CN113457741A - Preparation and application of multi-enzyme active three-layer FeOx @ ZnMnFeOY @ Fe-Mn bimetallic organogel - Google Patents
Preparation and application of multi-enzyme active three-layer FeOx @ ZnMnFeOY @ Fe-Mn bimetallic 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 19
- 229910015189 FeOx Inorganic materials 0.000 title claims abstract description 18
- 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 169
- 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 50
- 229960001180 norfloxacin Drugs 0.000 claims abstract description 50
- 229940074391 gallic acid Drugs 0.000 claims abstract description 36
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 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 25
- 238000011088 calibration curve Methods 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 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 16
- 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000008351 acetate buffer Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
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- 238000002835 absorbance Methods 0.000 claims description 10
- 238000000862 absorption spectrum Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 238000001035 drying Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 6
- 238000011481 absorbance measurement Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000011534 incubation Methods 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 229960004106 citric acid Drugs 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 239000011572 manganese Substances 0.000 description 29
- 239000011701 zinc Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000002789 catalaselike Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003814 drug Substances 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
- 244000269722 Thea sinensis Species 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 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
- 239000002253 acid Substances 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 235000009569 green tea Nutrition 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
- 238000011084 recovery Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-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
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000022159 cartilage development Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 201000000312 duodenum cancer Diseases 0.000 description 1
- 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
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 230000008764 nerve damage Effects 0.000 description 1
- 239000002405 nuclear magnetic resonance imaging agent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000003306 quinoline derived antiinfective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 208000019206 urinary tract infection Diseases 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- 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
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- 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
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Abstract
The invention relates to a three-layer FeO with multienzyme activityx@ZnMnFeOyThe preparation method of the @ Fe-Mn bimetal organogel comprises the following steps: s1: synthesizing Fe-Mn bimetallic organogel; s2: zn0.5Mn0.5Fe2O4Synthesizing; s3: ZnMnFeOyPreparing a nanoparticle-cysteine mixture; s4: three layers of FeOx@ZnMnFeOyAnd (3) synthesizing the @ Fe-Mn bimetallic organogel. The prepared catalyst is FeOx@ZnMnFeOyModified Fe-Mn bimetallic organogel-based nanoenzymes having the properties of a three-enzyme mimetic. Meanwhile, a three-layer FeO with multi-enzyme activity is providedx@ZnMnFeOyApplication of @ Fe-Mn bimetallic organogel to establish H2O2And a colorimetric detection method for 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 FeOx@ZnMnFeOyPreparation and application of @ Fe-Mn bimetal organogel.
Background
Citric Acid (CA) is used as an antioxidant and sour agent in food products. 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. Veterinary medicine 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, fast 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 of FeOx@ZnMnFeOyThe preparation of @ Fe-Mn bimetallic organogel (abbreviated as FO @ ZMFO @ FM-MOG) and the prepared catalyst are FeOx@ZnMnFeOy(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-) and peroxidase-like activity results from electron transport and hydroxyl radical (. OH). Meanwhile, the application of the FO @ ZMFO @ FM-MOG core-shell structure in an intelligent terminal platform is provided, namely the H is established based on the multi-enzyme activity of the FO @ ZMFO @ FM-MOG nanocomposite2O2A colorimetric method of citric acid, norfloxacin and gallic acid, a simple four-functional colorimetric sensing platform for detecting H2O2Citric 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 activityx@ZnMnFeOyThe preparation method of the @ Fe-Mn bimetal organogel comprises the following steps:
s1: synthesis of Fe-Mn bimetallic organogel
Weighing Mn (NO)3)2·4H2O and Fe (NO)3)3·9H2Dissolving 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：Zn0.5Mn0.5Fe2O4synthesis of (2)
Weighing polyvinylpyrrolidone, dissolving in ultrapure water, stirring, and adding Mn (NO)3)2·4H2O、Zn(NO3)2·6H2O and Fe (NO)3)3·9H2Continuously 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 Zn0.5Mn0.5Fe2O4Nanoparticles;
S3：ZnMnFeOypreparation of nanoparticle-cysteine mixture
Weighing Zn0.5Mn0.5Fe2O4Dissolving the nano particles and the cysteine in ethanol, stirring and dissolving, washing with ethanol, centrifuging and drying to obtain ZnMnFeOyStoring the nanoparticle-cysteine mixture at room temperature;
s4: three layers of FeOx@ZnMnFeOySynthesis of @ Fe-Mn bimetal organogel
Weighing ZnMnFeOyDissolving 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 FeOx@ZnMnFeOy@ Fe-Mn bimetallic organogels.
