CN109030598A - The preparation method of ratio electrochemistry creatinine sensor based on nano-complex modified electrode - Google Patents
The preparation method of ratio electrochemistry creatinine sensor based on nano-complex modified electrode Download PDFInfo
- Publication number
- CN109030598A CN109030598A CN201810741409.7A CN201810741409A CN109030598A CN 109030598 A CN109030598 A CN 109030598A CN 201810741409 A CN201810741409 A CN 201810741409A CN 109030598 A CN109030598 A CN 109030598A
- Authority
- CN
- China
- Prior art keywords
- nano
- complex
- carbon electrode
- nile blue
- dopamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application provides a kind of preparation method of ratio electrochemistry creatinine sensor based on nano-complex modified electrode, wherein, the glass-carbon electrode is modified by nano-complex, which includes or be made of copper nanoparticle, poly-dopamine, redox graphene and Nile blue.The electrode electro Chemical activity height, good biocompatibility, reference area greatly, rate signal strong antijamming capability, the preparation method of the application is easy to operate, at low cost, raw material is easy to get, the detection method of the application is easy flexibly, high sensitivity, strong antijamming capability, high-efficient, accuracy is good, the detection especially suitable for creatinine.
Description
Technical field
The application belongs to nanocomposite and electrochemical sensor interleaving techniques field, and in particular to based on nano combined
The preparation method of the ratio electrochemistry creatinine sensor of object modified electrode.
Background technique
Compared with carbon nanotube and fullerene, graphene oxide less expensive, raw material is also easy to get, and is expected to become super
Nano material is widely used in the numerous areas such as photoelectricity, sensor, electronics, capacitor.The main body of graphene oxide is by carbon original
The stabilization six-membered ring structure that son is constituted, edge can significantly increase containing functional groups such as a large amount of carboxyls, hydroxyl, epoxy groups
The reactivity of graphene oxide.The chemical property of redox graphene is much higher than graphene oxide, intermolecular Van der Waals force
Assemble it easily and reduce stability, therefore carries out effective functional modification to redox graphene to seem especially heavy
It wants.Dopamine hydrochloride has excellent Environmental compatibility, shows in terms of chemical method redox graphene environmental-friendly
The advantages of, three-dimensional structure is presented in poly-dopamine/redox graphene compound of preparation, and good conductivity, surface area is big to wait spies
Point can be used as a kind of novel functionalized nano material, receive significant attention in fields such as optics, electrochemistry, catalysis, batteries.
Summary of the invention
The application's is designed to provide a kind of ratio electrochemistry creatinine sensor based on nano-complex modified electrode
Preparation method, active height of the electrode electro Chemical, good biocompatibility, reference area greatly, rate signal strong antijamming capability,
The preparation method is easy to operate, at low cost, raw material is easy to get, the detection method easy flexible, high sensitivity, anti-interference ability
By force, high-efficient, accuracy is good, the detection especially suitable for creatinine.
The application is achieved through the following technical solutions:
Firstly, the application provides a kind of glass-carbon electrode, the glass-carbon electrode is modified by nano-complex, described nano combined
Include in the composition of object or is made of copper nano particles, poly-dopamine, redox graphene and Nile blue；
Further, the nano-complex is copper nano particles/poly-dopamine/redox graphene/Nile blue four
Component nano-complex；
Further, the nano-complex by nano-complex B with copper nanoparticle is compound obtains；
Further, the copper nanoparticle is electrodeposited in in-situ preparation on nano-complex B by a step；
Further, the nano-complex B is obtained by nano-complex A and Nile blue are compound；
Further, in one or more embodiments of the application, the nano-complex repairs glass-carbon electrode
Decorations are accomplished by the following way: in bare glassy carbon electrode after drop coating nano-complex B, the in-situ preparation copper on nano-complex B
Nanoparticle is up to copper nanoparticle/four component nano-complex of poly-dopamine/redox graphene/Nile blue and its glass of modification
Carbon electrode.
Further, in more specifically embodiment, the nano-complex to the modification of glass-carbon electrode by with
Under type is realized: being taken bare glassy carbon electrode, is carried out polishing grinding processing to its surface, drop coating nano-complex B is done at room temperature
It is dry, it is then added copper nitrate solution in nitrate solution, carries out cyclic voltammetry scan to get copper nanoparticle/poly-dopamine/also
The glass-carbon electrode of former four component nano-complex of graphene oxide/Nile blue modification.
Further, on glass-carbon electrode drop coating nano-complex B drop coating amount be 2-10 μ L, preferably 4-6 μ L, preferably
For 5 μ L；
Further, the nitrate solution pH is 3-6, preferably 4-5, preferably 4.8；
Further, the concentration of the copper nitrate solution is 1-100mM, preferably 5-50mM, more preferably 20mM；
Further, the cyclic voltammetry scan circle number is 5-25 circle, preferably 14-20 circle, most preferably 18 circles.
