CN109499582A - A kind of composite oxides analogue enztme material and its preparation method and application - Google Patents

A kind of composite oxides analogue enztme material and its preparation method and application Download PDF

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CN109499582A
CN109499582A CN201811424281.8A CN201811424281A CN109499582A CN 109499582 A CN109499582 A CN 109499582A CN 201811424281 A CN201811424281 A CN 201811424281A CN 109499582 A CN109499582 A CN 109499582A
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analogue enztme
composite oxides
composite
enztme material
preparation
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CN109499582B (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 present invention relates to simulate zymotechnic, specifically a kind of composite oxides (CoV composite oxides) analogue enztme material and its preparation and application.The laminated dihydroxy composite metal hydroxide precursor of CoV is prepared by precipitating reagent urea precipitation method, and the composite oxides analogue enztme material of CoV is then obtained by calcination process.Cobalt Vanadium Oxide analogue enztme provided by the invention has the multiple characteristics of oxidizing ferment and peroxidase activity simultaneously.Gained composite material has the characteristics that synthesis step is easy to operate, cost is small, significant effect, has broad application prospects in new catalytic Oxidation Analysis.

Description

A kind of composite oxides analogue enztme material and its preparation method and application
Technical field
The present invention relates to simulation zymotechnic, specifically a kind of composite oxides (CoV composite oxides) analogue enztme materials And its it prepares and applies.
Background technique
In recent years, with the exploitation of nanotechnology, more and more nano materials or nanocomposite are found to have The property of analogue enztme has greatly expanded the condition on probation of enzyme, such as ferriferrous oxide nano-particle, cerium dioxide nano material [Asati A,Kaittanis C,Santra S,et al.pH-tunable oxidase-like activity of cerium oxide nanoparticles achieving sensitive fluorigenic detection of Cancer biomarkers at neutral pH.Analytical Chemistry, 2011,83 (7): 2547-2553], carbon Nanotube, carbon quantum dot, noble metal nano particles gold, silver, platinum [Jiang H, Chen Z, Cao H, et al.Peroxidase- like activity of chitosan stabilized silver nanoparticles for visual and colorimetric detection of glucose.Analyst,2012,137(23):5560-5564；Moglianetti M,De Luca E,Pedone D,et al.Platinum nanozymes recover cellular ROS homeostasis in an oxidative stress-mediateddisease model.Nanoscale,2016,8(6): 3739-3752] etc. and bimetal nano material.
But nano particle with high surface energy, is then easy to happen reunion because size is small.Multifunctional composite nanometer Analogue enztme not only can control nano material size, unified pattern, moreover it is possible to it be made to keep high catalytic activity.This is deep to nanometer analogue enztme Enter developmental research with important theoretical direction and practical significance.
Summary of the invention
The purpose of the present invention is to provide a kind of composite oxides (CoV composite oxides) analogue enztme material and its preparation and Using.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of composite oxides analogue enztme material, the stratiform of CoV is prepared by precipitating reagent urea precipitation method Then dihydroxy composite metal hydroxide precursor obtains the composite oxides analogue enztme material of CoV by calcination process.
Further, by Co2+Soluble-salt and vanadium trichloride (VCl3) in substance 4~2:1 of amount ratio be mixing, Add urea (CO (NH2)2), it is soluble in water together after addition to mix up to clear, and be placed in hydrothermal reaction kettle Crystallization 12h under 120-150 DEG C (preferably 120 DEG C) takes out cleaning, dry after crystallization, after dry after cooled to room temperature 2h is roasted under 300-800 DEG C (preferably 300-500 DEG C) obtains Co-V-MMO analogue enztme material；Wherein, urea (CO (NH2)2) plus Amount is 1-3 times of the amount of the source Co substance.
Ultrapure water, ethanol washing are successively used after the Crystallizing treatment, are centrifugated 10min in 4000 turns/min after washing, Centrifuged deposit roast after 80 DEG C of dry 6h, drying obtains Co-V MMO analogue enztme material.
The Co2+Soluble-salt is cobalt nitrate, cobalt chloride or cobalt oxalate.
Composite oxides analogue enztme material prepares Co-V composite oxides analogue enztme material according to the method.
The application of composite oxides analogue enztme material, the composite oxides of the Co-V are as simulation oxide or peroxide Application in compound enzyme.
The composite oxides of the Co-V are carrying out catalysis oxidation also to substrate as oxide or Mimetic Peroxidase Original reaction.
The composite oxides of the Co-V in acid condition carry out substrate as oxide or Mimetic Peroxidase Catalytic oxidation-reduction reaction.
