CN111896529A - Preparation method and application of one-dimensional ferroferric oxide @ silicon dioxide magnetic nanochain and immobilized glucose oxidase thereof - Google Patents
Preparation method and application of one-dimensional ferroferric oxide @ silicon dioxide magnetic nanochain and immobilized glucose oxidase thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000004366 Glucose oxidase Substances 0.000 title claims abstract description 67
- 108010015776 Glucose oxidase Proteins 0.000 title claims abstract description 52
- 229940116332 glucose oxidase Drugs 0.000 title claims abstract description 52
- 235000019420 glucose oxidase Nutrition 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 83
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 83
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 83
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 83
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 65
- 239000008103 glucose Substances 0.000 claims abstract description 65
- 238000011049 filling Methods 0.000 claims abstract description 31
- 238000004401 flow injection analysis Methods 0.000 claims abstract description 30
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000001514 detection method Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000007885 magnetic separation Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 abstract description 6
- 102000004190 Enzymes Human genes 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229940088598 enzyme Drugs 0.000 abstract description 6
- 238000006911 enzymatic reaction Methods 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 4
- 230000005526 G1 to G0 transition Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 3
- 238000002038 chemiluminescence detection Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000002444 silanisation Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 50
- 239000000243 solution Substances 0.000 description 44
- 230000002572 peristaltic effect Effects 0.000 description 17
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 229920002527 Glycogen Polymers 0.000 description 4
- 229940096919 glycogen Drugs 0.000 description 4
- 239000002122 magnetic nanoparticle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 3
- 108010093096 Immobilized Enzymes Proteins 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000174 gluconic acid Substances 0.000 description 3
- 235000012208 gluconic acid Nutrition 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000006249 magnetic particle Substances 0.000 description 3
- 239000012982 microporous membrane Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000009229 glucose formation Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- BPQMEOUCORPWGE-UHFFFAOYSA-M C(CC(O)(C(=O)O)CC(=O)O)(=O)O.[Na+].O.O.[Cl-] Chemical compound C(CC(O)(C(=O)O)CC(=O)O)(=O)O.[Na+].O.O.[Cl-] BPQMEOUCORPWGE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000034659 glycolysis Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004130 lipolysis Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000009420 retrofitting Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
- G01N21/76—Chemiluminescence; Bioluminescence
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- C12Y101/03—Oxidoreductases acting on the CH-OH group of donors (1.1) with a oxygen as acceptor (1.1.3)
- C12Y101/03004—Glucose oxidase (1.1.3.4)
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Abstract
The invention discloses a preparation method and application of a one-dimensional ferroferric oxide @ silicon dioxide magnetic nanochain and immobilized glucose oxidase thereof, and the one-dimensional Fe with larger size is synthesized through the actions of silanization and an external magnetic field3O4@SiO2Magnetic nanochains, and GOX is fixed on the nanochains by an enzyme fixing technology, so that the nanochains have space gaps and catalytic performance; and using prepared immobilisationOne-dimensional Fe of glucose oxidase3O4@SiO2The magnetic nanochain is used as stationary phase filler, filled into a filling device and used as an enzyme reaction device, and coupled with a flow injection chemiluminescence apparatus, so that real-time continuous online chemiluminescence detection of glucose is realized.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a one-dimensional ferroferric oxide @ silicon dioxide magnetic nanochain and a preparation method and application of immobilized glucose oxidase thereof.
Background
Magnetic nanoparticles can self-assemble into one-, two-, and three-dimensional nanostructures, the physicochemical properties of which are still much different from those of bulk nanoparticles. It should be noted that many magnetic nanoparticles exhibit enhanced physicochemical properties when assembled into a certain structure or morphology. The size, morphology and arrangement of the magnetic nanoparticles can also affect their development. The self-assembly of magnetic nanoparticles into one-dimensional nanochain structures has been paid attention to and studied. However, the assembly process is often complicated, and the application range of the synthesized nanochain structure is relatively small. Therefore, it is important to develop a simpler assembly method and use the assembled nanochain structure for analysis and detection.