Further, in one or more embodiments of the invention, the nano-complex A is obtained as follows
: graphene oxide is prepared using Hummer ' s method in graphene；The graphene oxide and Dopamine hydrochloride are weighed, is added
Enter into Tris-HCl buffer, is stirred to react poly-dopamine/redox graphene nanometer is prepared at a certain temperature
Compound (i.e. nano-complex A)；
Further, the dosage (mass concentration) of the graphene oxide and Dopamine hydrochloride is than being 1:0.1-10, preferably
For 1:0.5-5, preferably 1:0.8；
Further, the concentration of the Tris-HCl buffer is 1-10mM, preferably 5-10mM, more preferably 10mM；
Further, the pH of the Tris-HCl buffer is 4-8, preferably 5-6.5, more preferably 6.5；
Further, the reaction temperature is 50-150 DEG C, preferably 60-90 DEG C, more preferably 80 DEG C；
Further, the reaction time be 2-48h, preferably 6-24h, more preferably for 24 hours.
Further, in one or more embodiments of the application, the nano-complex B is obtained as follows
: nano-complex A and Nile blue are added in weighing bottle together, is ultrasonically treated and poly-dopamine/reduction-oxidation graphite is made
Alkene/Nile blue nano-complex (i.e. nano-complex B)；
Further, the mass concentration ratio of the nano-complex A and Nile blue is 1:0.2-5, preferably 1:0.25-2；
Preferably 1:0.25-1 or 1:1-2, more preferably 1:0.5-1；Most preferably 1:0.5；
Further, the ultrasonic power is 120-200W, preferably 140-180W, more preferably 160W；
Further, the ultrasonic time is 1-10h, preferably 0.5-6h, preferably 2h.
Secondly, the described method comprises the following steps this application provides a kind of method for preparing above-mentioned glass-carbon electrode:
(1) graphene oxide is prepared using Hummer ' s method in graphene；
(2) graphene oxide and Dopamine hydrochloride obtained in step (1) are weighed, is added in Tris-HCl buffer,
It is stirred to react at a certain temperature and poly-dopamine/redox graphene nano-complex is prepared, hereinafter referred to as nanometer is multiple
Close object A；
(3) nano-complex A obtained in step (2) and Nile blue are added in weighing bottle together, ultrasonic treatment system
Obtain poly-dopamine/redox graphene/Nile blue nano-complex, hereinafter referred to as nano-complex B；
(4) bare glassy carbon electrode is taken, polishing grinding processing is carried out to its surface, the nanometer that then drop coating step (3) obtains is multiple
Object B is closed, is dried at room temperature for, copper nitrate solution is then added in nitrate solution, cyclic voltammetry scan is carried out and is received to get copper
The grain of rice/four component nano-complex of poly-dopamine/redox graphene/Nile blue modification glass-carbon electrode.
Further, in step (2), the dosage (mass concentration) of the graphene oxide and Dopamine hydrochloride is than being 1:
0.1-10, preferably 1:0.5-5, preferably 1:0.8；
Further, the concentration of the Tris-HCl buffer is 1-10mM, preferably 5-10mM, more preferably 10mM；
Further, in step (2), the pH of the Tris-HCl buffer is 4-8, preferably 5-6.5, more preferably
6.5；
Further, in step (2), the reaction temperature is 50-150 DEG C, preferably 60-90 DEG C, more preferably 80
℃；
Further, in step (2), the reaction time be 2-48h, preferably 6-24h, more preferably for 24 hours.
Further, in step (3), the mass concentration ratio of the nano-complex A and Nile blue is 1:0.2-5, excellent
It is selected as 1:0.25-2；Preferably 1:0.25-1 or 1:1-2, more preferably 1:0.5-1；Most preferably 1:0.5.
Further, in step (3), the ultrasonic power be 120-200W, preferably 140-180W, more preferably
160W；
Further, in step (3), the ultrasonic time is 1-10h, preferably 0.5-6h, preferably 2h.
Further, in step (4), the drop coating nano-complex B on glass-carbon electrode, drop coating amount is 2-10 μ L, preferably
For 4-6 μ L, preferably 5 μ L；
Further, in step (4), the nitrate solution pH is 3-6, preferably 4-5, preferably 4.8；
Further, in step (4), the concentration of the copper nitrate solution is 1-100mM, preferably 5-50mM, more excellent
It is selected as 20mM；
Further, in step (4), the cyclic voltammetry scan circle number is 5-25 circle, and preferably 14-20 circle is optimal
It is selected as 18 circles.
Again, this application provides a kind of electrochemical sensor, the sensor include glass-carbon electrode as described above and/
Or using glass-carbon electrode as described above as sensing interface；The sensor is preferably ratio electrochemical sensor.
