CN108746660A - A kind of preparation method of copper gold platinum composite nano materials and its application on detection cysteine - Google Patents

A kind of preparation method of copper gold platinum composite nano materials and its application on detection cysteine Download PDF

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CN108746660A
CN108746660A CN201810595045.6A CN201810595045A CN108746660A CN 108746660 A CN108746660 A CN 108746660A CN 201810595045 A CN201810595045 A CN 201810595045A CN 108746660 A CN108746660 A CN 108746660A
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solution
preparation
composite nano
nano materials
copper
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CN108746660B (en
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姜翠凤
包帅
魏晓秀
杨子润
莫贵和
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Yangcheng Institute of Technology
Yancheng Institute of Technology
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Yangcheng Institute of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/054Nanosized particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems 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
    • G01N21/78Systems 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

Abstract

Application the invention discloses a kind of preparation method of copper gold platinum composite nano materials and its on detection cysteine.Copper-bath and sodium citrate solution is added in Xiang Shuizhong, adds fresh NaBH4, after solution is in light yellow, HAuCl is added4After aqueous solution stirring, storage is placed at 12-16 DEG C to get Cu@AuNPs, is put into refrigerator that be protected from light refrigeration spare;Cu@AuNPs are taken to add to K2PtCl6In solution, after being heated to 80 DEG C while stirring, then ascorbic acid is added dropwise continues stirring and become black to solution, you can.The copper gold platinum composite nano materials that the present invention is prepared have peroxidase sample activity, TMB and hydrogen peroxide system can be made to be displayed in blue, and the addition of cysteine, peroxidase sample can be inhibited active, according to system color change, Visual retrieval semicystinol concentration can be realized.