The determination of glucose (Glu) is a detection item with great significance to clinic, because Glu content is an important human physiological index, the application is wide in clinic and the demand is great. Glu in the body is mainly derived from food, is a transportation form of sugar in the body, and has important significance for maintaining normal physiological functions of the body through mutual regulation and balance among glycogen generation and glycogen decomposition, glycogen xenogenesis and glycogen glycolysis, and fat formation and lipolysis.
Chemiluminescence (CL) detection has the advantages of high sensitivity, wide linear range, relatively simple instrument, simple operation and the like, and is receiving wide attention. In the prior art, when a chemiluminescence method is used for detecting glucose, the glucose needs to be catalyzed and hydrolyzed by a catalyst before detection, and the obtained hydrolysate is detected by the chemiluminescence method.
Disclosure of Invention
The invention aims to provide one-dimensional Fe3O4@SiO2The preparation method of the magnetic nanochain is simple, and the prepared one-dimensional Fe3O4@SiO2The magnetic nano chain has uniform size and better dispersity.
The invention also aims to provide one-dimensional Fe immobilized with glucose oxidase3O4@SiO2The preparation method of the magnetic nanochain comprises the steps of adding one-dimensional Fe3O4@SiO2The magnetic nanochain reacts with 3-aminopropyl triethoxysilane, glutaraldehyde and Glucose Oxidase (GOX) step by step, and finally the glucose oxidase is fixed on one-dimensional Fe3O4@SiO2On the magnetic nanochain, the method has high immobilization rate on the glucose oxidase, and the prepared one-dimensional Fe immobilized with the glucose oxidase3O4@SiO2The magnetic nano-chain nano-material can be further used as a filling material to be filled into a filling device, and the filling device is connected into a pipeline of a flow injection chemiluminescence apparatus, so that the rapid online detection of glucose is realized.
The present invention also aims to provide one-dimensional Fe immobilized with glucose oxidase3O4@SiO2The application of the magnetic nano-chain in catalyzing glucose hydrolysis and glucose detection.
The present invention also aims to provide one-dimensional Fe loaded with said immobilized glucose oxidase3O4@SiO2The filling device of the magnetic nano chain is applied to a flow injection chemiluminescence apparatus as an enzyme reaction device, is fixed in a pipeline for conveying a glucose solution, and can realize efficient and rapid online chemiluminescence detection on glucose.
The invention also aims to provide a flow injection chemiluminescence apparatus for detecting glucose, which is modified from the existing flow injection chemiluminescence apparatus, is connected with the filling device in a pipeline for conveying glucose solution, and generates glucose by virtue of enzyme reaction between GOX and glucoseH of (A) to (B)2O2Can generate chemiluminescence with luminol, thereby achieving the purpose of rapidly detecting glucose. Its advantage is one-dimensional Fe3O4@SiO2The magnetic nanochain is used as a carrier of immobilized glucose oxidase, can retain catalytic sites equivalent to zero-dimensional magnetic particles, can effectively overcome the problem of poor liquidity of a zero-dimensional stationary phase, and can smoothly realize coupling with a flow injection system. This lays the foundation of experiment for constructing high-efficiency immobilized enzyme flow injection analysis system.
The technical scheme adopted by the invention is as follows:
one-dimensional Fe3O4@SiO2A method for preparing a magnetic nanochain, the method comprising the steps of:
(1) preparation of Fe3O4Nanoparticles;
(2) mixing Fe3O4Fully mixing the dispersion liquid of the nano particles, tetraethyl silicate, ammonia water, deionized water and isopropanol, placing the mixture in an external magnetic field for reaction for 7 to 10 hours, and centrifuging and washing the mixture for multiple times after the reaction is finished to obtain one-dimensional Fe3O4@SiO2Magnetic nanochains. In the preparation method, tetraethyl silicate is quickly hydrolyzed and condensed under alkaline condition to generate SiO2And is coated with Fe3O4Surface of nanoparticles while Fe3O4Under the action of external magnetic field, the magnetic particles are spontaneously arranged in order along the direction of magnetic field force, and Fe passes through the particles3O4SiO of the surface2Are connected together to form one-dimensional Fe3O4@SiO2Magnetic nanochains.