Further, in step S1:
the Mn (NO)3)2·4H2O and Fe (NO)3)3·9H2The 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)3·9H21.5-2 times of O;
the standing time is 3.5-5 h.
Further, in step S2:
the Mn (NO)3)2·4H2O、Zn(NO3)2·6H2O and Fe (NO)3)3·9H2The dosage ratio of O is a molar ratio, and the molar ratio is 1: 1: 2-4;
the stirring time is 1-2 h;
the calcination temperature is 550-560 ℃, and the calcination time is 3-4 h.
Further, in step S3:
said Zn0.5Mn0.5Fe2O4The 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 12 h;
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 48 h.
According to a second aspect of the invention, three layers of FeO are producedx@ZnMnFeOyApplication of @ Fe-Mn bimetallic organogel to H2O2Detection of (2):
to a 0.2M acetate buffer solution at pH 3.5 was added three layers of FeO at a concentration of 12.5. mu.g/mLx@ZnMnFeOy@ Fe-Mn bimetallic organogel and 3,3', 5,5' -tetramethylbenzidine, then adding H at different concentrations2O2Incubating at 50 ℃ for 10min, and recording the absorbance at 652nm by using an ultraviolet spectrophotometer;
wherein:
said H2O2The linear detection concentration range of (1) is 37-337 muM;
the calibration curve is that y is 1.92521x +0.41151, R20.997, x is H2O2The concentration of (c).
According to a third aspect of the invention, three layers of FeO are producedx@ZnMnFeOyThe application of @ Fe-Mn bimetallic organogel to citric acid detection:
different concentrations ofCitric acid, and three layers of FeO with the volume of 100 mu L and the concentration of 1mg/mLx@ZnMnFeOy@ 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 ℃2O2After 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 79 nM;
the calibration curve is-0.2289 x +1.79865, R2X is the concentration of citric acid 0.99133.
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 pattern 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, in the mode Gray-C, the fitting equation is that Y is 15.2236+2.5257X, R2X is the concentration of citric acid 0.9942.
According to a fourth aspect of the invention, three layers of FeO are producedx@ZnMnFeOyThe application of @ Fe-Mn bimetallic organogel in detecting norfloxacin:
adding 12 μm citric acid solution and norfloxacin at different concentrations into acetate buffer solution 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/mLx@ZnMnFeOy@ Fe-Mn bimetallic organogels. Then, absorbance measurement of the reaction solution was performed 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 0.52 nM;
calibration curve y 0.1429x +0.28305, R20.99224 where x is norfloxacinThe concentration of (c).
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 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 a G/BC mode and an HC mode;
wherein, in the G/BC mode, the fitting equation is that Y is 0.9357+0.0041X, R20.9942, X is the concentration of norfloxacin;
in HC mode, the fitting equation is Y-183.9125-0.2488X, R2X is the concentration of norfloxacin 0.9936.