Description

The preparation method of a kind of copper gold platinum composite nano materials and its on detection cysteine Application
Technical field
The present invention relates to test chemical analysis technical fields, and in particular to a kind of preparation side of copper gold platinum composite nano materials Method and its application on detection cysteine.
Background technology
Cysteine plays highly important role, abnormal cysteine content in the physiology of people and pathologic process It may give rise to diseases.Therefore, the quantitative detection of cysteine is meaningful.And it is currently used for cysteine detection Method includes mainly enzyme parameters, electrochemical process, fluorescence method etc., and the sample preparation of these methods is cumbersome, and detection process is complicated.
Application number 2015101805572, it is entitled a kind of based on graphene oxide-Platinum Nanoparticles composite material half Guang ammonia of measurement The method of acid, it is characterized in that using graphene oxide-Platinum Nanoparticles Simulation of Composite peroxidase activity, catalyzing hydrogen peroxide The process color of 3,3',5,5'-tetramethylbenzidine hydrochloride is aoxidized, and cysteine can inhibit the color development system, to Detection for cysteine.Semicystinol concentration is within the scope of 25-5000 nmol/l, the absorbance of color product and half Guang Propylhomoserin log concentration is linearly related(r=0.998), detect and be limited to 1.2 nmol/l.The method can be used for cysteine capsule content It measures.
Graphene oxide is laminated structure, and size is generally other in the micron-scale, as catalyst, uniformity and monodisperse Property is not good enough.In addition, the preparation process of graphene oxide is more complicated, to equipment requirement height.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of preparation sides of copper gold platinum composite nano materials Method and its application on detection cysteine, the preparation method is simple, strong in the upper operability of cysteine detection, speed Soon, it is convenient for promoting.
A kind of preparation method of copper gold platinum composite nano materials, includes the following steps:
Step 1, the preparation of Cu@Au
20-80 μ l, 0.1 M CuSO are added into 5 ml water4With the aqueous solution of 20-80 μ l, 0.1M sodium citrates, then it is added NaBH fresh 0.5-1.5ml420-80 μ l, 0.1M HAuCl is added after solution is in light yellow in solution4Aqueous solution, stirring After 15-25 minutes, it is placed at 12-16 DEG C and stores 24 hours to get copper/gold composite nano materials Cu@AuNPs, be put into refrigerator It is spare to be protected from light refrigeration;Sodium borohydride used in the step needs fresh, prepares the time and grows, and sodium borohydride can be anti-with water It answers, acquired solution cannot participate in reaction at this stage, influence experimental result.
Step 2, the preparation of Cu@Au/Pt
The Cu@AuNPs for taking the above-mentioned preparations of 2ml, add to the K of 1.0 mM of 5ml2PtCl6In solution, it is heated to 80 DEG C while stirring Afterwards, then the ascorbic acid of a concentration of 5mM of 5ml is added dropwise, continues stirring and become black to solution to receive to get copper gold platinum is compound Rice material.
It is the fresh NaBH as improved4The preparation method of solution is to take 3.8 mg NaBH4It is dissolved in 4 ml ice In water, stirring is to being completely dissolved to get fresh NaBH4Solution.
Application of the copper gold platinum composite nano materials of above-mentioned preparation on detection cysteine.
It is that the detection range of the application is 0-3mM as improved.
It is that the detection of the application is limited to 6 μM as improved.
Advantageous effect:
Compared with prior art, the preparation method of a kind of copper gold platinum composite nano materials of the present invention and its on detection cysteine Application, it is proposed that a method of utilizing ternary composite metal nano material Visual retrieval cysteine, the preparation side Method is simple, low for equipment requirements, and the copper gold platinum composite nano materials being prepared have peroxidase sample activity, can make TMB (3,3', 5,5'- tetramethyl benzidine) and hydrogen peroxide system are displayed in blue, and the addition of cysteine, can be inhibited this Activity shows as system lighter.According to the variation of system color and the change of ultravioletvisible absorption, half Guang can be detected Propylhomoserin concentration, strong in the upper operability of cysteine detection, speed is fast, convenient for promoting.
Description of the drawings
Fig. 1 is the TMB+H added before and after Cu@Au/Pt2O2System variation diagram,(a)For color change figure;(b)TMB+H2O2 System abosrption spectrogram;
Fig. 2 is that TMB+H is added in the cysteine of various concentration2O2System variation diagram afterwards,(a)For color change figure;(b)It is different dense Abosrption spectrogram under the cysteine system of degree, lines indicate that the concentration of cysteine increases successively from top to bottom;(c)In wave Absorption value at a length of 652nm under the cysteine system of various concentration;
It is that TMB+H is added in different aminoacids at 652nm that Fig. 3, which is in wavelength,2O2The variation of system absorption value afterwards.
Specific implementation mode
The present invention is further described in detail below by specific embodiment.
Embodiment 1
A kind of preparation method of copper gold platinum composite nano materials, includes the following steps:
Step 1, the preparation of Cu@Au
CuSO is added into 5 ml water4(50 μ l, 0.1 M)And sodium citrate(50 μ l, 0.1 M)Aqueous solution, be then added 1 Sodium borohydride solution fresh ml(3.8 mg/4 ml H2O), after 15 minutes, HAuCl is added4Aqueous solution(50 μ l, 0.1M), stir After mixing 15-25 minutes, it is placed at 12-16 DEG C and stores 24 hours to get copper/gold composite nano materials Cu@AuNPs, be put into refrigerator In be protected from light refrigeration it is spare;
Step 2, the preparation of Cu@Au/Pt
The Cu@AuNPs for taking the above-mentioned preparations of 2ml, add to the K of 1.0 mM of 5ml2PtCl6In solution, it is heated to 80 DEG C while stirring Afterwards, then the L-ascorbic acid (ascorbic acid) of a concentration of 5mM of 5ml are added dropwise, continue to stir 30min to get copper gold Platinum composite nano materials.
Peroxidase sample active influence of 2 pH value of embodiment on copper gold platinum composite nano materials
PH ranging from 3.6-5.6 can be seen that from above-mentioned experiment when pH is 3.8, and the activity of peroxidase sample is most strong.
3 H of embodiment2O2Peroxidase sample active influence of the concentration on copper gold platinum composite nano materials
H2O2Concentration be respectively 0,1 mM, 2 mM, 3 mM, 4 mM, 5 mM, 8 mM, 10 mM, 15 mM, 20 mM, 30 mM, 40 mM。
H is can be seen that from above-mentioned experiment2O2A concentration of 20mM, peroxidase sample activity it is most strong.
Peroxidase sample active influence of 4 temperature of embodiment on copper gold platinum composite nano materials
Temperature is respectively 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60,70,80,90 DEG C,
Can be seen that temperature from above-mentioned experiment is 30 DEG C, and the activity of peroxidase sample is most strong.
Peroxidase sample active influence of the 5 TMB concentration of embodiment on copper gold platinum composite nano materials
TMB concentration is respectively 0,0.1 mM, 0.5 mM, 1 mM, 1.5 mM, 3 mM, 5 mM, 8 mM, 10 mM, 20 mM, 30 MM, 50 mM.
It can be seen that from above-mentioned experiment as a concentration of 20mM of TMB, peroxidase sample activity is most strong.
Embodiment 6
The cysteine of 100 μ l various concentrations is added to Cu@Au/Pt+TMB+H2O2In system, Cu@Au/Pt in the system (100μl), TMB(100μl), H2O2(100μl), sodium acetate buffer(100 μ l, 50mM), a period of time is reacted in a water bath Afterwards, the color change of system, such as Fig. 2 are observed(a)It is shown.From Fig. 2(b)In as can be seen that system color with cysteine The increase of concentration, gradually thin out, absorption value is reduced with the raising of semicystinol concentration in abosrption spectrogram.From Fig. 2(c)In As can be seen that detection is limited to 6 μM, detection range 0-3 mM.
According to above-mentioned step, the cysteine of various concentration is changed to the amino acid not of the same race of same concentration, is observed in wave The variation of each system absorption value at a length of 625nm.From Fig. 3 label 1-18 be followed successively by water, cysteine, leucine, tyrosine, Alanine, lysine, methionine, tryptophan, aspartic acid, isoleucine, arginine, threonine, phenylalanine, dried meat ammonia Acid, arginine monohydrochloride, glycine, glutamine, histidine, as can be seen from the figure only cysteine can utmostly press down The peroxidase sample activity of composite nano materials processed, so, which detects cysteine.
The foregoing is only a preferred embodiment of the present invention, protection scope of the present invention is without being limited thereto, it is any ripe Those skilled in the art are known in the technical scope of present disclosure, the letter for the technical solution that can be become apparent to Altered or equivalence replacement are each fallen in protection scope of the present invention.