Further, in the step (1), the Fe3O4The particle size of the nano particles is 150-350 nm, and Fe with the particle size3O4The nano particles are prepared into one-dimensional Fe fixed with glucose oxidase through subsequent steps3O4@SiO2After the magnetic nano-chain is filled into a filling device, a larger stacking gap can be formed, and the full reaction can be carried out after glucose enters the device.
In the step (1), theFe3O4The preparation method of the nano particles comprises the following steps: the ferric chloride, the glycol, the sodium acetate and the sodium citrate dihydrate are fully mixed and then are subjected to solvothermal reaction to prepare the ferric chloride-sodium citrate dihydrate.
The sufficient mixing is mixing and stirring for 30-60min at the temperature of 10-35 ℃.
The conditions of the solvothermal reaction are as follows: reacting at 180 ℃ and 220 ℃ for 10-12 h.
The dosage ratio of the ferric chloride, the glycol, the sodium acetate and the sodium citrate dihydrate is 1.3 g: 30-40 mL: 2.0-2.4 g: 0.2-0.5 g.
Fe prepared under the above reaction conditions3O4The nano particles have uniform particle size and good dispersibility, and the particle size is 200-300 nm.
Further, in the step (2), the Fe3O4The volume ratio of the nano particle dispersion liquid to the tetraethyl silicate to the ammonia water to the deionized water to the isopropanol is 200: 10-20: 20-40: 400: 1000.
in the step (2), the Fe3O4The concentration of the nanoparticle dispersion was 10 mg/mL.
The invention also provides one-dimensional Fe immobilized with glucose oxidase3O4@SiO2The preparation method of the magnetic nanochain comprises the following steps: the one-dimensional Fe prepared by the above method3O4@SiO2Stirring and reacting magnetic nano-chain and aqueous solution of 3-aminopropyltriethoxysilane in Fe3O4@SiO2Modifying amino on the magnetic nanochain, stirring and reacting with glutaraldehyde after separation and cleaning, reacting with glucose oxidase after separation and cleaning, and obtaining the one-dimensional Fe fixed with the glucose oxidase after separation and cleaning3O4@SiO2Magnetic nanochains.
Further, one-dimensional Fe3O4@SiO2The mass ratio of the magnetic nanochain to the glucose oxidase is 8-10: 1.
One-dimensional Fe3O4@SiO2Reaction of magnetic nanochain with 3-aminopropyltriethoxysilane, glutaraldehyde and glucose oxidaseThe time interval is 18 to 22 hours, 1.5 to 2.5 hours and 18 to 22 hours respectively.
The reaction with glucose oxidase is a standing reaction, but the reaction is shaken up every 2 h; the reaction temperature is 2-6 ℃.
The solvents used for the three times of separation and cleaning are PBS buffer solutions with pH7.3, 6.5 and 6.0 respectively, and in the first step, after the surface of the nano chain is modified by amino, the nano chain needs to be stored under the condition of near neutrality after being cleaned; secondly, after cross-linking reaction of glutaraldehyde, washing and storing at pH6.5 at which the GOX activity is optimal; the final step of GOX immobilization process is characterized in that the activity of the enzyme is optimal under the condition of pH6.5, the enzyme immobilization is facilitated, and the activity is maintained under the condition of pH6.0 after the enzyme is finally stored.
The method of separation may be centrifugation or magnetic separation.
The one-dimensional Fe immobilized with glucose oxidase prepared by the preparation method3O4@SiO2The magnetic nanochain is a one-dimensional nanochain structure, and a large stacking gap can be formed in space after the structure is stacked, so that the magnetic nanochain has good liquidity when used as a filling material and can be in full contact reaction with a flowing substance.
The invention also provides the one-dimensional Fe fixed with the glucose oxidase3O4@SiO2The application of the magnetic nanochain in catalyzing hydrolysis of glucose can catalyze hydrolysis of glucose into gluconic acid and hydrogen peroxide.