According to a fifth aspect of the invention, three layers of FeO are producedx@ZnMnFeOyThe application of @ Fe-Mn bimetallic organogel to the detection of gallic acid:
to a buffer solution of acetate at a concentration of 0.2M, a volume of 2.2mL and a pH of 3.5, 1mg/mL of three-layer FeO was addedx@ZnMnFeOyIncubation of reaction mixture at 37 ℃ for 30min with a @ Fe-Mn bimetallic organogel catalyst, 5mM 3,3', 5,5' -tetramethylbenzidine solution and gallic acid of different concentrations, and recording the ultraviolet absorption spectrum at 652nm wavelength;
the linear detection concentration of the gallic acid is 0.4762-5.2632 mu M, and the lower limit of detection is 0.079 mu M;
the calibration curve is-0.0615 x +0.76644, R2X is the concentration of gallic acid 0.9979.
The invention has the beneficial effects that:
(1) synthesizes and constructs a new compound with FeOx@ZnMnFeOy(FO @ ZMFO) modified Fe-Mn bimetallic organogel (FM-MOG) based 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-) and peroxidase-like activity results from electron transport and hydroxyl radical selfFrom the group (. OH).
(2) The peroxidase-like activity of FO @ ZMFO @ FM-MOG is utilized to establish H2O2A 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 79 nM. 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 colorimetric sensor and an intelligent terminal detection platform of norfloxacin 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 0.409 mu M to 4.706 mu M, and the lower limit of detection (LOD) is 52 nM. 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 gallic acid sensor was established using similar oxidase-like activity of FO @ ZMFO @ FM-MOG, with a linear range of 0.4762 μ M to 5.2632 μ M and a lower limit of detection (LOD) of 0.079 μ 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-MOG2O2Ultraviolet spectrogram of (A) and (B) for detecting H2O2The calibration curve of (1).
In fig. 5: (A) an ultraviolet spectrogram for detecting citric acid for FO @ ZMFO @ FM-MOG, (B) a calibration curve for detecting citric acid, and (C) a Gray-C mode fitting curve for detecting citric acid for an intelligent terminal platform APP.
In fig. 6: (A) the method comprises the following steps of (1) 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) UV spectrogram for detecting gallic acid for FO @ ZMFO @ FM-MOG and (B) calibration curve for detecting gallic acid.
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 FeOx@ZnMnFeOyThe preparation of @ Fe-Mn bimetallic organogel (abbreviated as FO @ ZMFO @ FM-MOG) and the prepared catalyst are FeOx@ZnMnFeOy(abbreviated as FO @ ZMFO) modified Fe-Mn bimetallic organogel (abbreviated as 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-) and peroxidase-like activity results from electron transport and hydroxyl radical (. OH). Meanwhile, the application of the FO @ ZMFO @ FM-MOG core-shell structure in an intelligent terminal platform is provided, namely the H is established based on the multi-enzyme activity of the FO @ ZMFO @ FM-MOG nanocomposite2O2A colorimetric method of citric acid, norfloxacin and gallic acid, a simple four-functional colorimetric sensing platform for detecting H2O2Citric 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 activityx@ZnMnFeOyThe preparation method of the @ Fe-Mn bimetal organogel comprises the following steps:
s1: synthesis of Fe-Mn bimetallic organogel
Weighing Mn (NO)3)2·4H2O and Fe (NO)3)3·9H2Dissolving 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：Zn0.5Mn0.5Fe2O4synthesis of (2)
Weighing polyvinylpyrrolidone, dissolving in ultrapure water, stirring, and adding Mn (NO)3)2·4H2O、Zn(NO3)2·6H2O and Fe (NO)3)3·9H2Continuously 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 Zn0.5Mn0.5Fe2O4Nanoparticles;
S3：ZnMnFeOypreparation of nanoparticle-cysteine mixture
Weighing Zn0.5Mn0.5Fe2O4Dissolving the nano particles and the cysteine in ethanol, stirring and dissolving, washing with ethanol, centrifuging and drying to obtain ZnMnFeOyStoring the nanoparticle-cysteine mixture at room temperature;
s4: three layers of FeOx@ZnMnFeOySynthesis of @ Fe-Mn bimetal organogel
Weighing ZnMnFeOyDissolving 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 FeOx@ZnMnFeOy@ Fe-Mn bimetallic organogels.
