasma analysis (ICP) of FO @ ZMFO @ FM-MOG. ICP mass analysis indicates that the actual Fe content in FO @ ZMFO @ FM-MOG is as high as 96.79%, much greater than manganese (2.92%) and zinc (0.29%). The actual manganese and zinc contents are much lower than the theoretical contents, compared to the theoretical contents of Mn (47.73%) and Zn (2.27%), demonstrating the significant reduction in Zn and Mn contents of the FO @ ZMFO @ FM-MOG surface. While the Mn content inside the FO @ ZMFO @ FM-MOG material is comparable to that of C and O because Mn at the surface of the material is corroded away by the acid solution, thereby forming nuclei. The FO @ ZMFO @ FM-MOG prepared by the invention is a core-shell structure material with an outermost FeO shell, low external manganese content and high internal manganese content.
TABLE 1 inductively coupled plasma analysis of FO @ ZMFO @ FM-MOG
Application of (di) FO @ ZMFO @ FM-MOG to H 2 O 2 Example of detection of
To 2170. Mu.L of acetic acid buffer solution at 0.2M with pH =3.5, FO @ ZMFO @ FM-MOG with a concentration of 12.5. Mu.g/mL and 5mM 3,3',5,5' -tetramethylbenzidine (abbreviated as TMB) were added, and then H with different concentrations was added 2 O 2 Incubating at 50 ℃ for 10min, and recording the absorbance at 652nm by using an ultraviolet spectrophotometer;
wherein: h 2 O 2 The linear detection concentration range of (1) is 37-337 muM; the calibration curve is y =1.92521x +0.41151 2 =0.997,x is H 2 O 2 The concentration of (2).
H 2 O 2 The increase in concentration resulted in a color change from colorless to blue as a result of the production of OH by FO @ ZMFO @ FM-MOG nanocomposites. As shown in FIG. 4 (A), the absorbance from c-b-a increases from bottom to top as the concentration increases, i.e., A 652nm Signal with H 2 O 2 Gradually increases from 37 μ M to 337 μ M. As shown in FIG. 4 (B), A was observed at a concentration ranging from 37. Mu.M to 337. Mu.M 652nm And H 2 O 2 There is a good linear relationship between, and y =1.92521x +0.41151 (R) of the calibration curve 2 = 0.997). This example establishes a H by the peroxidase-like activity of FO @ ZMFO @ FM-MOG 2 O 2 A colorimetric sensor.
TABLE 2 FO @ ZMFO @ FM-MOG catalytic colorimetric sensor vs. H in water 2 O 2 Analytical Properties of detection
To test the utility of the method, different concentrations of H were used 2 O 2 Add to three water samples and proceed according to standard addition methods. As shown in Table 2, H 2 O 2 The Relative Standard Deviation (RSD) of (a) is between 97% and 106%. Experimental result verifiesThe colorimetric method is used for H in actual samples 2 O 2 Reliability and practicality of analysis.
Example of application of (tri) FO @ ZMFO @ FM-MOG to citric acid
Different concentrations of 100. Mu.L citric acid, FO ZMFO @ FM-MOG at a volume of 100. Mu.L and a concentration of 1mg/mL, and 3,3',5,5' -tetramethylbenzidine at a volume of 100. Mu.L and a concentration of 5mM were added to 1.8mL of acetate buffer pH =3.5, and H at a concentration of 10mM at a volume of 100. Mu.L at 50 ℃ 2 O 2 After adding the mixture for 10min, recording the ultraviolet absorption spectrum; the linear detection concentration of the citric acid is 0.415 mu M-6.21 mu M, and the lower detection limit is 79nM; the calibration curve is y = -0.2289x +1.79865 2 =0.99133, x is the concentration of citric acid. Establishing an intelligent terminal platform APP, collecting colorimetric photos and colorimetric signals through an intelligent terminal, adding citric acid with different concentrations into a reaction system, then selecting a photo specific region through the intelligent terminal platform APP, recording a mode, and displaying an automatically generated fitting equation on a screen of the intelligent terminal; the mode is one of G/B-C, R/B-C, R/G-C, R-C, G-C, B-C, gray-C and S/V-C; wherein, under the mode Gray-C, the fitting equation is Y =15.2236+2.5257X 2 =0.9942, x is the concentration of citric acid.