The invention also provides the one-dimensional Fe fixed with the glucose oxidase3O4@SiO2The application of the magnetic nano-chain in the aspect of glucose detection. Using the one-dimensional Fe immobilized with glucose oxidase3O4@SiO2The magnetic nano-chain is used as a filling medium to catalyze hydrolysis of glucose to generate hydrogen peroxide, and glucose is detected based on hydrogen peroxide-luminol chemiluminescence.
The invention also provides one-dimensional Fe filled with the immobilized glucose oxidase3O4@SiO2Filling device of magnetic nano chain.
Further, theThe filling device is a hollow cavity with an inlet end and an outlet end, and the one-dimensional Fe fixed with the glucose oxidase is filled in the hollow cavity3O4@SiO2A magnetic nanochain material; the inlet and outlet ends are sealed by microporous filter membranes to prevent the filler from leaking.
The specification of the microporous filter membrane is 0.45 mu m.
The one-dimensional Fe immobilized with glucose oxidase3O4@SiO2The filling amount of the magnetic nano-chain material can be changed according to the amount of glucose, and the relative amount of the magnetic nano-chain material and the glucose is one-dimensional Fe fixed with glucose oxidase3O4@SiO2Magnetic nanochain material: glucose (10-40) mg: (0.1-0.3) mol.
A flow injection chemiluminescence apparatus for detecting glucose is provided, wherein a pipeline for conveying glucose is connected with the filling device.
The structure of the flow injection chemiluminescence apparatus comprises a pipeline A, a pipeline B, a pipeline C, a mixer, a reactor and a detector; the pipeline A is internally provided with a peristaltic pump 1 and a peristaltic pump 2, and the filling device is connected between the peristaltic pump 1 and the peristaltic pump 2; peristaltic pumps 3 are arranged in the pipeline B and the pipeline C, and the peristaltic pumps 3 can drive or simultaneously drive the liquid in the pipeline B and the liquid in the pipeline C to be mixed in the mixer; the pipeline A and the mixer are connected to the reactor through the same pipeline, and finally, photoelectric signals are displayed in the detector.
When glucose detection is carried out, a glucose solution enters the filling device through a pipeline A under the conveying of the peristaltic pump 1, and glucose and one-dimensional Fe fixed with glucose oxidase in the filling device3O4@SiO2And (3) carrying out reaction on the magnetic nano-chain material, hydrolyzing glucose into gluconic acid and hydrogen peroxide under the catalysis of glucose oxidase, then flowing out of the packed column, mixing and reacting with luminol solution conveyed through a pipeline B in a reactor under the drive of a peristaltic pump 2 to generate chemiluminescence, and carrying out online detection through a detector, thereby realizing the purpose of continuously detecting the glucose online.
The invention synthesizes the one-dimensional Fe with larger size through the actions of silanization and an external magnetic field3O4@SiO2Magnetic nanochains, and GOX is immobilized on the nanochains by an enzyme immobilization technology, so that the nanochains have space gaps and catalytic performance. At the same time, one-dimensional Fe immobilized with glucose oxidase is used3O4@SiO2The magnetic nanochain is used as stationary phase filler, filled into a filling device and used as an enzyme reaction device, and coupled with a flow injection chemiluminescence apparatus, so that real-time continuous online chemiluminescence detection of glucose is realized.
The invention discloses one-dimensional Fe fixed with glucose oxidase3O4@SiO2The magnetic nano-chain nano-material has a larger size in structure, and larger gaps can be generated when a large amount of nano-chain nano-materials are stacked, so that the nano-chain nano-material can not generate large blockage and has better flow-through property after being filled into an enzyme reaction device. Meanwhile, the immobilized enzyme has good immobilization rate due to the silanized one-dimensional nano chain, and the glucose can be catalyzed due to the high catalytic activity of the enzyme, so that the purpose of detecting the glucose can be achieved. And the preparation method of the one-dimensional nano chain is simple, and the one-dimensional nano chain can be recycled and is environment-friendly.