In step S1: mn (NO)3)2·4H2O and Fe (NO)3)3·9H2The dosage ratio of O is a molar ratio, and the molar ratio is 2-3: 1; the molar amount of the trimesic acid is Fe (NO)3)3·9H21.5-2 times of O; standing for 3.5-5 h.
In step S2: mn (NO)3)2·4H2O、Zn(NO3)2·6H2O and Fe (NO)3)3·9H2The dosage ratio of O is a molar ratio, and the molar ratio is 1: 1: 2-4; the stirring time is 1-2 h; the calcination temperature is 550-560 ℃, and the calcination time is 3-4 h.
In step S3: zn0.5Mn0.5Fe2O4The 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 12 h;
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 bimetallic organogel is not less than 48 h.
Applying the prepared FO @ ZMFO @ FM-MOG to H2O2Detection of (2):
FO @ ZMFO @ FM-MOG and 3,3', 5,5' -tetramethylbenzidine were added at a concentration of 12.5. mu.g/mL to 0.2M acetic acid buffer at pH 3.5, followed by different concentrations of H2O2Incubating at 50 ℃ for 10min, and recording the absorbance at 652nm by using an ultraviolet spectrophotometer;
wherein:
H2O2the linear detection concentration range of (1) is 37-337 muM;
the calibration curve is that y is 1.92521x +0.41151, R20.997, x is H2O2The 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 3,3', 5,5' -tetramethylbenzidine at a concentration of 5mM in a volume of 100. mu.L were added to acetate buffer at pH 3.5, and H at a concentration of 10mM in a volume of 100. mu.L was added at 50 ℃2O2After 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 79 nM;
the calibration curve is-0.2289 x +1.79865, R2X is the concentration of citric acid 0.99133.
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, in the mode Gray-C, the fitting equation is that Y is 15.2236+2.5257X, R2X is the concentration of citric acid 0.9942.
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, 12 μm citric acid solution and various concentrations of norfloxacin were added, and after incubation at 50 ℃ for 10min, 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 detection limit is 0.52 nM;
calibration curve y 0.1429x +0.28305, R2X is the concentration of norfloxacin 0.99224.
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 a G/BC mode and an HC mode;
wherein, in the G/BC mode, the fitting equation is that Y is 0.9357+0.0041X, R2＝0.9942, X is the concentration of norfloxacin;
in HC mode, the fitting equation is Y-183.9125-0.2488X, R2X is the concentration of norfloxacin 0.9936.
The prepared FO @ ZMFO @ FM-MOG is applied to detection of gallic acid:
to an acetate buffer solution at a concentration of 0.2M, a volume of 2.2mL and a pH of 3.5, 1mg/mL of Zn was added0.5Mn0.5Fe2O4@ FeMn-MOG catalyst, 5mM 3,3', 5,5' -tetramethylbenzidine solution and gallic acid of different concentrations, incubating the reaction mixture at 37 ℃ for 30min, and recording the ultraviolet absorption spectrum at 652nm wavelength;
the linear detection concentration of the gallic acid is 0.4762-5.2632. mu.M, and the lower limit of the detection is 0.079. mu.M;
the calibration curve is-0.0615 x +0.76644, R2X is the concentration of gallic acid 0.9979.
