CN109650463A - The preparation method and purposes of cobaltosic sulfide --- Mimetic Peroxidase material - Google Patents

The preparation method and purposes of cobaltosic sulfide --- Mimetic Peroxidase material Download PDF

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CN109650463A
CN109650463A CN201811535535.3A CN201811535535A CN109650463A CN 109650463 A CN109650463 A CN 109650463A CN 201811535535 A CN201811535535 A CN 201811535535A CN 109650463 A CN109650463 A CN 109650463A
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preparation
mimetic peroxidase
analogue enztme
peroxidase
mimetic
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王瑾
王毅
张盾
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Institute of Oceanology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/30—Sulfides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G01—MEASURING; TESTING
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    • 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
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

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Abstract

The present invention proposes a kind of preparation and application with Mimetic Peroxidase (POD) active cobaltosic sulfide nano material.This method belongs to mimetic enzyme catalysis oxidation technology field.The present invention passes through urea precipitation method first and prepares presoma, then vulcanizes to obtain the high cobaltosic sulfide analogue enztme material of activity function by thioacetamide.Nano material prepared by the present invention has many advantages, such as that synthetic method is simple, at low cost, performance is significant, has broad application prospects in nano material catalysis oxidation field.

Description

The preparation method and purposes of cobaltosic sulfide --- Mimetic Peroxidase material
Technical field
The present invention relates to simulation zymotechnic, specifically a kind of Co3S4Analogue enztme material and its preparation and application.
Background technique
The intracorporal organized enzyme of biology has high specific and catalytic activity, is widely used in bio-sensing, health care, ring Many fields such as border protection, food industry.But since most of natural enzyme stabilities are poor, vulnerable to temperature, pH value and albumen The inevitably influence of condition such as there is and inactivate in enzyme, its preparation, cost for purification are high in addition, significantly limit answering for they With.Therefore, the research for developing the strong and at low cost analogue enztme material of, stability simple with preparation method seems extremely heavy It wants.
In recent years, with the study found that more and more nano materials or nanocomposite have analogue enztme by verification Property, such as Cu2(OH)3、Cl-CeO2[1]、Ag3PO4[2], c-based nanomaterial [3,4] etc..Compared to the acquisition side of native enzyme On the one hand method reduces material cost, second is that simple synthetic method, unit operation is easily achieved.
1.Wang N,Sun JC,Chen LJ,Fan H,Ai SY(2015)A Cu2(OH)3Cl- CeO2nanocomposite with peroxidase-like activity,and its application to the determination of hydrogen peroxide,glucose and cholesterol.Microchim Acta 182 (9-10):1733-1738.
2.Liu YJ,Zhu GX,Yang,J,Yuan AH,Shen XP(2014)Peroxide-like catalytic activity of Ag3PO4nanocrystals prepared by a colloidal route.PLoS One9(10): e109158.
3.Song YJ,Wang XH,Zhao C,Qu KG,Ren JS,Qu XG(2010)Label-free colorimetric detection of single nucleotide polymorphism bby using single- walled carbon nanotube intrinsic peroxidase-like activity.Chem Eur J16(12): 3617-3621.
4.Cui RJ,Han ZD,Zhu JJ(2011)Helical carbon nanotubes:intrinsic peroxidase catalytic activity and its application for biocatalysis and biosensing.Chem Eur J17(34):9377-9284.
Summary of the invention
One of the objects of the present invention is to provide the preparations and application of a kind of cobaltosic sulfide analogue enztme material.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of Mimetic Peroxidase nano material is prepared by cobalt salt and urea precipitation containing cobalt Then presoma vulcanizes to obtain chemical constituent to be Co by hydro-thermal method3S4Nano material.
Further,
1) by cobalt salt and urea (CO (NH2)2) powder mixing, add deionized water and obtain mixed liquor, adjust pH of mixed to 12-14h is crystallized at 100-120 DEG C after acidity mixing, obtains presoma；Wherein, Co in cobalt salt2+Molar ratio with urea is 2:1- 1:2；
2) it after mixing presoma and thioacetamide powder, is dissolved in deionized water and being uniformly dispersed, then in 180-200 DEG C vulcanization 12-14h obtain Co3S4Nano material；Wherein, Co in cobalt salt2+Molar ratio with thioacetamide is 2-1:1-3.
Cooled to room temperature after the step 1) crystallization takes out presoma, is successively centrifuged with ultrapure water and dehydrated alcohol It cleans repeatedly, 60-80 DEG C of drying, for use.
It is 1-6 that the step 1), which adjusts mixed liquor pH value,.
The cobalt salt is cobalt chloride hexahydrate or cabaltous nitrate hexahydrate；
The Co2+Optimum molar ratio with urea is 1:1；Co2+Molar ratio with thioacetamide is 1:1.
The step 2) is dissolved in deionized water after mixing presoma and thioacetamide, and magnetic agitation 20-40min is obtained Finely dispersed mixture, then carries out vulcanization reaction, cooled to room temperature after vulcanization reaction, successively with ultrapure water and anhydrous Ethyl alcohol centrifugation is cleaned repeatedly, and 60-80 DEG C is dried to obtain cobaltosic sulfide analogue enztme material.