Drawings
FIG. 1 shows Fe prepared in example 13O4NPs (left) and one-dimensional Fe3O4@SiO2Transmission electron microscopy of magnetic nanochains (right);
FIG. 2 shows one-dimensional Fe prepared in example 13O4@SiO2Scanning electron microscopy of magnetic nanochains;
FIG. 3 shows one-dimensional Fe prepared in example 13O4@SiO2XPS plot of magnetic nanochains;
FIG. 4 shows one-dimensional Fe prepared in example 13O4@SiO2An infrared spectrum of the magnetic nanochain;
FIG. 5 is Fe prepared in example 23O4@SiO2-scanning electron micrographs of GOX;
FIG. 6 shows pure GOX (a), and Fe in application example 13O4@SiO2-GOX(b)、Fe3O4@SiO2(c) A comparison of chemiluminescence intensities produced by the catalyzed glucose reaction;
FIG. 7 shows Fe at different catalytic times3O4@SiO2-map of chemiluminescence intensities resulting from GOX-catalyzed glucose production;
FIG. 8 shows different Fe3O4@SiO2At GOX concentration, Fe3O4@SiO2-map of chemiluminescence intensities resulting from GOX-catalyzed glucose production;
FIG. 9 shows application example 2 in which Fe was filled3O4@SiO2Schematic representation of a filling device for GOX, a being sealed at one end with a microporous membrane and B being sealed at both ends with a microporous membrane;
FIG. 10 is a graph showing the comparison of the analysis and detection effects of two filling devices in application example 2 after being applied to a flow injection chemiluminescence apparatus;
FIG. 11 is a graph showing the comparison of the analytical results of different concentrations of glucose in the modified flow injection chemiluminescence apparatus of application example 3, wherein a-2mM glucose solution, b-4mM glucose solution, and c-10mM glucose solution;
FIG. 12 is a block diagram of a conventional flow injection chemiluminescence apparatus;
figure 13 is a diagram of a flow injection chemiluminescence apparatus after retrofitting.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
One-dimensional Fe3O4@SiO2A method for preparing a magnetic nanochain, the method comprising the steps of
(1) Preparation of Fe3O4Nanoparticle: dissolving 1.3g of ferric chloride, 2.4g of sodium acetate and 0.5g of sodium citrate in 40mL of ethylene glycol, and fully mixing and stirring for 30 min; carrying out solvothermal reaction on the solution at the high temperature of 200 ℃ and under the high pressure for 10h, cleaning and separating, and carrying out vacuum drying to obtain a product, namely Fe3O4Nanoparticles.
(2) Preparation of one-dimensional Fe3O4@SiO2Nano-chain: 200. mu.L of 10mg/mL Fe3O4Fully and uniformly mixing the dispersion liquid, 400 mu L of deionized water, 1000 mu L of isopropanol, 20 mu L of LTEOS and 40 mu L of ammonia water, transferring the solution to a position 1.5cm beside a magnet, and standing for reaction for 7 hours; after the reaction is finished, cleaning and separating to obtain a product, namely Fe3O4@SiO2And (4) nano-chains.
Fe prepared in the steps (1) and (2)3O4NPs and Fe3O4@SiO2The nano-chain is detected by a transmission electron microscope, the specific result is shown in figure 1, and Fe3O4The particle size is 200-300nm, and the length of the nano-chain is 10-40 μm.
For the Fe prepared in the step (2)3O4@SiO2The specific result of the nano-chain detected by a scanning electron microscope is shown in fig. 2, and the structure of the nano-chain is stable and uniform.
For the Fe prepared in the step (2)3O4@SiO2The specific result of XPS spectrum detection of the nano-chain is shown in FIG. 3, and as can be seen from FIG. 3, Fe3O4@SiO2The nano-chain contains four elements of carbon, iron, oxygen and silicon.
FIG. 4 shows Fe prepared in the above step (2)3O4@SiO2The infrared spectrum of the nano-chain is characterized in that the vibration of the iron-oxygen bond and the stretching vibration of the Si-O bond of the nano-chain can be seen from figure 4.