Again, present invention also provides a kind of method for detecting creatinine, the method uses glass-carbon electrode as described above
Or use (being based on) electrochemical sensor as described above；And/or further, the method is with above-mentioned glass-carbon electrode
Sensing interface measures the oxidation peak current volume efficiency of the creatinine-copper ion complex and Nile blue under different creatine concentrations, intends
Close the linear relationship of different rate values with corresponding creatine concentration.
Further, the creatinine linear concentration range is 0.1-100mM, preferably 1-100mM, more preferably 2-
80mM；
Further, the creatinine detection is limited to 0.01-0.1 μM, preferably 0.012-0.06 μM, most preferably 0.02 μ
M。
In one or more embodiments, it is described detection creatinine method the following steps are included:
(1) graphene oxide is prepared using Hummer ' s method in graphene；
(2) graphene oxide and Dopamine hydrochloride obtained in step (1) are weighed, is added in Tris-HCl buffer,
It is stirred to react at a certain temperature and poly-dopamine/redox graphene nano-complex is prepared, hereinafter referred to as nanometer is multiple
Close object A；
(3) nano-complex A obtained in step (2) and Nile blue are added in weighing bottle together, ultrasonic treatment system
Obtain poly-dopamine/redox graphene/Nile blue nano-complex, hereinafter referred to as nano-complex B；
(4) bare glassy carbon electrode is taken, polishing grinding processing is carried out to its surface, the nanometer that then drop coating step (3) obtains is multiple
Object B is closed, is dried at room temperature for, copper nitrate solution then is added in the electrolytic cell using Tris-HCl buffer as electrolyte, into
Row cyclic voltammetry scan is repaired to get copper nanoparticle/four component nano-complex of poly-dopamine/redox graphene/Nile blue
The glass-carbon electrode of decorations；
(5) glass-carbon electrode obtained using step (4) measures creatinine-copper ion under different creatine concentrations as sensing interface
The oxidation peak current volume efficiency of complex and Nile blue, is fitted the linear relationship of different rate values with corresponding creatine concentration.
Further, in step (2), the dosage ratio of the graphene oxide and Dopamine hydrochloride is 1:0.1-10,
Preferably 1:0.5-5, preferably 1:0.8；
Further, the concentration of the Tris-HCl buffer is 1-10mM, preferably 5-10mM, more preferably 10mM；
Further, in step (2), the pH of the Tris-HCl buffer is 4-8, preferably 5-6.5, more preferably
6.5；
Further, in step (2), the reaction temperature is 50-150 DEG C, preferably 60-90 DEG C, more preferably 80
℃；
Further, in step (2), the reaction time be 2-48h, preferably 6-24h, more preferably for 24 hours；
Further, in step (3), the mass concentration ratio of the nano-complex A and Nile blue is 1:0.2-5, excellent
It is selected as 1:0.25-2；Preferably 1:0.25-1 or 1:1-2, more preferably 1:0.5-1；Most preferably 1:0.5；
Further, in step (3), the ultrasonic power be 120-200W, preferably 140-180W, more preferably
160W；
Further, in step (3), the ultrasonic time is 1-10h, preferably 0.5-6h, preferably 2h；
Further, in step (4), the drop coating nano-complex B on glass-carbon electrode, drop coating amount is 2-10 μ L, preferably
For 4-6 μ L, preferably 5 μ L；
Further, in step (4), the nitrate solution pH is 3-6, preferably 4-5, preferably 4.8；
Further, in step (4), the concentration of the copper nitrate solution is 1-100mM, preferably 5-50mM, more excellent
It is selected as 20mM；
Further, in step (4), the cyclic voltammetry scan circle number is 5-25 circle, and preferably 14-20 circle is optimal
It is selected as 18 circles；
Further, in step (5), the creatinine linear concentration range be 0.1-100mM, preferably 1-100mM, more
Preferably 2-80mM；
Further, in step (5), the creatinine detection is limited to 0.01-0.1 μM, preferably 0.012-0.06 μM, most
Preferably 0.02 μM.
It is substrate that the application, which selects graphene oxide, and Dopamine hydrochloride is reducing agent, is generated in Tris-HCl buffer
Poly-dopamine/redox graphene compound (nano-complex A), through ultrasound by this compound and Nile blue by π-π and
Electrostatic interaction combines, and forms poly-dopamine/redox graphene/Nile blue compound (nano-complex B).Nitre is added
Sour copper solution carries out cyclic voltammetry scan, a step electro-deposition in-situ preparation copper nanoparticle, obtained copper nanoparticle/poly-dopamine/go back
Former graphene oxide/Nile blue compound and its glass-carbon electrode of modification.It measures under different creatine concentrations, creatinine-copper ion is matched
The oxidation peak current volume efficiency for closing object and Nile blue, is fitted the linear relationship of different rate values with corresponding creatine concentration.