Above-mentioned steps 1) and step 2) in washing be first through ultrapure water centrifuge washing 2-4 times, then again through anhydrous second Alcohol centrifuge washing 2-4 times；Centrifugal condition is 4000 turns/min, is centrifuged 10min.
A kind of Mimetic Peroxidase material of the preparation method preparation: cobaltosic sulfide is prepared according to the method Analogue enztme material.
A kind of application of Mimetic Peroxidase material, the cobaltosic sulfide analogue enztme material is as peroxidase In application.
The cobaltosic sulfide analogue enztme material is anti-carrying out catalytic oxidation-reduction to substrate as Mimetic Peroxidase It answers.
The cobaltosic sulfide analogue enztme material is in acid condition catalyzed substrate as Mimetic Peroxidase Redox reaction.
The substrate is TMB and H2O2。
Compared with prior art, the present invention having the following advantages and outstanding effects:
The present invention prepares presoma by urea precipitation method, then obtains four vulcanizations by thioacetamide vulcanizing treatment Three cobalts --- Mimetic Peroxidase material.Resulting materials of the present invention are at low cost, preparation method is simple, reproducible；The material can It is had potential application as a kind of novel analogue enztme in fields such as immunoassay, biological detection and clinical diagnosises, new It has broad application prospects in the analysis of type catalysis oxidation.
Detailed description of the invention:
Fig. 1 is the TEM figure for the nano material that case study on implementation of the present invention provides；
Fig. 2 is the x-ray diffraction pattern for the qualitative analysis material composition that case study on implementation of the present invention provides；
Fig. 3 is the ratio chromatic graph of nano material Mimetic enzyme provided in an embodiment of the present invention catalysis.
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:
12mmol CoCL2 6H2O (CoCl is separately added into beaker2·6H2O), 12mmol urea (CO (NH2)2) and 60mL deionized water, adjusting pH is 2.05, is uniformly mixed, and transfer is as crystallizing 12h at 100 DEG C of 100mL hydrothermal reaction kettle.It is brilliant Cooled to room temperature after change, take out presoma, first through ultrapure water centrifuge washing 3 times, then again through dehydrated alcohol from The heart washs 2-4 times；Centrifugal condition be 4000 turns/min, be centrifuged 10min, 60 DEG C of dryings after washing, for use.
400mg presoma, 375mg thioacetamide and 60mL deionized water, magnetic agitation one are separately added into beaker The section time, so that precursor powder is uniformly dispersed in the solution, be transferred to 180 DEG C of vulcanization 12h in 100mL hydrothermal reaction kettle.Reaction After, reaction kettle cooled to room temperature, by above-mentioned steps cleaning, drying, obtain cobaltosic sulfide analogue enztme material (referring to Fig. 1).XRD test result shows that product is Co3S4(see Fig. 2).
The cobaltosic sulfide nano material synthesized as seen from Figure 1 is the hollow structure of tubulose, and precursor powder is dispersed In thioacetyl amine aqueous solution, sulphur is diffused into nanoneedle presoma surface, and sulphur and cobalt ions interaction generate cobaltosic sulfide, Sulphion forms the hollow knot of tubulose due to the difference of sulphion and cobalt ions diffusion velocity from surface internally diffusion into the surface Structure.Synthesize cobaltosic sulfide nano material and ingredient and Co as seen from Figure 2 simultaneously3S4Standard card (JCPDS No.42- 1448) it matches.
Embodiment 2-7:
Preparation process:
12mmol CoCL2 6H2O (CoCl is separately added into 6 beakers2·6H2O), 12mmol urea (CO (NH2)2) With 60mL deionized water, adjust pH be respectively 1.15,2.05,3.05,4.05,5.05,6.05, be uniformly mixed, transfer as 12h is crystallized at 100 DEG C of 100mL hydrothermal reaction kettle.Cooled to room temperature after crystallization takes out presoma, first through ultrapure Water centrifuge washing 3 times, then again through dehydrated alcohol centrifuge washing 2-4 times；Centrifugal condition is 4000 turns/min, is centrifuged 10min, washes 60 DEG C of dryings after washing, for use.
400mg presoma, 375mg thioacetamide and 60mL deionized water, magnetic agitation are separately added into 6 beakers For a period of time, so that precursor powder is uniformly dispersed in the solution, be transferred to 180 DEG C of vulcanization 12h in 100mL hydrothermal reaction kettle.Instead After answering, reaction kettle cooled to room temperature obtains cobaltosic sulfide analogue enztme material by above-mentioned steps cleaning, drying. XRD test result shows that product is Co3S4(referring to table 1).
Table 1
Application examples
In 0.2mM H2O2, 0.15mM TMB, 0.3mg/mL nano material, pH be 3.05 PBS buffer solution system in test Simulate enzyme performance.When there was only hydrogen peroxide and analogue enztme material in system, when TMB not being added, solution is in colourless.And when in solution Only TMB and analogue enztme material, when being not added with hydrogen peroxide, solution illustrates that nano material does not have oxidation enzymatic property in colourless； When analogue enztme material is added into TMB and hydrogen peroxide system, solution becomes extremely apparent blue；And then the visible present invention mentions The nano material of confession has Mimetic Peroxidase activity.