In this example, FO @ ZMFO @ FM-MOG catalyzed TMB/H with increasing citric acid content 2 O 2 The system showed a weak color change. Therefore, as shown in FIG. 5 (A), the absorbance from c-b-a increases from bottom to top as the concentration decreases, and the UV-Vis spectrum shows a decrease in signal. As shown in FIG. 5 (B), the citric acid concentration decreased linearly in absorbance at 652nm from 0.415. Mu.M to 6.21. Mu.M. The equation can be written as y = -0.2289x +1.79865 (R) 2 = 0.99133). The lower limit of detection (LOD) calculated from S/N =3 was 79nM. As shown in fig. 5 (C), a convenient intelligent terminal platform is established, which integrates colorimetric signals to enable convenient visual detection of citric acid. Citric acid with different concentrations is added into a reaction system, and colorimetric photos are collected through an intelligent terminal. Then, selecting a specific area of the photo through the self-developed APP and recording. It can then analyze the acquired images on-line and intelligently calculate statistics using different patterns of G/B-C, R/B-C, R/G-C, R-C, G-C, B-C and Gray-C, S/V-C. Finally, due to the better linear relationship with citric acid concentration, the Gray-C mode was selected and the automatically generated fitting equation Y =15.2236+2.5257x (R) 2 = 0.9942) is displayed on the screen of the intelligent terminal. Therefore, an intuitive and convenient field detection method for the concentration of the citric acid can be established without using expensive equipment. The established sensor requires little expensive reagents and instruments and provides a convenient and rapid quantitative citric acid detection route.
TABLE 3 analytic Performance of FO @ ZMFO @ FM-MOG catalytic colorimetric sensor for citric acid in fruit juices
To test the utility of the method, citric acid at various concentrations was mixed into the juice sample and performed according to standard addition methods. As shown in table 3, the Relative Standard Deviation (RSD) of citric acid was between 95% and 105%. The experimental result verifies the reliability and the practicability of the colorimetric method for analyzing the citric acid in the actual sample.
Example of application of (tetra) FO @ ZMFO @ FM-MOG to norfloxacin
To acetate buffer solution with a concentration of 0.2M, pH =3.5 was added citric acid solution of 12 μm and norfloxacin (abbreviation: NOR) of various concentrations, after incubation for 10min at 50 ℃,3,3 ',5,5' -tetramethylbenzidine with a concentration of 5mM and fo @ zmfo @ fm-MOG with a concentration of 1 mg/mL. Then, absorbance measurement of the reaction solution was performed at 625nm by an ultraviolet-visible spectrophotometer; the linear detection concentration of norfloxacin is 0.409 mu M-4.706 mu M, and the lower limit of detection is 0.52nM; the calibration curve is y =0.1429x +0.28305 2 =0.99224,x is the concentration of norfloxacin.
And an intelligent terminal platform APP is further established, colorimetric photos and colorimetric signals are collected through an intelligent terminal, norfloxacin with different concentrations is added into a reaction system, and thenSelecting a specific area of a photo through an intelligent terminal platform APP, carrying out a recording mode, and displaying an automatically generated fitting equation on a screen of an intelligent terminal; the mode is one of a G/BC mode and an HC mode; wherein, in the G/BC mode, the fitting equation is Y =0.9357+0.0041X 2 =0.9942,x is the concentration of norfloxacin; in HC mode, the fitting equation is Y =183.9125-0.2488X 2 =0.9936,x is the concentration of norfloxacin.
The embodiment establishes a method for detecting norfloxacin by a colorimetric method and a smart phone. As shown in FIG. 6 (A), the absorbance from c-b-a increases from bottom to top with increasing concentration, i.e., with increasing norfloxacin, FO @ ZMFO @ FM-MOG/TMB/H 2 O 2 The UV-visible absorption intensity of citric acid increases. As shown in FIG. 6 (B), norfloxacin was monitored to have a good linear relationship ranging from 0.409. Mu.M to 4.706. Mu.M (R) 2 = 0.99224), detection limit 52nM, calibration curve y =0.1429x +0.28305, R 2 =0.99224,x is the concentration of norfloxacin. As shown in fig. 6 (C) and (D), different concentrations of NOR were analyzed by the smart terminal. The G/BC mode and HC mode are chosen because they both have good linearity in dual mode, and the automatically generated fitting equation Y =0.9357+0.0041X (R) 2 = 0.9942) and Y =183.9125-0.2488X (R) 2 = 0.9936) is displayed on the smart terminal screen. Compared with other methods for monitoring norfloxacin by simulating enzyme, the colorimetric sensor disclosed by the invention is sensitive to most of sensors based on other nano-enzymes.