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)2·4H2O (manganese nitrate) and 0.6g of Fe (NO)3)3·9H2Dissolving O (ferric nitrate) in 10mL of ethanol, weighing 0.5g of trimesic acid, dissolving in 10mL of ethanol, adding 0.5mL of triethylamine, standing for 4h, washing with ethanol for three times after standing, and freeze-drying to obtain Fe-Mn bimetallic organogel (FM-MOG);
S2：Zn0.5Mn0.5Fe2O4synthesis of (2)
3g of polyvinylpyrrolidone is weighed, dissolved in 100mL of ultrapure water and stirred for 2h, and then the mixture is stirred according to the molar ratio of 1: 1: 2 weighing 0.01255g of Mn (NO)3)2·4H2O (manganese nitrate), 0.0149g of Zn (NO)3)2·6H2O (Zinc nitrate) and 0.0404g of Fe (NO)3)3·9H2Stirring for 1 hr after O (ferric nitrate), oven drying overnight to obtain dry powder, and placing the dry powder in muffle furnaceCalcining at 550 ℃ for 3h to obtain Zn0.5Mn0.5Fe2O4Nanoparticles;
S3：ZnMnFeOypreparation of nanoparticle-cysteine mixture
0.03g of Zn was weighed0.5Mn0.5Fe2O4Dissolving the nano particles and 0.3g of cysteine in 100mL of ethanol, stirring for 12h to dissolve, washing with ethanol, centrifuging and drying to obtain ZnMnFeOyStoring the nanoparticle-cysteine mixture at room temperature;
s4: three layers of FeOx@ZnMnFeOySynthesis of @ Fe-Mn bimetallic organogel (FO @ ZMFO @ FM-MOG)
Weighing ZnMnFeOyThe nanoparticle-cysteine mixture was dissolved in 2- (N-morpholino) 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 FeOx@ZnMnFeOy@ Fe-Mn bimetallic organogel (FO @ ZMFO @ FM-MOG).
As shown in FIGS. 1-3, FO @ ZMFO @ FM-MOG was prepared using the 4-step method described above, where TEM showed that FM-MOG is a nanorod (FIG. 1) and ZMFO is a nanoparticle (FIG. 2), and the successful preparation of the FO @ ZMFO @ FM-MOG composite was demonstrated by loading ZMFO on the surface of FM-MOG (FIG. 3).
Table 1 shows inductively coupled plasma analysis (ICP) of FO @ ZMFO @ FM-MOG. ICP mass analysis indicated that the actual Fe content in FO @ ZMFO @ FM-MOG was as high as 96.79%, much greater than manganese (2.92%) and zinc (0.29%). The actual manganese and zinc contents were much lower than theoretical contents, compared to theoretical contents of Mn (47.73%) and Zn (2.27%), demonstrating a significant reduction in Zn and Mn contents at the surface of FO @ ZMFO @ FM-MOG. 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 etched 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 (II) FO @ ZMFO @ FM-MOG to H2O2Example of detection of
To 2170. mu.L of acetic acid buffer solution at pH 3.5 and 0.2M, FO @ ZMFO @ FM-MOG at a concentration of 12.5. mu.g/mL and 3,3', 5,5' -tetramethylbenzidine (abbreviated as TMB) at a concentration of 5mM were added, followed by H at different concentrations2O2Incubating at 50 ℃ for 10min, and recording the absorbance at 652nm by using an ultraviolet spectrophotometer;
wherein: h2O2The linear detection concentration range of (1) is 37-337 muM; the calibration curve is that y is 1.92521x +0.41151, R20.997, x is H2O2The concentration of (c).
H2O2The increase in concentration resulted in a color change from colorless to blue, as a result of the OH production of the FO @ ZMFO @ FM-MOG nanocomposite. As shown in FIG. 4(A), the absorbance from c-b-a increases from bottom to top as the concentration increases, i.e., A652nmSignal with H2O2Gradually 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.M652nmAnd H2O2Has good linear relation, and the y of the calibration curve is 1.92521x +0.41151 (R)20.997). This example establishes a H assay using peroxidase-like activity of FO @ ZMFO @ FM-MOG2O2A colorimetric sensor.
TABLE 2 FO @ ZMFO @ FM-MOG catalytic colorimetric sensor vs. H in water2O2Analytical Properties of detection
To test the utility of the method, different concentrations of H were used2O2Adding into three water samples according to standard addition methodThe method is carried out. As shown in Table 2, H2O2The Relative Standard Deviation (RSD) of (a) is between 97% and 106%. The experimental result proves that the provided colorimetric method is used for H in the actual sample2O2Reliability and practicality of analysis.