Example 2
One-dimensional Fe immobilized with glucose oxidase3O4@SiO2The preparation method of the magnetic nanochain comprises the following steps:
40mg of Fe prepared in example 13O4@SiO2Mixing nanochain with 4mL of 2% 3-Aminopropyltriethoxysilane (APTES) water solution, stirring for 20h, separating by magnetic separation, and washing with PBS buffer solution of pH7.3;
adding 200 mu L of glutaraldehyde, and fully mixing and stirring for 2 h; separating the product by magnetic separation with a magnet, and washing with PBS buffer solution with pH 6.5;
adding 4mg GOX, shaking at 4 deg.C once every 2 hr, reacting for 20 hr, magnetically separating the product, washing with PBS buffer solution of pH6.0, and separating to obtain one-dimensional Fe fixed with GOX3O4@SiO2The SEM image of the nanochain is shown in FIG. 5.
Application example 1
In this application example Fe3O4@SiO2GOX solution, Fe3O4@SiO2The solution is respectively Fe3O4@SiO2-GOX、Fe3O4@SiO2Dispersing in PBS buffer solution with pH of 6.0 to obtain; the glucose oxidase solution is prepared by dissolving glucose oxidase in PBS buffer solution with pH of 6.0; the glucose solution is aqueous solution of glucose; the luminol solution is an aqueous solution of luminol.
1) This application example discusses GOX-immobilized Fe3O4@SiO2The immobilization rate of GOX of the nano-chain is as follows: GOX-immobilized Fe3O4@SiO2Nanochain (Fe)3O4@SiO2-GOX) solution and glucose solution are mixed for reaction, the nanochains are separated after the reaction is finished, the supernatant is detected by a conventional flow injection chemiluminescence apparatus, the structure diagram is shown in figure 12, and the intensity of a chemiluminescence signal is observed. And pure GOX and one-dimensional Fe3O4@SiO2Nano-chain replacing Fe fixed with GOX3O4@SiO2The nanochain is used as a contrast to compare the magnitude of the signal generated by the three.
In the above monitoring method, 10mg/mL Fe3O4@SiO21mL of GOX solution, 20mL of 10mM glucose solution, 1mM of luminol solution; the reaction temperature is 25-30 ℃, and the reaction time is 10-30 min.
The method specifically comprises the following steps:
three 50mL centrifuge tubes were prepared, and 20mL of 10mM glucose solution was added to each tube, followed by 1mL of 1.0mg/mL glucose oxidase solution (No. 1) and 1mL of 1.0mg/mL Fe3O4@SiO2GOX solution (a)No. 2) and 1mL of 1.0mg/mL Fe3O4@SiO2And (3) putting the solution (No. 3) in a centrifuge tube, fully mixing, placing the centrifuge tube at room temperature for reaction for 30min, separating the magnetic nanochains in the centrifuge tubes No. 2 and No. 3 by using a magnet respectively, and taking supernate. And (3) respectively detecting the solutions of the three centrifuge tubes on a flow injection chemiluminescence apparatus, collecting and detecting signals of the solutions, and analyzing results. During detection, the solution in the centrifuge tube is injected into the pipeline A of the flow injection chemiluminescence apparatus, and 1mM luminol solution is injected into the pipeline B.
The specific results are shown in FIG. 6, which are pure GOX and Fe respectively3O4@SiO2、Fe3O4@SiO2Comparison of the chemiluminescence intensities produced by the reaction of glucose catalyzed by GOX, from which Fe can be seen3O4@SiO2After GOX reacts with glucose, the reaction solution also can generate higher reflection intensity after reacting with the luminol solution, and therefore, the GOX can be seen in one-dimensional Fe3O4@SiO2The curing rate on the magnetic nanochain is high.