TABLE 4 analysis Performance of the FO @ ZMFO @ FM-MOG catalytic colorimetric sensor for detecting norfloxacin in drugs
To test the utility of the method, norfloxacin at various concentrations was mixed into the drug and performed according to standard addition methods. As shown in table 4, the Relative Standard Deviation (RSD) for norfloxacin was within 6%, indicating good reproducibility. It can be concluded that this method can be used to detect norfloxacin concentrations.
Example of detection of application of (penta) FO @ ZMFO @ FM-MOG to gallic acid
To an acetate buffer solution at a concentration of 0.2M, a volume of 2.2mL and a pH =3.5 were added 1mg/mL FO @ ZMFO @ FM-MOG catalyst and 5mM 3,3',5,5' -tetramethylbenzidine solution and different concentrations of gallic acid, the reaction mixture was incubated at 37 ℃ for 30min, and the UV absorption spectrum at 652nm wavelength was recorded; the linear detection concentration of the gallic acid is 0.4762-5.2632 muM, and the lower detection limit is 0.079 muM; the calibration curve is y = -0.0615x +0.76644 2 =0.9979,x is the concentration of gallic acid.
FIG. 7 (A) shows that the absorbance from c-b-a increases from bottom to top in order as the concentration decreases, i.e., the UV-visible absorption spectrum signal decreases as the concentration of gallic acid increases. As shown in fig. 7 (B), the correlation between the change in the ultraviolet-visible absorption spectrum signal and the concentration of gallic acid showed a good linear relationship in the range of 0.4762 μ M to 5.2632 μ M. The fitted linear equation is y = -0.0615x +0.76644 (R) 2 = 0.9979) detection limit 0.079 μ M, where y is absorbance and x is concentration of gallic acid. Compared with the prior art, the FO @ ZMFO @ FM-MOG nanoenzyme is an effective candidate for constructing the gallic acid colorimetric sensor.
TABLE 5 analysis of gallic acid in Green tea by FO @ ZMFO @ FM-MOG catalytic colorimetric sensor
To test the utility of this method, different concentrations of gallic acid were mixed into green tea samples and performed according to standard addition methods. As shown in table 5, to demonstrate the specificity and accuracy of the gallic acid test, recovery of gallic acid was found to be acceptable, and the recovery of tea was in the range of 95-105%, both below 5% relative standard deviation, indicating that the test was sufficiently accurate for gallic acid detection.
Three layers of FeO with multi-enzyme activity x @ZnMnFeO y @FThe preparation method and the application of the e-Mn bimetal organogel have the following technical principles and technical effects:
(1) Synthesizes and constructs a new compound with FeO x @ZnMnFeO y (FO @ ZMFO) modified Fe-Mn bimetallic organogel (FM-MOG) based nanoenzymes with properties of a three-enzyme mimetic including peroxidase-like, catalase-like and oxidase-like. The oxidase-like catalytic mechanism originates from oxygen vacancies and superoxide radicals (. O) 2 - ) Whereas peroxidase-like activity results from electron transport capability and hydroxyl radical (. OH).
(2) The peroxidase-like activity of FO @ ZMFO @ FM-MOG was utilized to establish H 2 O 2 A colorimetric sensor having a linear range of 37 μ M to 337 μ M.
(3) A colorimetric sensor and an intelligent terminal detection platform of citric acid are established by using peroxidase-like activity of FO @ ZMFO @ FM-MOG, the linear range of the colorimetric sensor and the intelligent terminal detection platform is 0.415 mu M to 6.21 mu M, and the lower limit of detection (LOD) is 79nM. An intuitive and convenient field detection method for the concentration of the citric acid can be established without using expensive equipment. Established sensors require little expensive reagents and instrumentation and provide a convenient and rapid quantitative citric acid detection route.
(4) A norfloxacin colorimetric sensor and an intelligent terminal detection platform are established by utilizing peroxidase-like activity of FO @ ZMFO @ FM-MOG, the linear range of the norfloxacin colorimetric sensor and the intelligent terminal detection platform is 0.409 mu M to 4.706 mu M, and the lower limit of detection (LOD) is 52nM. The established intelligent terminal detection platform integrates colorimetric signals, and can realize intuitive norfloxacin detection. Compared with other methods for monitoring norfloxacin by simulating enzyme, the colorimetric sensor disclosed by the invention is more sensitive than most of sensors based on other nano-enzyme.