Compared with prior art, the glass-carbon electrode electro-chemical activity height, good biocompatibility of the application, large specific surface area,
Rate signal strong antijamming capability, the preparation method of the glass-carbon electrode of the application is easy to operate, at low cost, raw material is easy to get, this Shen
Detection method please is easy flexibly, high sensitivity, strong antijamming capability, high-efficient, accuracy is good, the inspection especially suitable for creatinine
It surveys.
Detailed description of the invention
Hereinafter, the embodiment that the application is described in detail in conjunction with attached drawing, in which:
Fig. 1 is copper nanoparticle/four component nano-complex of poly-dopamine/redox graphene/Nile blue of the application
Structure and its preparation process schematic diagram；
Fig. 2 is the line chart in the application embodiment, wherein (a) is under different creatine concentrations, in the application embodiment
The corresponding square wave volt-ampere curve of ratio electrochemical sensor；(b) under different creatine concentrations, corresponding creatinine-copper ion cooperates
The oxidation peak current volume efficiency of object and Nile blue, the different rate values of fitting and the linear relationship of corresponding creatine concentration.
Specific embodiment
Combined with specific embodiments below, the application is further described.It should be understood that these embodiments are merely to illustrate the application
Rather than limitation scope of the present application.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part or according to the normal condition proposed by manufacturer.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art
Justice is identical.In addition, any method similar to or equal to what is recorded and material all can be applied in the application method.Wen Zhong
The preferred implement methods and materials are for illustrative purposes only.
Embodiment 1
(1) graphene oxide is prepared using Hummer ' s method in graphene；
(2) graphene oxide and Dopamine hydrochloride that step (1) obtains are weighed, wherein graphene oxide and Dopamine hydrochloride
Dosage (mass concentration) than be 1:0.1, be added in the Tris-HCl buffer of 1mM, wherein pH be 4.5, stirred at 60 DEG C
Mix reaction, reaction time 4h.Prepare poly-dopamine/redox graphene nano-complex A；
(3) nano-complex A and Nile blue that step (2) obtains are added to title with the mass concentration proportion of 1:2 together
In measuring bottle, poly-dopamine/redox graphene/Nile blue nano-complex B is made by 120W ultrasonic treatment 2h；
(4) bare glassy carbon electrode is taken, polishing grinding processing is carried out to its surface, then the nanometer of 2 μ L step (3) of drop coating preparation
Compound B, is dried at room temperature for, and then in the nitrate solution (pH 4.5) containing 10mM copper nitrate, carries out cyclic voltammetric
10 circle of scanning, realizes a step electro-deposition in-situ preparation copper nanoparticle, obtains copper nanoparticle/poly-dopamine/reduction-oxidation graphite
Four component nano-complex of alkene/Nile blue and its glass-carbon electrode of modification；
(5) the copper nanoparticle/four component nanometer of poly-dopamine/redox graphene/Nile blue obtained with step (4) is multiple
The glass-carbon electrode for closing object modification is sensing interface, is measured under different creatine concentrations, creatinine-copper ion complex and Nile blue oxygen
Change peak current volume efficiency, is fitted the linear relationship of different rate values with corresponding creatine concentration, wherein the linear concentration model of creatinine
Enclosing is 1~100 μM, and creatinine detection is limited to 0.1 μM.
Embodiment 2
(1) graphene oxide is prepared using Hummer ' s method in graphene；
(2) graphene oxide and Dopamine hydrochloride that step (1) obtains, the use of graphene oxide and Dopamine hydrochloride are weighed
(mass concentration) is measured than being 1:0.5, pH=5 in the Tris-HCl buffer of 2mM is added to, 6h preparation is stirred to react at 80 DEG C
Poly-dopamine/redox graphene nano-complex A；
(3) nano-complex A and Nile blue that step (2) obtains are added to title with the mass concentration proportion of 1:1 together
In measuring bottle, poly-dopamine/redox graphene/Nile blue nano-complex B is made by 150W ultrasonic treatment 4h；
(4) bare glassy carbon electrode is taken, polishing grinding processing is carried out to its surface, then the nanometer of 4 μ L step (3) of drop coating preparation
Compound B, is dried at room temperature for, and then in the nitrate solution (pH 5) containing 20mM copper nitrate, carries out cyclic voltammetric and sweeps
Retouch 15 circles, realize a step electro-deposition in-situ preparation copper nanoparticle, obtain copper nanoparticle/poly-dopamine/redox graphene/
Four component nano-complex of Nile blue and its glass-carbon electrode of modification；
(5) the copper nanoparticle/four component nanometer of poly-dopamine/redox graphene/Nile blue obtained with step (4) is multiple
The glass-carbon electrode for closing object modification is sensing interface, is measured under different creatine concentrations, creatinine-copper ion complex and Nile blue oxygen
Change peak current volume efficiency, be fitted the linear relationship of different rate values with corresponding creatine concentration, develops into and can be used for creatinine inspection
The ratio electrochemical sensor of survey, the linear concentration range of creatinine are 0.1~50 μM, and creatinine detection is limited to 0.05 μM.
