CN109499582B - Composite oxide mimic enzyme material and preparation method and application thereof - Google Patents

Composite oxide mimic enzyme material and preparation method and application thereof Download PDF

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CN109499582B
CN109499582B CN201811424281.8A CN201811424281A CN109499582B CN 109499582 B CN109499582 B CN 109499582B CN 201811424281 A CN201811424281 A CN 201811424281A CN 109499582 B CN109499582 B CN 109499582B
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composite oxide
mimic enzyme
enzyme material
oxide
mimic
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CN109499582A (en
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陈超
王毅
张盾
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Institute of Oceanology of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/531—Production of immunochemical test materials
    • G01N33/532—Production of labelled immunochemicals
    • G01N33/535—Production of labelled immunochemicals with enzyme label or co-enzymes, co-factors, enzyme inhibitors or enzyme substrates

Abstract

The invention relates to a mimic enzyme technology, in particular to a complex oxide (CoV complex oxide) mimic enzyme material and preparation and application thereof. Preparing a layered double-hydroxyl composite metal hydroxide precursor of CoV by a precipitant urea precipitation method, and then roasting to obtain the composite oxide mimic enzyme material of CoV. The cobalt vanadium oxide mimic enzyme provided by the invention has multiple characteristics of oxidase and peroxidase activities. The obtained composite material has the characteristics of easy operation of synthesis steps, low cost, obvious effect and the like, and has wide application prospect in novel catalytic oxidation analysis.