(5) A colorimetric sensor of gallic acid is established by utilizing similar oxidase-like activity of FO @ ZMFO @ FM-MOG, the linear range of the colorimetric sensor is 0.4762 mu M to 5.2632 mu M, and the lower limit of detection (LOD) is 0.079 mu M. Compared with the prior art, the FO @ ZMFO @ FM-MOG nanoenzyme is an effective candidate for constructing a gallic acid colorimetric sensor.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. Three-layer FeO with multi-enzyme activity x @ZnMnFeO y The preparation method of the @ Fe-Mn bimetal organogel is characterized by comprising the following steps: the method comprises the following steps:
s1: synthesis of Fe-Mn bimetallic organogel
Weighing Mn (NO) 3 ) 2 ·4H 2 O and Fe (NO) 3 ) 3 ·9H 2 Dissolving O in ethanol, weighing trimesic acid, dissolving in ethanol, adding triethylamine, standing, washing with ethanol for three times, and freeze-drying to obtain Fe-Mn bimetallic organogel;
S2：Zn 0.5 Mn 0.5 Fe 2 O 4 synthesis of (2)
Weighing polyvinylpyrrolidone, dissolving in ultrapure water, stirring, and adding Mn (NO) 3 ) 2 ·4H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 Continuously stirring after O, drying the mixture in an oven overnight to obtain dry powder, and calcining the dry powder in a muffle furnace to obtain Zn 0.5 Mn 0.5 Fe 2 O 4 Nanoparticles;
S3：ZnMnFeO y preparation of nanoparticle-cysteine mixture
Weighing Zn 0.5 Mn 0.5 Fe 2 O 4 Dissolving the nano particles and the cysteine in ethanol, stirring and dissolving, washing with ethanol, centrifuging and drying to obtain ZnMnFeO y Storing the nanoparticle-cysteine mixture at room temperature;
s4: three layers of FeO x @ZnMnFeO y @ Fe-Mn bimetallic organicSynthesis of gels
Weighing ZnMnFeO y Dissolving the nanoparticle-cysteine mixture in 2- (N-morpholine) ethanesulfonic acid containing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, stirring, adding Fe-Mn bimetallic organogel, stirring, washing with ethanol for three times, centrifuging, and freeze-drying to obtain three layers of FeO x @ZnMnFeO y @ Fe-Mn bimetallic organogels;
wherein:
in step S1: the Mn (NO) 3 ) 2 ·4H 2 O and Fe (NO) 3 ) 3 ·9H 2 The dosage ratio of O is a molar ratio, and the molar ratio is 2-3:1;
the mol dosage of the trimesic acid is Fe (NO) 3 ) 3 ·9H 2 1.5-2 times of O;
the standing time is 3.5-5h;
in step S2: the Mn (NO) 3 ) 2 ·4H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The dosage ratio of O is a molar ratio, and the molar ratio is 1:1:2-4;
the stirring time is 1-2h;
the calcination temperature is 550-560 ℃, and the calcination time is 3-4h;
in step S3: said Zn 0.5 Mn 0.5 Fe 2 O 4 The dosage ratio of the nano particles to the cysteine is a mass ratio, and the mass ratio is 10:1;
the stirring time is at least 12h;
in step S4: the dosage ratio of the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 2- (N-morpholine) ethanesulfonic acid of the N-hydroxysuccinimide is a mass ratio of (5-6): 4; the stirring time for adding the Fe-Mn bimetallic organogel is not less than 48h.
2. Three-layer FeO with multi-enzyme activity x @ZnMnFeO y The application of the @ Fe-Mn bimetal organogel is characterized in that: a process as claimed in claim 1Enzymatically active three-layer FeO x @ZnMnFeO y Preparation method of @ Fe-Mn bimetallic organogel x @ZnMnFeO y Application of @ Fe-Mn bimetal organogel to H 2 O 2 Detection of (2):
to a 0.2M acetic acid buffer solution having pH =3.5 was added three-layer FeO having a concentration of 12.5. Mu.g/mL x @ZnMnFeO y The method comprises the steps of @ Fe-Mn bimetallic organogel and 3,3',5,5' -tetramethylbenzidine, and then adding H with different concentrations 2 O 2 Incubating at 50 ℃ for 10min, and recording the absorbance at 652nm by using an ultraviolet spectrophotometer;
wherein:
said H 2 O 2 The linear detection concentration range of (1) is 37-337 muM;
the calibration curve is y =1.92521x +0.41151 2 =0.997,x is H 2 O 2 The concentration of (c).