Example of applying (III) FO @ ZMFO @ FM-MOG to citric acid
mu.L of citric acid at various concentrations, FO @ ZMFO @ FM-MOG at a concentration of 1mg/mL at a volume of 100. mu.L, and 3,3', 5,5' -tetramethylbenzidine at a concentration of 5mM at a volume of 100. mu.L were added to 1.8mL of acetate buffer at pH 3.5, and H at a concentration of 10mM at a volume of 100. mu.L at 50 ℃ was added2O2After 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 79 nM; the calibration curve is-0.2289 x +1.79865, R2X is the concentration of citric acid 0.99133. 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, in the mode Gray-C, the fitting equation is that Y is 15.2236+2.5257X, R2X is the concentration of citric acid 0.9942.
In this example, FO @ ZMFO @ FM-MOG catalyzed TMB/H with increasing citric acid content2O2The system shows 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. This equation can be written as y ═ 0.2289x +1.79865 (R)20.99133). The lower limit of detection (LOD) calculated from S/N-3 was 79 nM. 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. Adding citric acid of different concentrations to the reactionIn the system, colorimetric photos are collected through an intelligent terminal. Then, a photo specific area is selected and recorded by the self-developed APP. 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, the Gray-C mode was chosen because of the better linear relationship with citric acid concentration, and the automatically generated fitting equation Y is 15.2236+2.5257X (R)20.9942) is displayed on the smart terminal screen. Therefore, 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.
TABLE 3 analysis of citric acid in juice performance of FO @ ZMFO @ FM-MOG catalytic colorimetric sensor
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 proves 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
A12 μm citric acid solution and norfloxacin (abbreviated as NOR) at various concentrations were added to acetate buffer at a concentration of 0.2M, pH ═ 3.5, and after incubation at 50 ℃ for 10min, 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 detection limit is 0.52 nM; calibration curve y 0.1429x +0.28305, R2X is the concentration of norfloxacin 0.99224.
And further establishes an intelligent terminal platformThe APP collects colorimetric photos and colorimetric signals through the intelligent terminal, norfloxacin with different concentrations is added into the reaction system, then, a photo specific area is selected through the APP of the intelligent terminal platform, a recording mode is carried out, and an automatically generated fitting equation is displayed on a screen of the 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 that Y is 0.9357+0.0041X, R20.9942, X is the concentration of norfloxacin; in HC mode, the fitting equation is Y-183.9125-0.2488X, R2X is the concentration of norfloxacin 0.9936.
In the embodiment, a method for detecting norfloxacin by a colorimetric method and a smart phone is established. As shown in FIG. 6(A), the absorbance from c-b-a increases from bottom to top with increasing concentration, i.e., FO @ ZMFO @ FM-MOG/TMB/H with increasing norfloxacin2O2The UV-visible absorption intensity of citric acid increases. As shown in FIG. 6(B), norfloxacin was observed to have a good linear relationship ranging from 0.409. mu.M to 4.706. mu.M (R)20.99224), detection limit of 52nM, calibration curve y 0.1429x +0.28305, R2X is the concentration of norfloxacin 0.99224. 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 the dual mode, and the automatically generated fitting equation Y is 0.9357+0.0041X (R)20.9942) and Y183.9125-0.2488X (R)20.9936) 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 sensors based on other nano-enzyme.
TABLE 4 analytical Performance of FO @ ZMFO @ FM-MOG catalytic colorimetric sensor for detection of 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 applying FO @ ZMFO @ FM-MOG to gallic acid detection
To an acetate buffer solution at a concentration of 0.2M, a volume of 2.2mL and a pH of 3.5, 1mg/mL of FO @ ZMFO @ FM-MOG catalyst and 5mM of a solution of 3,3', 5,5' -tetramethylbenzidine and different concentrations of gallic acid were added, the reaction mixture was incubated at 37 ℃ for 30min, and uv absorption spectra at a wavelength of 652nm were recorded; the linear detection concentration of the gallic acid is 0.4762-5.2632. mu.M, and the lower limit of the detection is 0.079. mu.M; the calibration curve is-0.0615 x +0.76644, R2X is the concentration of gallic acid 0.9979.