The substrate is TMB；Or TMB and H2O2。
Compared with prior art, the present invention having the following advantages and outstanding effects:
The present invention prepares CoV composition metal precursor by urea precipitation method, then by calcination process obtain it is dispersed it is high, The double enzymatic activity materials of cobalt vanadium oxides composite oxide analogue enztme and Mimetic Peroxidase with activity function；And it simulates Enzyme material has high chemical stability in acid condition, while the cost of material is low, preparation method is simple, repeatability by the present invention It is good；There is potential application value in fields such as immunoassay, biological detection and clinical diagnosises as a kind of novel analogue enztme；Together When analogue enztme have broad application prospects in new catalytic Oxidation Analysis.
Detailed description of the invention:
Fig. 1 is the composite nano materials TEM figure that case study on implementation of the present invention provides；
Fig. 2 is the qualitative analysis material composition x-ray diffraction pattern that case study on implementation of the present invention provides；
Fig. 3 be composite Nano analogue enztme provided in an embodiment of the present invention similar to Catalyzed Synthesis By Peroxidase activity when colorimetric shine Piece figure.
Specific embodiment
Below by way of specific embodiment, the invention will be further described, facilitates those skilled in the art more It is fully understood by the present invention, but do not limit the invention in any way.
Embodiment 1:
2.4mmol CoCL2 6H2O, 0.8mmol vanadium trichloride (VCl3) and 5mmol urea (CO (NH2)2) it is dissolved in 35mL water In stir to clarify transparent, clear liquid is placed in 40mL hydrothermal reaction kettle crystallization 12h at 120 DEG C, after crystallization from It is so cooled to room temperature, takes out after being cooled to room temperature and be successively cleaned by ultrasonic respectively 3 times with ultrapure water, dehydrated alcohol, in 80 after cleaning Then DEG C dry 6h obtains Co-V-MMO analogue enztme material with roasting 2h at 400 DEG C of Muffle furnace.Co-V-MMO analogue enztme material shape Looks TEM is as shown in Figure 1.700 DEG C of XRD test results show that product is Co3O4/Co3V2O8(see Fig. 2).
Scheming visible CoV-MMO by Fig. 1 TEM is the uniform nanometer sheet of pattern；Cobalt vanadium composite Nano material is synthesized as seen from Figure 2 Material and ingredient by with Co3O4And Co3V2O8The standard card Co of standard3O4(43-1003) and Co3V2O8(16-0675) kissing It closes, does not in addition occur other any impurity phases in map.
Embodiment 2-18
Preparation process:
Vanadium trichloride (the VCl of 2.4mmol CoCL2 6H2O and Different adding amount3) and 5mmol urea (CO (NH2)2) be dissolved in Stir to clarify transparent in 35mL water, clear liquid is placed in 40mL hydrothermal reaction kettle crystallization 12h at 120 DEG C, crystallization knot It takes out after cooled to room temperature after beam and is successively cleaned by ultrasonic respectively 3 times with ultrapure water, dehydrated alcohol, 80 DEG C of dryings after cleaning Then 6h is Co with roasting 2h at 300-800 DEG C of Muffle furnace to obtain chemical component3O4/Co3V2O8Co-V-MMO analogue enztme material (referring to table 1).Each synthesis cobalt vanadium composite nano materials and ingredient Co3O4And Co3V2O8Standard card (the JCPDS No.47- of standard 1049 and JCPDS No.74-1394) compare match, there are not other any impurity phases.
Table 1
Application examples
Take 100 μ L3mM H2O2, 100 μ L 3mM TMB, the sodium-acetate buffer that 750 μ L pH are 4, adding concentration is 50 Above-described embodiment of μ g/ml obtains analogue enztme material；Simultaneously the system of above-mentioned analogue enztme material not to be added as compareing 1, not The system of hydrogen peroxide and TMB is added as control 2, the system of TMB is not added as control 3, it is pair that hydrogen peroxide is not added According to 4.Reaction (test wavelength range internal absorbance changes referring to Fig. 3) under (25 DEG C) at room temperature, analogue enztme is not added as seen from Figure 3 The control 1 of aqueous solution, hydrogen peroxide does not have oxidation activity to TMB；And work as and be added without hydrogen peroxide and TMB control 2, solution is also Show slightly light yellow；When being added without TMB control 3, solution is also to show slightly light yellow；When being added without hydrogen peroxide control 4, solution shoals Blue illustrates that composite nano materials have oxidation enzymatic property；Simulation enzyme aqueous solution, solution blue are added as TMB and hydrogen peroxide It is deeper compared with control group 4, illustrate that composite nano materials have Mimetic Peroxidase activity.
After centrifuge washing, analogue enztme material is not supplemented, is recycled 6 times, is simulated enzyme performance kept stable, is illustrated to simulate Enzyme stability of material is preferable.