2) This application example also discusses Fe3O4@SiO2Effect of GOX on the chemiluminescence intensity by catalyzing different reaction times of glucose
6 50mL centrifuge tubes were prepared, 20mL of 10mM glucose solution was added to each tube, and 1mL of 10mg/mL Fe was added3O4@SiO2GOX solution in centrifuge tubes. Reacting at room temperature for 1, 2, 5, 10, 20 and 30min, separating magnetic nano-chain in the centrifugal tube with magnet, and collecting supernatant. And (3) respectively detecting the supernatants on a conventional flow injection chemiluminescence apparatus, collecting and detecting signals of the supernatants, and analyzing results. During detection, the supernatant liquid is injected into the pipeline A of the flow injection chemiluminescence apparatus, and the 1mM luminol solution is injected into the pipeline B. As shown in FIG. 7, the chemiluminescence intensity increased with the increase in the reaction time.
3) The application example also discusses the catalytic activity of the magnetic nano-chain immobilized GOX, and the detection method comprises the following steps: GOX-immobilized Fe of different masses3O4@SiO2The nano-chain is mixed with glucose solution and reacts, separates the nano-chain after the reaction, and the supernatant is detected through flow injection chemiluminescence appearance, observes the power of chemiluminescence signal, specifically is:
6 50mL centrifuge tubes were prepared, 20mL of 10mM glucose solution was added to each tube, and then Fe was added at concentrations of 5, 10, 15, 20, 25, and 30mg/mL3O4@SiO21mL of GOX solution is put into a centrifuge tube, and after reaction is carried out for 30min at room temperature, magnetic particles in the centrifuge tube are separated by a magnet, and then supernatant is taken. And (3) respectively detecting the supernatants on a conventional flow injection chemiluminescence apparatus, collecting and detecting signals of the supernatants, and analyzing results.
As shown in FIG. 8, the intensity of chemiluminescence increased with the increase in the amount of immobilized enzyme added.
Application example 2
One-dimensional Fe loaded with glucose oxidase immobilized prepared in example 23O4@SiO2The filling device of the magnetic nanochain is characterized in that the filling device is a hollow cavity with an inlet end and an outlet end, and 20mg of one-dimensional Fe fixed with glucose oxidase is filled in the hollow cavity3O4@SiO2Magnetic nanochain material, as shown in fig. 9.
The two ends of the inlet and the outlet are required to be filled with microporous filter membranes, so that the inlet and the outlet can be used as plugs to prevent the leakage of the filler on one hand, and the solution can flow through the inlet and the outlet without obstruction on the other hand.
For comparison, two filling devices were prepared, one with a microporous membrane only at the outlet end; and the other is provided with a microporous filter membrane at both the inlet and the outlet, as shown in figure 9.
And the conventional flow injection chemiluminescence apparatus is modified by two filling devices respectively, and the specific modification is as follows: the filling device is arranged in a pipeline for conveying glucose solution, peristaltic pumps are respectively arranged at the front and the back of the filling device, and the structure of the modified flow injection chemiluminescence apparatus is shown in figure 12, and specifically comprises the following steps: the structure of the flow injection chemiluminescence apparatus comprises a pipeline A, a pipeline B, a pipeline C, a mixer, a reactor and a detector; the pipeline A is internally provided with a peristaltic pump 1 and a peristaltic pump 2, and the filling device is connected between the peristaltic pump 1 and the peristaltic pump 2; peristaltic pumps 3 are arranged in the pipeline B and the pipeline C, and the peristaltic pumps 3 can drive or simultaneously drive the liquid in the pipeline B and the liquid in the pipeline C to be mixed in the mixer; the pipeline A and the mixer are connected to the reactor through the same pipeline, and finally, photoelectric signals are displayed in the detector.
When glucose detection is carried out, a glucose solution enters the filling device through a pipeline A under the conveying of the peristaltic pump 1, and glucose and one-dimensional Fe fixed with glucose oxidase in the filling device3O4@SiO2And (3) carrying out reaction on the magnetic nano-chain material, hydrolyzing glucose into gluconic acid and hydrogen peroxide under the catalysis of glucose oxidase, then flowing out of the packed column, mixing and reacting with luminol solution conveyed through a pipeline B in a reactor under the drive of a peristaltic pump 2 to generate chemiluminescence, and carrying out online detection through a detector, thereby realizing the purpose of continuously detecting the glucose online.