Embodiment 3
(1) graphene oxide is prepared using Hummer ' s method in graphene；
(2) it weighs step (1) and obtains graphene oxide and Dopamine hydrochloride, wherein graphene oxide and Dopamine hydrochloride
Dosage (mass concentration) is added in the Tris-HCl buffer of 5mM, pH=5.5 than being 1:1, is stirred to react 8h at 100 DEG C
Prepare poly-dopamine/redox graphene nano-complex A；
(3) nano-complex A and Nile blue that step (2) obtains are added to title with the mass concentration proportion of 2:1 together
In measuring bottle, poly-dopamine/redox graphene/Nile blue nano-complex B is made by 180W ultrasonic treatment 6h；
(4) bare glassy carbon electrode is taken, polishing grinding processing is carried out to its surface, then the nanometer of 6 μ L step (3) of drop coating preparation
Compound B, is dried at room temperature for, and then in the nitrate solution (pH 5) containing 50mM copper nitrate, carries out cyclic voltammetric and sweeps
Retouch 20 circles, realize a step electro-deposition in-situ preparation copper nanoparticle, obtain copper nanoparticle/poly-dopamine/redox graphene/
Four component nano-complex of Nile blue and its glass-carbon electrode of modification；
(5) the copper nanoparticle/four component nanometer of poly-dopamine/redox graphene/Nile blue obtained with step (4) is multiple
The glass-carbon electrode for closing object modification is sensing interface, is measured under different creatine concentrations, creatinine-copper ion complex and Nile blue oxygen
Change peak current volume efficiency, be fitted the linear relationship of different rate values with corresponding creatine concentration, develops into and can be used for creatinine inspection
The ratio electrochemical sensor of survey, the linear concentration range of creatinine are 0.1~100 μM, and creatinine detection is limited to 0.02 μM.
Embodiment 4
(1) graphene oxide is prepared using Hummer ' s method in graphene；
(2) step (1) graphene oxide and Dopamine hydrochloride are weighed, wherein the dosage of graphene oxide and Dopamine hydrochloride
(mass concentration) is added in the Tris-HCl buffer of 10mM, pH 6 than being 1:1.5,10h system is stirred to react at 120 DEG C
The nano-complex A of standby poly-dopamine/redox graphene；
(3) nano-complex A and Nile blue that step (2) obtains are added to title with the mass concentration proportion of 4:1 together
In measuring bottle, poly-dopamine/redox graphene/Nile blue nano-complex B is made by 200W ultrasonic treatment 8h；
(4) naked glass carbon is taken, polishing grinding processing is carried out to its electrode surface, then the nanometer of 8 μ L step (3) of drop coating preparation
Compound B, is dried at room temperature for, and then in the nitrate solution (pH 6) containing 80mM copper nitrate, carries out cyclic voltammetric and sweeps
Retouch 25 circles, realize a step electro-deposition in-situ preparation copper nanoparticle, obtain copper nanoparticle/poly-dopamine/redox graphene/
Four component nano-complex of Nile blue and its glass-carbon electrode of modification；
(5) to obtain copper nanoparticle/poly-dopamine/four component of redox graphene/Nile blue with step (4) nano combined
The glass-carbon electrode of object modification is sensing interface, is measured under different creatine concentrations, the oxidation of creatinine-copper ion complex and Nile blue
Peak current volume efficiency is fitted the linear relationship of different rate values with corresponding creatine concentration, develops into and can be used for creatinine detection
Ratio electrochemical sensor, the linear concentration range of creatinine is 0.1~100 μM, and creatinine detection is limited to 0.01 μM.
Embodiment 5
(1) graphene oxide is prepared using Hummer ' s method in graphene；
(2) step (1) graphene oxide and Dopamine hydrochloride are weighed, wherein the dosage of graphene oxide and Dopamine hydrochloride
(mass concentration) is added in the Tris-HCl buffer of 10mM, pH 6.5, is stirred to react for 24 hours at 80 DEG C than being 1:0.8
Prepare poly-dopamine/redox graphene nano-complex A；
(3) nano-complex A and Nile blue that step (2) obtains are added to together with the mass concentration proportion of 1:0.5
In weighing bottle, poly-dopamine/redox graphene/Nile blue nano-complex B is made by 160W ultrasonic treatment 2h；
(4) naked glass carbon is taken, polishing grinding processing is carried out to its electrode surface, then the nanometer of 5 μ L step (3) of drop coating preparation
Compound B, is dried at room temperature for, and then in the nitrate solution (pH 4.8) containing 20mM copper nitrate, carries out cyclic voltammetric
18 circle of scanning, realizes a step electro-deposition in-situ preparation copper nanoparticle, obtains copper nanoparticle/poly-dopamine/reduction-oxidation graphite
Four component nano-complex of alkene/Nile blue and its glass-carbon electrode (Fig. 1) of modification；
(5) to obtain copper nanoparticle/poly-dopamine/four component of redox graphene/Nile blue with step (4) nano combined
The glass-carbon electrode of object modification is sensing interface, is measured under different creatine concentrations, the oxidation of creatinine-copper ion complex and Nile blue
Peak current volume efficiency is fitted linear relationship (Fig. 2) of the different rate values with corresponding creatine concentration, develops into and can be used for creatinine
The ratio electrochemical sensor of detection, the linear concentration range of creatinine are 2-80 μM, and creatinine detection is limited to 0.02 μM.