Claims (9)

1. a kind of preparation method of composite oxides analogue enztme material, it is characterised in that: prepared by precipitating reagent urea precipitation method Then the laminated dihydroxy composite metal hydroxide precursor of CoV obtains the composite oxides analogue enztme material of CoV by calcination process Material.
2. by the preparation method of composite oxides analogue enztme material described in claim 1, it is characterised in that: by Co2+Soluble-salt With vanadium trichloride (VCl3) in substance 4~2:1 of amount ratio be mixing, add urea (CO (NH2)2), it is molten together after addition Yu Shuizhong is mixed up to clear, and is placed in hydrothermal reaction kettle crystallization 12h at 120-150 DEG C, natural after crystallization Cleaning, drying are taken out after being cooled to room temperature, and are roasted 2h at 300-800 DEG C after dry and are obtained Co-V-MMO analogue enztme material.
3. pressing the preparation method of composite oxides analogue enztme material as claimed in claim 1 or 2, it is characterised in that: at the crystallization Ultrapure water, ethanol washing are successively used after reason, is centrifuged after washing, and roast obtains Co-V MMO analogue enztme material after precipitating is dry.
4. pressing the preparation method of composite oxides analogue enztme material as claimed in claim 1 or 2, it is characterised in that: the Co2+It is solvable Property salt be cobalt nitrate, cobalt chloride or cobalt oxalate.
5. by the composite oxides analogue enztme material of preparation described in claim 1, it is characterised in that: by side described in claim 1 Method prepares Co-V composite oxides analogue enztme material.
6. the application of composite oxides analogue enztme material as described in claim 5, it is characterised in that: the composite oxygen of the Co-V Compound is as the application in simulation oxide or peroxidase.
7. the application of composite oxides analogue enztme material according to claim 6, it is characterised in that: the composite oxygen of the Co-V Compound is carrying out catalytic oxidation-reduction reaction to substrate as oxide or Mimetic Peroxidase.
8. the application of composite oxides analogue enztme material according to claim 7, it is characterised in that: the composite oxygen of the Co-V Compound carries out catalytic oxidation-reduction reaction to substrate in acid condition as oxide or Mimetic Peroxidase.
9. the application of composite oxides analogue enztme material according to claim 6, it is characterised in that: the substrate be TMB or TMB and H2O2。
CN201811424281.8A 2018-11-27 2018-11-27 Composite oxide mimic enzyme material and preparation method and application thereof Active CN109499582B (en)

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CN111054357A (en) * 2019-12-12 2020-04-24 中国科学院海洋研究所 Cerium-containing composite oxide mimic enzyme material and preparation and application thereof
CN112630179A (en) * 2020-12-09 2021-04-09 安徽师范大学 Prussian blue quantum dot with oxide mimic enzyme property, preparation method thereof and method for detecting L-cysteine

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CN111054357A (en) * 2019-12-12 2020-04-24 中国科学院海洋研究所 Cerium-containing composite oxide mimic enzyme material and preparation and application thereof
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CN112630179A (en) * 2020-12-09 2021-04-09 安徽师范大学 Prussian blue quantum dot with oxide mimic enzyme property, preparation method thereof and method for detecting L-cysteine

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