Description

Composite oxide mimic enzyme material and preparation method and application thereof
Technical Field
The invention relates to a mimic enzyme technology, in particular to a complex oxide (CoV complex oxide) mimic enzyme material and preparation and application thereof.
Background
In recent years, with the development of nanotechnology, more and more nanomaterials or nanocomposites have been found to have enzyme-mimetic properties, greatly expanding the enzyme test conditions, such as ferroferric oxide nanoparticles, cerium oxide nanomaterials [ assay A, Kaitanis C, Santra S, et al.pH-soluble oxide-activity of ceramic oxide nanoparticles acetic detection of cancer biological catalysts at neutral pH.analytical Chemistry,2011,83(7):2547 + 2553], carbon nanotubes, carbon quantum dots, noble metal nanoparticles gold, silver, platinum [ junction H, Chemistry Z, Cao H, et al.2012.21 activity of ceramic nanoparticles for biological assays, 5523; moglianetti M, De Luca E, Pedone D, et al, platinum nanoparticles ROS mesoporous-catalytic disease model Nanoscale,2016,8(6):3739-3752, and the like, and bimetallic nanomaterials.
However, nanoparticles are small in size and have high surface energy, and thus are prone to agglomeration. The multifunctional composite material nanometer mimic enzyme not only can control the size and unify the appearance of the nanometer material, but also can keep the high catalytic activity of the nanometer material. The method has important theoretical guidance and practical significance for the deep development and research of the nano mimic enzyme.
Disclosure of Invention
The invention aims to provide a composite oxide (CoV composite oxide) mimic enzyme material, and preparation and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a composite oxide mimic enzyme material comprises the steps of preparing a layered double-hydroxyl composite metal hydroxide precursor of CoV by a precipitant urea precipitation method, and then roasting to obtain the composite oxide mimic enzyme material of CoV.
Further, Co is added2+Soluble salts with vanadium trichloride (VCl)3) Mixing according to the ratio of 4-2: 1 of the amount of the substances, and adding urea (CO (NH)2)2) Adding the obtained product into water, uniformly mixing the obtained product until the obtained product is clear and transparent, then placing the obtained product in a hydrothermal reaction kettle for crystallization for 12 hours at the temperature of 150 ℃ (preferably 120 ℃), naturally cooling the obtained product to room temperature after crystallization, taking out the obtained product for cleaning and drying, and roasting the obtained product for 2 hours at the temperature of 800 ℃ (preferably 300 ℃) to obtain a Co-V-MMO mimic enzyme material after drying; wherein urea (CO (NH)2)2) The addition amount is 1-3 times of the amount of Co source material.
And washing the crystal with ultrapure water and ethanol in sequence after the crystallization treatment, centrifuging the washed crystal at 4000 rpm for 10min, centrifuging the washed crystal, precipitating the crystal, drying the crystal at 80 ℃ for 6h, and roasting the crystal after drying to obtain the Co-V MMO mimic enzyme material.
The Co2+The soluble salt is cobalt nitrate, cobalt chloride or cobalt oxalate.
The Co-V composite oxide mimic enzyme material is prepared according to the method.
The application of the composite oxide mimic enzyme material and the application of the Co-V composite oxide as mimic oxide or peroxidase.
The Co-V composite oxide is used as an oxide or a peroxide mimic enzyme to perform catalytic oxidation-reduction reaction on a substrate.
The Co-V composite oxide is used as an oxide or a peroxide mimic enzyme to perform catalytic oxidation-reduction reaction on a substrate under an acidic condition.
The substrate is TMB; or TMB and H2O2。
Compared with the prior art, the invention has the following advantages and prominent effects:
the CoV composite metal precursor is prepared by a urea precipitation method, and then a cobalt-vanadium composite oxide mimic enzyme and peroxide mimic enzyme double-enzyme active material with high dispersity and activating performance is obtained by roasting treatment; the mimic enzyme material has high chemical stability under an acidic condition, and meanwhile, the material is low in cost, simple in preparation method and good in repeatability; the mimic enzyme has potential application value in the fields of immunoassay, biological detection, clinical diagnosis and the like as a novel mimic enzyme; meanwhile, the mimic enzyme has wide application prospect in novel catalytic oxidation analysis.
Description of the drawings:
FIG. 1 is a TEM image of a composite nanomaterial provided by an embodiment of the present invention;
FIG. 2 is an X-ray diffraction diagram of the composition of a qualitative analytic material provided by an embodiment of the present invention;
FIG. 3 is a photograph of a color comparison of a composite biomimetic nanomanidase according to an embodiment of the present invention with peroxidase-like catalytic activity.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to provide a more complete understanding of the invention by one of ordinary skill in the art, and are not intended to be limiting in any way.
Example 1:
2.4mmol of cobalt chloride hexahydrate, 0.8mmol of vanadium trichloride (VCl)3) And 5mmol of urea (CO (NH)2)2) Dissolving the mixture in 35mL of water, stirring the mixture until the mixture is clear and transparent, placing the clear and transparent liquid in a 40mL hydrothermal reaction kettle for crystallization for 12 hours at 120 ℃, naturally cooling the liquid to room temperature after the crystallization is finished, taking the liquid out after the crystallization is cooled to room temperature, respectively ultrasonically cleaning the liquid for 3 times by using ultrapure water and absolute ethyl alcohol in sequence, drying the liquid for 6 hours at 80 ℃ after the cleaning, and then roasting the liquid for 2 hours at 400 ℃ in a muffle furnace to obtain the Co-V-MMO mimic enzyme material. The morphology TEM of the Co-V-MMO mimic enzyme material is shown in FIG. 1. 700 ℃ XRD test junctionThe fruit showed the product to be Co3O4/Co3V2O8(see FIG. 2).
The TEM image of FIG. 1 shows that CoV-MMO is a nanosheet with uniform morphology; from FIG. 2, it can be seen that the synthesized cobalt-vanadium composite nano material and the components pass through with Co3O4And Co3V2O8Standard card Co3O4(43-1003) and Co3V2O8(16-0675) and any other impurity phase is not present in the pattern.
Examples 2 to 18
The preparation process comprises the following steps:
2.4mmol of cobalt chloride hexahydrate and different addition amounts of vanadium trichloride (VCl)3) And 5mmol of urea (CO (NH)2)2) Dissolving the raw materials in 35mL of water, stirring the mixture until the mixture is clear and transparent, placing the clear and transparent liquid in a 40mL hydrothermal reaction kettle for crystallization for 12 hours at 120 ℃, naturally cooling the crystallized liquid to room temperature, taking the crystallized liquid out, respectively ultrasonically cleaning the crystallized liquid for 3 times by using ultrapure water and absolute ethyl alcohol in sequence, drying the cleaned liquid for 6 hours at 80 ℃, and roasting the dried liquid for 2 hours at 800 ℃ by using a muffle furnace to obtain the chemical component Co3O4/Co3V2O8The Co-V-MMO mimic enzyme material (see Table 1). Composite nano cobalt-vanadium material and Co as component3O4And Co3V2O8The standard cards (JCPDS No.47-1049 and JCPDS No.74-1394) match, and no other impurity phase appears.
TABLE 1
Figure BDA0001881211820000031
Application example
Take 100. mu.L of 3mM H2O2mu.L of 3mM TMB and 750 mu.L of sodium acetate buffer solution with the pH value of 4 are added, and the mimic enzyme material obtained in the previous embodiment with the concentration of 50 mu g/ml is added; meanwhile, a system without the above mimic enzyme material is used as a control 1, a system without hydrogen peroxide and TMB is used as a control 2, a system without TMB is used as a control 3, and hydrogen peroxide is not used as a control 4. At room temperatureReaction (change in absorbance within the range of the test wavelength, see FIG. 3) at 25 ℃ in the reaction, and it can be seen from FIG. 3 that control 1, to which the mimetic enzyme aqueous solution was not added, has no oxidation activity of hydrogen peroxide on TMB; while the solution was also slightly yellowish when no hydrogen peroxide and TMB control 2 were added; when no TMB control 3 was added, the solution was also slightly yellowish; when no hydrogen peroxide is added for comparison with the solution 4, the solution turns light blue, which indicates that the composite nano material has the property of oxidase; when TMB and hydrogen peroxide are added into the mimic enzyme aqueous solution, the blue color of the solution is darker than that of the control group 4, which indicates that the composite nano material has the peroxide mimic enzyme activity.
After centrifugal washing, the mimic enzyme material is not supplemented, the cycle is 6 times, the mimic enzyme performance basically keeps stable, and the mimic enzyme material has better stability.