Claims (5)

1. a kind of preparation method of copper gold platinum composite nano materials, which is characterized in that include the following steps:
Step 1, the preparation of Cu@Au
20-80 μ l, 0.1 M copper-baths and 20-80 μ l, 0.1M sodium citrate solutions are added into 5 mL water, is then added NaBH fresh 0.5-1.5ml420-80 μ l, 0.1M HAuCl is added after solution is in light yellow in solution4Aqueous solution, stirring After 15-25 minutes, it is placed at 12-16 DEG C and stores 24 hours to get copper/gold composite nano materials Cu@AuNPs, be put into refrigerator It is spare to be protected from light refrigeration;
Step 2, the preparation of Cu@Au/Pt
The Cu@AuNPs for taking the above-mentioned preparations of 2ml, add to the K of 1.0 mM of 5ml2PtCl6In solution, it is heated to 80 DEG C while stirring Afterwards, then the ascorbic acid of a concentration of 5mM of 5ml is added dropwise, continues stirring to solution and becomes black to get copper gold platinum composite Nano Material.
2. a kind of preparation method of copper gold platinum composite nano materials according to claim 1, which is characterized in that described fresh NaBH4The preparation method of solution is to take 3.8 mg NaBH4It is dissolved in 4 ml ice water, shakes to being completely dissolved to get fresh NaBH4Solution.
3. application of the copper gold platinum composite nano materials based on claim 1 preparation on detection cysteine.
4. application according to claim 3, which is characterized in that the detection range of the application is 0-3mM.
5. application according to claim 3, which is characterized in that the detection of the application is limited to 6 μM.
CN201810595045.6A 2018-06-11 2018-06-11 Preparation method of copper-gold-platinum composite nano material and application of copper-gold-platinum composite nano material in cysteine detection Active CN108746660B (en)

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CN109781719A (en) * 2019-02-27 2019-05-21 福建医科大学 A kind of kit detecting trypsase and its inhibitor based on platinum cluster
CN113325179A (en) * 2021-04-14 2021-08-31 中国农业科学院烟草研究所(中国烟草总公司青州烟草研究所) Immunochromatographic test strip based on Au @ Pt enzyme and preparation method thereof
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CN113750235A (en) * 2021-10-29 2021-12-07 中国科学院高能物理研究所 Inorganic nano MoSx/gamma-MnS composite material and preparation method and application thereof
CN113750235B (en) * 2021-10-29 2022-06-10 中国科学院高能物理研究所 Inorganic nano MoSx/gamma-MnS composite material and preparation method and application thereof
CN114392773A (en) * 2021-12-30 2022-04-26 中南大学 Cu/Au/Pt-MOFs composite material with enhanced peroxidase activity and preparation method and application thereof

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