Claims (10)
1. a kind of glass-carbon electrode, is modified by nano-complex, the nano-complex includes or by copper nano particles, poly- DOPA
Amine, redox graphene and Nile blue are combined；
Further, the nano-complex is copper nano particles/poly-dopamine/four component of redox graphene/Nile blue
Nano-complex.
2. a kind of method for preparing glass-carbon electrode described in claim 1, which is characterized in that the described method comprises the following steps:
(1) graphene oxide is prepared using Hummer ' s method in graphene；
(2) graphene oxide and Dopamine hydrochloride obtained in step (1) are weighed, is added in Tris-HCl buffer, one
Determine to be stirred to react at temperature and poly-dopamine/redox graphene nano-complex, hereinafter referred to as nano-complex is prepared
A；
(3) nano-complex A obtained in step (2) and Nile blue are added in weighing bottle together, are ultrasonically treated and are made poly-
Dopamine/redox graphene/Nile blue nano-complex, hereinafter referred to as nano-complex B；
(4) bare glassy carbon electrode is taken, polishing grinding processing, the nano-complex that then drop coating step (3) obtains are carried out to its surface
B is dried at room temperature for, and copper nitrate solution is then added in nitrate solution, carries out cyclic voltammetry scan to get copper nanometer
The glass-carbon electrode of four component nano-complex of grain/poly-dopamine/redox graphene/Nile blue modification.
3. according to the method described in claim 2, it is characterized in that, in step (2), the graphene oxide and hydrochloric acid DOPA
Amount ratio of the amine in terms of mass concentration is 1:0.1-10, preferably 1:0.5-5, preferably 1:0.8；
Further, the concentration of the Tris-HCl buffer is 1-10mM, preferably 5-10mM, more preferably 10mM；
Further, in step (2), the pH of the Tris-HCl buffer is 4-8, preferably 5-6.5, more preferably 6.5；
Further, in step (2), the reaction temperature is 50-150 DEG C, preferably 60-90 DEG C, more preferably 80 DEG C；
Further, in step (2), the reaction time be 2-48h, preferably 6-24h, more preferably for 24 hours.
4. according to the method described in claim 2, it is characterized in that, in step (3), the nano-complex A and Nile blue
Mass concentration ratio be 1:0.2-5, preferably 1:0.25-2；Preferably 1:0.25-1 or 1:1-2, more preferably 1:0.5-1；Most
Preferably 1:0.5；
Further, in step (3), the ultrasonic power is 120-200W, preferably 140-180W, more preferably 160W；
Further, in step (3), the ultrasonic time is 1-10h, preferably 0.5-6h, preferably 2h.
5. according to the method described in claim 2, it is characterized in that, drop coating is nano combined on glass-carbon electrode in step (4)
Object B, drop coating amount are 2-10 μ L, preferably 4-6 μ L, preferably 5 μ L；
Further, in step (4), the nitrate solution pH is 3-6, preferably 4-5, preferably 4.8；
Further, in step (4), the concentration of the copper nitrate solution is 1-100mM, preferably 5-50mM, more preferably
20mM；
Further, in step (4), the cyclic voltammetry scan circle number is 5-25 circle, and preferably 14-20 is enclosed, most preferably
18 circles.
6. a kind of electrochemical sensor, the sensor is comprising glass-carbon electrode described in claim 1 and/or with claim 1
The glass-carbon electrode is sensing interface.
7. a kind of method for detecting creatinine, the method use glass-carbon electrode or as claimed in claim 6 described in claim 1
Electrochemical sensor；And/or further, the method is using glass-carbon electrode described in claim 1 as sensing interface, measurement
The oxidation peak current volume efficiency of creatinine-copper ion complex and Nile blue under different creatine concentrations, is fitted different rate values
With the linear relationship of corresponding creatine concentration.
8. the method according to the description of claim 7 is characterized in that the creatinine linear concentration range is 0.1-100mM, preferably
For 1-100mM, more preferably 2-80mM；
Further, the creatinine detection is limited to 0.01-0.1 μM, preferably 0.012-0.06 μM, most preferably 0.02 μM.