Claims (10)

1. a kind of preparation method of Mimetic Peroxidase nano material, it is characterised in that: prepared by cobalt salt and urea precipitation The presoma containing cobalt is obtained, then vulcanizes to obtain chemical constituent to be Co by hydro-thermal method3S4Nano material.
2. by the preparation method of Mimetic Peroxidase material described in claim 1, it is characterised in that:
1) by cobalt salt and urea (CO (NH2)2) powder mixing, it adds deionized water and obtains mixed liquor, adjust pH of mixed to acidity 12-14h is crystallized after mixing at 100-120 DEG C, obtains presoma；Wherein, Co in cobalt salt2+Molar ratio with urea is 2:1-1:2；
2) it after mixing presoma and thioacetamide powder, is dissolved in deionized water and being uniformly dispersed, then in 180-200 DEG C of sulphur Change 12-14h and obtains Co3S4Nano material；Wherein, Co in cobalt salt2+Molar ratio with thioacetamide is 2-1:1-3.
3. by the preparation method of Mimetic Peroxidase material described in claim 2, it is characterised in that: after the step 1) crystallization Cooled to room temperature takes out presoma, is successively cleaned repeatedly with ultrapure water and dehydrated alcohol centrifugation, 60-80 DEG C of drying, to With.
4. by the preparation method of Mimetic Peroxidase material described in claim 2, it is characterised in that: the step 1) adjusts mixed Conjunction liquid pH value is 1-6.
5. by the preparation method of Mimetic Peroxidase material described in claim 2, it is characterised in that: the step 2) is by forerunner It is dissolved in deionized water after body and thioacetamide mixing, magnetic agitation 20-40min obtains finely dispersed mixture, and laggard Row vulcanization reaction, cooled to room temperature after vulcanization reaction are successively cleaned with ultrapure water and dehydrated alcohol centrifugation, 60-80 repeatedly DEG C it is dried to obtain cobaltosic sulfide analogue enztme material.
6. by the Mimetic Peroxidase material of preparation described in claim 1, it is characterised in that: press claim 1 the method Prepare cobaltosic sulfide analogue enztme material.
7. the application of composite oxides analogue enztme material according to claim 6, it is characterised in that: the cobaltosic sulfide mould Intend enzyme material as the application in peroxidase.
8. the application of composite oxides analogue enztme material according to claim 7, it is characterised in that: the cobaltosic sulfide mould Quasi- enzyme material is carrying out catalytic oxidation-reduction reaction to substrate as Mimetic Peroxidase.
9. the application of composite oxides analogue enztme material according to claim 8, it is characterised in that: the cobaltosic sulfide mould Intend enzyme material as Mimetic Peroxidase, catalytic oxidation-reduction reaction is carried out to substrate in acid condition.
10. the application of composite oxides analogue enztme material according to claim 7, it is characterised in that: the substrate be TMB and H2O2。
CN201811535535.3A 2018-12-14 2018-12-14 The preparation method and purposes of cobaltosic sulfide --- Mimetic Peroxidase material Pending CN109650463A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111039328A (en) * 2019-12-26 2020-04-21 中国科学院海洋研究所 Composite metal nano material and preparation and application thereof
CN114477306A (en) * 2022-03-01 2022-05-13 中国科学院海洋研究所 Composite metal sulfide with broad-spectrum bactericidal performance and preparation thereof
CN114618531A (en) * 2022-03-01 2022-06-14 中国科学院海洋研究所 Preparation and application of photocatalyst with visible light sterilization performance