The two groups of modified flow injection chemiluminescence apparatuses are verified in glucose detection effect, wherein the concentration of a glucose solution is 10mM, the concentration of a luminol solution is 1mM, two groups of detection signals are compared, and a relatively good experimental device is selected. The specific results are shown in fig. 10, which shows that the filling device with the microporous filter membranes added at both the inlet and outlet ends has better effect, and the experiment in the following application example 3 is performed by using the modified flow injection chemiluminescence apparatus.
Application example 3
Respectively pumping 2mM, 4mM and 10mM glucose solutions into the modified flow injection chemiluminescence apparatus through a pipeline A, respectively pumping 1mM luminol solution into the modified flow injection chemiluminescence apparatus through a pipeline B, and observing the reaction efficiency of glucose with different concentrations in the reaction device and the intensity of generated chemiluminescence signals through continuous online detection. As shown in FIG. 11, the intensity of the generated chemical signal increased with the increase of the glucose concentration.
The above detailed descriptions of the preparation method and application of the one-dimensional ferroferric oxide @ silica magnetic nanochain and the immobilized glucose oxidase thereof with reference to the examples are illustrative and not restrictive, and several examples can be cited according to the limited scope, so that changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. One-dimensional Fe3O4@SiO2The preparation method of the magnetic nanochain is characterized by comprising the following steps of:
(1) preparation of Fe3O4Nanoparticles;
(2) mixing Fe3O4Fully mixing the dispersion liquid of the nano particles, tetraethyl silicate, ammonia water, deionized water and isopropanol, placing the mixture in an external magnetic field for reaction for 7 to 10 hours, and centrifuging and washing the mixture for multiple times after the reaction is finished to obtain one-dimensional Fe3O4@SiO2Magnetic nanochains.
2. The method according to claim 1, wherein in the step (2), the Fe3O4The volume ratio of the nano particle dispersion liquid to the tetraethyl silicate to the ammonia water to the deionized water to the isopropanol is 200: 10-20: 20-40: 400: 1000, parts by weight; said Fe3O4The concentration of the nanoparticle dispersion was 10 mg/mL.
3. One-dimensional Fe immobilized with glucose oxidase3O4@SiO2The preparation method of the magnetic nanochain is characterized by comprising the following steps of: one-dimensional Fe prepared by the method of claim 13O4@SiO2Stirring and reacting the magnetic nanochain with an aqueous solution of 3-aminopropyltriethoxysilane, stirring and reacting with glutaraldehyde after separation and cleaning, reacting with glucose oxidase after separation and cleaning, and obtaining the one-dimensional Fe immobilized with the glucose oxidase after separation and cleaning3O4@SiO2Magnetic nanochains.
4. The method according to claim 3, wherein the Fe is one-dimensional3O4@SiO2The reaction time of the magnetic nanochain with 3-aminopropyltriethoxysilane, glutaraldehyde and glucose oxidase is 18-22 h, 1.5-2.5 h and 18-22 h respectively.
5. The method according to claim 3, wherein the solvents used in the three separation washes are PBS buffer solutions with pH7.3, 6.5, 6.0; the method of separation may be centrifugation or magnetic separation.
6. The glucose oxidase-immobilized one-dimensional Fe prepared by the preparation method according to any one of claims 3 to 53O4@SiO2Magnetic nanochains.
7. The one-dimensional Fe immobilized with glucose oxidase of claim 63O4@SiO2The application of the magnetic nano-chain in catalyzing the hydrolysis of glucose.
8. The one-dimensional Fe immobilized glucose oxidase of claim 63O4@SiO2The application of the magnetic nano-chain in the aspect of glucose detection.
9. One-dimensional Fe loaded with immobilized glucose oxidase of claim 63O4@SiO2Filling device of magnetic nano chain.
10. A flow injection chemiluminescence apparatus for detecting glucose, wherein a filling device according to claim 9 is connected to a conduit for transporting glucose in the flow injection chemiluminescence apparatus.
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