9. method according to claim 7 or 8, which is characterized in that the described method comprises the following steps:
(1) graphene oxide is prepared using Hummer ' s method in graphene；
(2) graphene oxide and Dopamine hydrochloride obtained in step (1) are weighed, is added in Tris-HCl buffer, one
Determine to be stirred to react at temperature and poly-dopamine/redox graphene nano-complex, hereinafter referred to as nano-complex is prepared
A；
(3) nano-complex A obtained in step (2) and Nile blue are added in weighing bottle together, are ultrasonically treated and are made poly-
Dopamine/redox graphene/Nile blue nano-complex, hereinafter referred to as nano-complex B；
(4) bare glassy carbon electrode is taken, polishing grinding processing, the nano-complex that then drop coating step (3) obtains are carried out to its surface
B is dried at room temperature for, and copper nitrate solution then is added in the electrolytic cell using Tris-HCl buffer as electrolyte, is followed
Ring voltammetric scan is to get copper nanoparticle/four component nano-complex of poly-dopamine/redox graphene/Nile blue modification
Glass-carbon electrode；
(5) glass-carbon electrode obtained using step (4) measures creatinine-copper ion cooperation under different creatine concentrations as sensing interface
The oxidation peak current volume efficiency of object and Nile blue, is fitted the linear relationship of different rate values with corresponding creatine concentration.
10. according to the method described in claim 9, it is characterized in that, the graphene oxide and hydrochloric acid are more in step (2)
The dosage ratio of bar amine is 1:0.1-10, preferably 1:0.5-5, preferably 1:0.8；
Further, the concentration of the Tris-HCl buffer is 1-10mM, preferably 5-10mM, more preferably 10mM；
Further, in step (2), the pH of the Tris-HCl buffer is 4-8, preferably 5-6.5, more preferably 6.5；
Further, in step (2), the reaction temperature is 50-150 DEG C, preferably 60-90 DEG C, more preferably 80 DEG C；
Further, in step (2), the reaction time be 2-48h, preferably 6-24h, more preferably for 24 hours；
Further, in step (3), the mass concentration ratio of the nano-complex A and Nile blue is 1:0.2-5, preferably
1:0.25-2；Preferably 1:0.25-1 or 1:1-2, more preferably 1:0.5-1；Most preferably 1:0.5；
Further, in step (3), the ultrasonic power is 120-200W, preferably 140-180W, more preferably 160W；
Further, in step (3), the ultrasonic time is 1-10h, preferably 0.5-6h, preferably 2h；
Further, in step (4), the drop coating nano-complex B on glass-carbon electrode, drop coating amount is 2-10 μ L, preferably 4-6
μ L, preferably 5 μ L；
Further, in step (4), the nitrate solution pH is 3-6, preferably 4-5, preferably 4.8；
Further, in step (4), the concentration of the copper nitrate solution is 1-100mM, preferably 5-50mM, more preferably
20mM；
Further, in step (4), the cyclic voltammetry scan circle number is 5-25 circle, and preferably 14-20 is enclosed, most preferably
18 circles；
Further, in step (5), the creatinine linear concentration range be 0.1-100mM, preferably 1-100mM, more preferably
For 2-80mM；
Further, in step (5), the creatinine detection is limited to 0.01-0.1 μM, preferably 0.012-0.06 μM, most preferably
It is 0.02 μM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810741409.7A CN109030598B (en) | 2018-07-06 | 2018-07-06 | Method for detecting creatinine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810741409.7A CN109030598B (en) | 2018-07-06 | 2018-07-06 | Method for detecting creatinine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109030598A true CN109030598A (en) | 2018-12-18 |
| CN109030598B CN109030598B (en) | 2020-09-04 |
Family
ID=64640852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810741409.7A Active CN109030598B (en) | 2018-07-06 | 2018-07-06 | Method for detecting creatinine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109030598B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117288820A (en) * | 2023-09-26 | 2023-12-26 | 天津大学 | Three-way electrochemical sensing system and method based on Internet of things communication |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104634842A (en) * | 2015-02-13 | 2015-05-20 | 西安石油大学 | Method for preparing electrode modified by copper/graphene nanocomposite and application of modified electrode |
| CN107153089A (en) * | 2017-05-10 | 2017-09-12 | 青岛大学 | A kind of preparation method of dendroid nano-complex Doxorubicin electrochemical sensor |
| CN107860805A (en) * | 2017-11-03 | 2018-03-30 | 青岛大学 | A kind of preparation method of ratio electrochemistry dopamine aptamer sensor |
-
2018
- 2018-07-06 CN CN201810741409.7A patent/CN109030598B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104634842A (en) * | 2015-02-13 | 2015-05-20 | 西安石油大学 | Method for preparing electrode modified by copper/graphene nanocomposite and application of modified electrode |
| CN107153089A (en) * | 2017-05-10 | 2017-09-12 | 青岛大学 | A kind of preparation method of dendroid nano-complex Doxorubicin electrochemical sensor |