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1819860A1 (en) * 1991-01-09 1993-06-07 Viktoriya D Chunaeva Method for production of cobalt sulfide
CN105692719A (en) * 2016-03-10 2016-06-22 太原理工大学 Preparation method of cobalt sulfide nanomaterial and method for detecting hydrogen peroxide with cobalt sulfide nanomaterial
CN105845448A (en) * 2016-03-17 2016-08-10 安徽师范大学 Homogeneous core-shell structure cobaltosic sulfide nanometer material, preparation method and application of being as super capacitor electrode material thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1819860A1 (en) * 1991-01-09 1993-06-07 Viktoriya D Chunaeva Method for production of cobalt sulfide
CN105692719A (en) * 2016-03-10 2016-06-22 太原理工大学 Preparation method of cobalt sulfide nanomaterial and method for detecting hydrogen peroxide with cobalt sulfide nanomaterial
CN105845448A (en) * 2016-03-17 2016-08-10 安徽师范大学 Homogeneous core-shell structure cobaltosic sulfide nanometer material, preparation method and application of being as super capacitor electrode material thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
QIAN ZHOU ET AL.: "Co3S4 polyaniline nanotubes as high performance anode materials for sodium ion batteries", 《J. MATER. CHEM. A》 *
YANG RONG ET AL.: "Two-dimentional Transition-metal Dichalcogenide Nanocomposites as Novel Enzyme Mimics: An Overview", 《PROGRESS IN BIOCHEMISTRY AND BIOPHYSICS》 *
刁金香等: "介孔Co3S4纳米棒的制备及电催化产氧性能的研究", 《人工晶体学报》 *
杨立新: "《无机化学实验》", 30 September 2011 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111039328A (en) * 2019-12-26 2020-04-21 中国科学院海洋研究所 Composite metal nano material and preparation and application thereof
CN114477306A (en) * 2022-03-01 2022-05-13 中国科学院海洋研究所 Composite metal sulfide with broad-spectrum bactericidal performance and preparation thereof
CN114618531A (en) * 2022-03-01 2022-06-14 中国科学院海洋研究所 Preparation and application of photocatalyst with visible light sterilization performance
CN114477306B (en) * 2022-03-01 2023-05-09 中国科学院海洋研究所 Composite metal sulfide with broad-spectrum sterilization performance and preparation thereof
CN114618531B (en) * 2022-03-01 2023-09-26 中国科学院海洋研究所 Preparation and application of photocatalyst with visible light sterilization performance

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