Claims (6)

1. A preparation method of a composite oxide mimic enzyme material is characterized by comprising the following steps: preparing a layered double-hydroxyl composite metal hydroxide precursor of CoV by a precipitant urea precipitation method, and then roasting to obtain a composite oxide simulated oxidase or peroxidase of CoV;
mixing Co2+Soluble salt and vanadium trichloride VCl3Mixing the materials according to the mass ratio of 4-2: 1, and adding urea CO (NH)2)2Adding the obtained product into water, uniformly mixing the obtained product until the obtained product is clear and transparent, then placing the obtained product in a hydrothermal reaction kettle for crystallization for 12 hours at the temperature of 120-;
washing the crystal with ultrapure water and ethanol in sequence after the crystallization treatment, centrifuging, drying the precipitate, and roasting to obtain a Co-V MMO mimic enzyme material;
the Co2+The soluble salt is cobalt nitrate, cobalt chloride or cobalt oxalate.
2. A composite oxide mimetic enzyme material produced by the process of claim 1, wherein: the Co-V composite oxide mimic enzyme material prepared by the method of claim 1.
3. The use of a composite oxide mimic enzyme material according to claim 2, wherein: the Co-V composite oxide is applied to being used as a mimic oxide or peroxidase.
4. Use of a composite oxide mimic enzyme material according to claim 3, characterized in that: the Co-V composite oxide is used as an oxide or a peroxide mimic enzyme to perform catalytic oxidation-reduction reaction on a substrate.
5. The use of a composite oxide mimic enzyme material according to claim 4, wherein: the Co-V composite oxide is used as an oxide or a peroxide mimic enzyme to perform catalytic oxidation-reduction reaction on a substrate under an acidic condition.
6. Use of a composite oxide mimic enzyme material according to claim 5, characterized in that: the substrate is TMB or TMB and H2O2。
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CN111054357B (en) * 2019-12-12 2022-11-22 中国科学院海洋研究所 Cerium-containing composite oxide mimic enzyme material and preparation and application thereof
CN112630179B (en) * 2020-12-09 2023-07-21 安徽师范大学 Prussian blue quantum dot with oxide mimic enzyme property, preparation method thereof and method for detecting L-cysteine

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104568934A (en) * 2015-01-05 2015-04-29 上海纳米技术及应用国家工程研究中心有限公司 Application of nanometer cobaltosic oxide used as peroxide enzyme mimic for measuring concentration of hydrogen peroxide
CN104596956A (en) * 2015-01-05 2015-05-06 上海纳米技术及应用国家工程研究中心有限公司 Application of nano-nickel oxide as mimetic peroxidase for detecting hydrogen peroxide
CN105798324A (en) * 2016-03-21 2016-07-27 中山大学 Mimic enzyme based on self-assembly structure as well as preparation method and application thereof
CN107376961A (en) * 2017-07-25 2017-11-24 江苏大学 Preparation and application of the integrated CoP nano-chip arrays as monoblock type class peroxidase
CN108786830A (en) * 2018-06-29 2018-11-13 中国科学院海洋研究所 A kind of nickel vanadium oxides composite analogue enztme material and its preparation method and application
CN108872216A (en) * 2018-05-24 2018-11-23 首都师范大学 A kind of cobalt nickel nano-wire array and the preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104568934A (en) * 2015-01-05 2015-04-29 上海纳米技术及应用国家工程研究中心有限公司 Application of nanometer cobaltosic oxide used as peroxide enzyme mimic for measuring concentration of hydrogen peroxide
CN104596956A (en) * 2015-01-05 2015-05-06 上海纳米技术及应用国家工程研究中心有限公司 Application of nano-nickel oxide as mimetic peroxidase for detecting hydrogen peroxide
CN105798324A (en) * 2016-03-21 2016-07-27 中山大学 Mimic enzyme based on self-assembly structure as well as preparation method and application thereof
CN107376961A (en) * 2017-07-25 2017-11-24 江苏大学 Preparation and application of the integrated CoP nano-chip arrays as monoblock type class peroxidase
CN108872216A (en) * 2018-05-24 2018-11-23 首都师范大学 A kind of cobalt nickel nano-wire array and the preparation method and application thereof
CN108786830A (en) * 2018-06-29 2018-11-13 中国科学院海洋研究所 A kind of nickel vanadium oxides composite analogue enztme material and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"新型过氧化物模拟酶纳米材料在可视化检测葡萄糖中的应用";苏莉;《中国博士学位论文全文数据库工程俄科技I辑》;20131015(第10期);B020-41 *

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