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 linear equation fitted is-0.0615 x +0.76644 (R)20.9979), detection limit of 0.079 μ M, where y is absorbance and x is gallic acid concentration. Compared with the prior art, the FO @ ZMFO @ FM-MOG nanoenzyme is an effective candidate for constructing a gallic acid colorimetric sensor.
TABLE 5 analysis of gallic acid in Green tea by FO @ ZMFO @ FM-MOG catalyzed 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 activityx@ZnMnFeOyThe preparation and application of the @ Fe-Mn bimetal organogel have the following technical principles and technical effects:
(1) synthesizes and constructs a new compound with FeOx@ZnMnFeOy(FO @ ZMFO) modified Fe-Mn bimetallic organogel (FM-MOG) based 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-) and peroxidase-like activity results from electron transport and hydroxyl radical (. OH).
(2) The peroxidase-like activity of FO @ ZMFO @ FM-MOG is utilized to establish H2O2A 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 79 nM. 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 colorimetric sensor and an intelligent terminal detection platform of norfloxacin 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 0.409 mu M to 4.706 mu M, and the lower limit of detection (LOD) is 52 nM. 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 gallic acid sensor was established using similar oxidase-like activity of FO @ ZMFO @ FM-MOG, with a linear range of 0.4762 μ M to 5.2632 μ M and a lower limit of detection (LOD) of 0.079 μ 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 (10)
1. Three-layer FeO with multi-enzyme activityx@ZnMnFeOyThe preparation method of the @ Fe-Mn bimetal organogel is characterized by comprising the following steps:
s1: synthesis of Fe-Mn bimetallic organogel
Weighing Mn (NO)3)2·4H2O and Fe (NO)3)3·9H2Dissolving 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：Zn0.5Mn0.5Fe2O4synthesis of (2)
Weighing polyvinylpyrrolidone, dissolving in ultrapure water, stirring, and adding Mn (NO)3)2·4H2O、Zn(NO3)2·6H2O and Fe (NO)3)3·9H2Continuously 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 Zn0.5Mn0.5Fe2O4Nanoparticles;
S3：ZnMnFeOypreparation of nanoparticle-cysteine mixture
Weighing Zn0.5Mn0.5Fe2O4Dissolving the nano particles and the cysteine in ethanol, stirring and dissolving, washing with ethanol, centrifuging and drying to obtain ZnMnFeOyNanoparticle-cysteine mixture, storage at room temperature；
S4: three layers of FeOx@ZnMnFeOySynthesis of @ Fe-Mn bimetal organogel
Weighing ZnMnFeOyDissolving 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 FeOx@ZnMnFeOy@ Fe-Mn bimetallic organogels.
2. Multi-enzyme active, three-layer FeO according to claim 1x@ZnMnFeOyThe preparation of the @ Fe-Mn bimetallic organogel is characterized in that, in step S1:
the Mn (NO)3)2·4H2O and Fe (NO)3)3·9H2The 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)3·9H21.5-2 times of O;
the standing time is 3.5-5 h.
3. Multi-enzyme active, three-layer FeO according to claim 1 or 2x@ZnMnFeOyThe preparation of the @ Fe-Mn bimetallic organogel is characterized in that, in step S2:
the Mn (NO)3)2·4H2O、Zn(NO3)2·6H2O and Fe (NO)3)3·9H2The dosage ratio of O is a molar ratio, and the molar ratio is 1: 1: 2-4;
the stirring time is 1-2 h;
the calcination temperature is 550-560 ℃, and the calcination time is 3-4 h.
4. Multi-enzyme active, three-layer FeO according to claim 1 or 2x@ZnMnFeOyThe preparation method of @ Fe-Mn bimetal organogel is characterized in that,
in step S3:
said Zn0.5Mn0.5Fe2O4The 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 12 h;
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 48 h.