| CN107860805A (en) * | 2017-11-03 | 2018-03-30 | 青岛大学 | A kind of preparation method of ratio electrochemistry dopamine aptamer sensor |
Non-Patent Citations (2)
| Title |
|---|
| HUI JIN ET AL.: "Reduced graphene oxide/nile blue/gold nanoparticles complex modifiedglassy carbon electrode used as a sensitive and label-free aptasensor for ratiometric electrochemical sensing of dopamine", 《ANALYTICA CHIMICA ACTA》 * |
| YANLAN LIU ET AL.: "Polydopamine and Its Derivative Materials: Synthesis and Promising Applications in Energy, Environmental, and Biomedical Fields", 《CHEM. REV.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117288820A (en) * | 2023-09-26 | 2023-12-26 | 天津大学 | Three-way electrochemical sensing system and method based on Internet of things communication |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109030598B (en) | 2020-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Peng et al. | A novel electrochemical sensor of tryptophan based on silver nanoparticles/metal–organic framework composite modified glassy carbon electrode | |
| CN108445057B (en) | Preparation and analysis method of electrochemical sensor for detecting heavy metal ions | |
| Lu et al. | Ni-MOF nanosheet arrays: efficient non-noble-metal electrocatalysts for non-enzymatic monosaccharide sensing | |
| Li et al. | Synthesis of a manganese dioxide nanorod-anchored graphene oxide composite for highly sensitive electrochemical sensing of dopamine | |
| CN103278541B (en) | Electrochemical biosensor for detecting bisphenol-A, and preparation method and application thereof | |
| Salimi et al. | Carbon Nanotubes‐Ionic Liquid and Chloropromazine Modified Electrode for Determination of NADH and Fabrication of Ethanol Biosensor | |
| CN105954336B (en) | A kind of no enzyme superoxide anion electrochemical sensor and its preparation method and application | |
| Zhang et al. | A novel nonenzymatic glucose sensor based on magnetic copper ferrite immobilized on multiwalled carbon nanotubes | |
| Zhang et al. | Synthesis of Au nanoparticles dispersed on halloysite nanotubes–reduced graphene oxide nanosheets and their application for electrochemical sensing of nitrites | |
| CN108732216A (en) | The application of heavy metal hexavalent chromium in a kind of electrochemical reduction oxidation graphene modified electrode and its detection water | |
| Li et al. | Direct electrochemistry of hemoglobin immobilized in CuO nanowire bundles | |
| CN106442667B (en) | A kind of method of the persimmon tannin@graphene@Pt-Pd without enzyme sensor detection blood glucose | |
| CN105606684B (en) | A kind of graphene based on protein-single-walled carbon nanotube-nano-Au composite preparation method and applications | |
| Rezaei et al. | Electrochemical determination of papaverine on Mg-Al layered double hydroxide/graphene oxide and CNT modified carbon paste electrode | |
| Hamidi et al. | Fabrication of bulk-modified carbon paste electrode containing α-PW12O403− polyanion supported on modified silica gel: Preparation, electrochemistry and electrocatalysis | |
| CN109187678A (en) | Utilize the nitrite detection device of nanogold graphene modified electrochemical method | |
| CN106248769A (en) | The method of hydroquinone concentration in detection solution | |
| Li et al. | 3D pothole-rich hierarchical carbon framework-encapsulated Ni nanoparticles for highly selective nonenzymatic cysteine detection | |
| CN108845007A (en) | A kind of platinum/graphen paper nanometer combined electrode material and preparation method thereof for detecting hydrogen peroxide | |
| Yang et al. | Electrochemical sensor based on MWCNTs/AuNPs/GCE for sensitive determination of Sudan I content in food samples | |
| CN110361431A (en) | A kind of combination electrode and preparation method thereof and method for ammonia nitrogen detection | |
| CN109030598A (en) | The preparation method of ratio electrochemistry creatinine sensor based on nano-complex modified electrode | |
| Hassanzadeh et al. | Selective electrochemical sensing of dopamine and ascorbic acid using carbon paste electrode modified with cobalt Schiff Base complex and a surfactant | |
| Zhang et al. | Facile and controllable synthesis of Prussian blue nanocubes on TiO 2–graphene composite nanosheets for nonenzymatic detection of hydrogen peroxide | |
| Shi et al. | Synthesis of a novel hedgehog-shaped Bi 2 S 3 nanostructure for a sensitive electrochemical glucose biosensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 266061 No. 7 East Hongkong Road, Laoshan District, Shandong, Qingdao Patentee after: QINGDAO University Address before: 266061 No. 7 East Hongkong Road, Shandong, Qingdao Patentee before: QINGDAO University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220914 Address after: Room 202, Ma Technology Enterprise Accelerator, Hedong Road, Shangma Street, Chengyang District, Qingdao City, Shandong Province, 266108 Patentee after: Longke Biology (Qingdao) Co.,Ltd. Address before: 266061 Hongkong East Road, Laoshan District, Qingdao, Shandong Province, No. 7 Patentee before: QINGDAO University |