3. Three-layer FeO with multi-enzyme activity x @ZnMnFeO y The application of the @ Fe-Mn bimetal organogel is characterized in that: the multienzyme active three-layer FeO of claim 1 x @ZnMnFeO y Preparation method of @ Fe-Mn bimetallic organogel x @ZnMnFeO y The application of @ Fe-Mn bimetallic organogel to citric acid detection:
citric acid with different concentrations, three layers of FeO with the volume of 100 mu L and the concentration of 1mg/mL x @ZnMnFeO y @ Fe-Mn bimetallic organogel and 5mM 3,3',5,5' -tetramethylbenzidine in a volume of 100. Mu.L were added to pH =3.5 acetate buffer, and H in a volume of 100. Mu.L and a concentration of 10mM was added at 50 ℃ 2 O 2 Adding the mixture for 10min, and recording ultraviolet absorption spectrum;
the linear detection concentration of the citric acid is 0.415-6.21 mu M, and the lower detection limit is 79nM;
the calibration curve is y = -0.2289x +1.79865 2 =0.99133,x is the concentration of citric acid.
4. According to claim 3The three layers of multi-enzyme active FeO x @ZnMnFeO y The application of the @ Fe-Mn bimetal organogel is characterized in that:
establishing an intelligent terminal platform APP, collecting colorimetric photos and colorimetric signals through an intelligent terminal, adding citric acid with different concentrations into a reaction system, then selecting a photo specific region through the intelligent terminal platform APP, carrying out a recording mode, and displaying an automatically generated fitting equation on a screen of the intelligent terminal;
wherein the mode is one of G/B-C, R/B-C, R/G-C, R-C, G-C, B-C, gray-C and S/V-C;
wherein, under the mode Gray-C, the fitting equation is Y =15.2236+2.5257X 2 =0.9942, x is the concentration of citric acid.
5. Three-layer FeO with multi-enzyme activity x @ZnMnFeO y The application of the @ Fe-Mn bimetal organogel is characterized in that: the multienzyme-active three-layer FeO of claim 1 x @ZnMnFeO y Preparation method of @ Fe-Mn bimetallic organogel x @ZnMnFeO y The application of @ Fe-Mn bimetallic organogel in detecting norfloxacin:
adding 12 μm citric acid solution and norfloxacin at different concentrations in acetate buffer with concentration of 0.2M, pH =3.5, incubating at 50 deg.C for 10min, adding 3,3',5,5' -tetramethylbenzidine at concentration of 5mM and three layers of FeO at concentration of 1mg/mL x @ZnMnFeO y @ Fe-Mn bimetallic organogel, and then, measuring the absorbance of the reaction solution at 625nm by an ultraviolet-visible spectrophotometer;
the linear detection concentration of the norfloxacin is 0.409 mu M-4.706 mu M, and the lower detection limit is 0.52nM;
the calibration curve is y =0.1429x +0.28305 2 =0.99224,x is the concentration of norfloxacin.
6. Multi-enzyme active tri-layer FeO according to claim 5 x @ZnMnFeO y The application of the @ Fe-Mn bimetal organogel is characterized in that:
establishing an intelligent terminal platform APP, collecting colorimetric photos and colorimetric signals through an intelligent terminal, adding norfloxacin with different concentrations into a reaction system, then selecting a photo specific area through the intelligent terminal platform APP, carrying out a recording mode, and displaying an automatically generated fitting equation on a screen of the intelligent terminal;
wherein the mode is one of a G/BC mode and an HC mode;
wherein, in the G/BC mode, the fitting equation is Y =0.9357+0.0041X 2 =0.9942,x is the concentration of norfloxacin;
in HC mode, the fitting equation is Y =183.9125-0.2488X 2 =0.9936,x is the concentration of norfloxacin.
7. Three-layer FeO with multi-enzyme activity x @ZnMnFeO y The application of the @ Fe-Mn bimetal organogel is characterized in that: the multienzyme active three-layer FeO of claim 1 x @ZnMnFeO y Preparation method of @ Fe-Mn bimetallic organogel x @ZnMnFeO y The application of @ Fe-Mn bimetallic organogel to the detection of gallic acid:
1mg/mL of three-layer FeO was added to an acetate buffer solution having a concentration of 0.2M, a volume of 2.2mL and a pH =3.5 x @ZnMnFeO y A @ Fe-Mn bimetallic organogel catalyst, 5mM 3,3',5,5' -tetramethylbenzidine solution and gallic acid with different concentrations were incubated at 37 ℃ for 30min, and the UV absorption spectrum at 652nm wavelength was recorded;
the linear detection concentration of the gallic acid is 0.4762-5.2632 muM, and the lower detection limit is 0.079 muM;
the calibration curve is y = -0.0615x +0.76644 2 =0.9979,x is the concentration of gallic acid.
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