5. Three-layer FeO with multi-enzyme activityx@ZnMnFeOyUse of @ Fe-Mn bimetallic organogels, characterised in that the three-layer FeO prepared according to any of claims 1 to 4 is usedx@ZnMnFeOyApplication of @ Fe-Mn bimetallic organogel to H2O2Detection of (2):
to a 0.2M acetate buffer solution at pH 3.5 was added three layers of FeO at a concentration of 12.5. mu.g/mLx@ZnMnFeOy@ Fe-Mn bimetallic organogel and 3,3', 5,5' -tetramethylbenzidine, then adding H at different concentrations2O2Incubating at 50 ℃ for 10min, and recording the absorbance at 652nm by using an ultraviolet spectrophotometer;
wherein:
said H2O2The linear detection concentration range of (1) is 37-337 muM;
the calibration curve is that y is 1.92521x +0.41151, R20.997, x is H2O2The concentration of (c).
6. Three-layer FeO with multi-enzyme activityx@ZnMnFeOyUse of @ Fe-Mn bimetallic organogels, characterised in that the three-layer FeO prepared according to any of claims 1 to 4 is usedx@ZnMnFeOyThe application of @ Fe-Mn bimetallic organogel to citric acid detection:
citric acid with different concentrations is added,Three layers of FeO with the volume of 100 mu L and the concentration of 1mg/mLx@ZnMnFeOy@ 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 ℃2O2After 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 79 nM;
the calibration curve is-0.2289 x +1.79865, R2X is the concentration of citric acid 0.99133.
7. Multi-enzyme active tri-layer FeO according to claim 6x@ZnMnFeOyThe 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 pattern 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, in the mode Gray-C, the fitting equation is that Y is 15.2236+2.5257X, R2X is the concentration of citric acid 0.9942.
8. Three-layer FeO with multi-enzyme activityx@ZnMnFeOyUse of @ Fe-Mn bimetallic organogels, characterised in that the three-layer FeO prepared according to any of claims 1 to 4 is usedx@ZnMnFeOyThe application of @ Fe-Mn bimetallic organogel in detecting norfloxacin:
adding 12 μm citric acid solution and norfloxacin at different concentrations into acetate buffer solution 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/mLx@ZnMnFeOy@ Fe-Mn bimetallic organogels. Then, absorbance measurement of the reaction solution was performed 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 0.52 nM;
calibration curve y 0.1429x +0.28305, R2X is the concentration of norfloxacin 0.99224.
9. The multi-enzyme active, three-layer FeO according to claim 8x@ZnMnFeOyThe 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 that Y is 0.9357+0.0041X, R20.9942, X is the concentration of norfloxacin;
in HC mode, the fitting equation is Y-183.9125-0.2488X, R2X is the concentration of norfloxacin 0.9936.
10. Three-layer FeO with multi-enzyme activityx@ZnMnFeOyUse of @ Fe-Mn bimetallic organogels, characterised in that the three-layer FeO prepared according to any of claims 1 to 4 is usedx@ZnMnFeOyThe application of @ Fe-Mn bimetallic organogel to the detection of gallic acid:
to a buffer solution of acetate at a concentration of 0.2M, a volume of 2.2mL and a pH of 3.5, 1mg/mL of three-layer FeO was addedx@ZnMnFeOyIncubation of reaction mixture at 37 ℃ for 30min with a @ Fe-Mn bimetallic organogel catalyst, 5mM 3,3', 5,5' -tetramethylbenzidine solution and gallic acid of different concentrations, and recording the ultraviolet absorption spectrum at 652nm wavelength;
the linear detection concentration of the gallic acid is 0.4762-5.2632 mu M, and the lower limit of detection is 0.079 mu M;
the calibration curve is-0.0615 x +0.76644, R2X is the concentration of gallic acid 0.9979.
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