CN103913496A - Preparation method and application of modified glassy carbon electrode - Google Patents
Preparation method and application of modified glassy carbon electrode Download PDFInfo
- Publication number
- CN103913496A CN103913496A CN201410072153.7A CN201410072153A CN103913496A CN 103913496 A CN103913496 A CN 103913496A CN 201410072153 A CN201410072153 A CN 201410072153A CN 103913496 A CN103913496 A CN 103913496A
- Authority
- CN
- China
- Prior art keywords
- carbon electrode
- bpy
- glassy carbon
- electrode
- modified glassy
- 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
Abstract
The invention discloses a preparation method for a Ru(bpy)3<2+>-gold nanoparticle-DNA-ferrocene functionalized graphene modified glassy carbon electrode. The method comprises the following concrete steps: polishing of a glassy carbon electrode; coating of Ru(bpy)3<2+> to prepare a Ru(bpy)3<2+> modified glassy carbon electrode; coating of gold nanoparticles to prepare a Ru(bpy)3<2+>-gold nanoparticle modified glassy carbon electrode; coating of single-stranded DNA to prepare a Ru(bpy)3<2+>-gold nanoparticle-DNA modified glassy carbon electrode, wherein the sequence of the single-stranded DNA is rich in T bases, a stable double-stranded DNA structure can be formed after bonding with Hg2+, and the 5' end of the sequence of the single-stranded DNA is connected with an SH-(CH2)6 group; and coating pf ferrocene functionalized graphene so as to prepare the Ru(bpy)3<2+>-gold nanoparticle-DNA-ferrocene functionalized graphene modified glassy carbon electrode. The modified glassy carbon electrode prepared in the invention can be used for detecting the content of mercury ions in a water sample and has good electrochemiluminescence performance, excellent stability and reproducibility and high sensitivity; and operation of the method is easy and convenient.
Description
Technical field
The present invention relates to electrochemiluminescence field, be specifically related to a kind of Ru (bpy)
3 2+preparation method and the application thereof of-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode.
Background technology
Mercury is a kind of toxic metal element being distributed widely in environment, is one of conventional heavy metal of the industry such as battery, mining.Mercury can pass through the different approaches such as respiratory tract, skin or alimentary canal and invade human body, and food chain has extremely strong accumulation ability for mercury, and the toxicity of mercury accumulates, taking chronic as common, taking spirit-dysautonomia, gingivitis, tremble as cardinal symptom.Therefore, the qualitative detection of mercury ion and quantitative test all have great importance to life, environment and medical science and industrial and agricultural production etc.
At present, in aqueous solution, the detection of mercury ion and the classic method of quantitative test have: spectrophotometric method, atomic absorption spectrum, plasma emission spectrum, Cold Atomic Fluorescent Mercury spectrum, gas chromatography etc., detecting principle is that Photoinduced Electron shifts (PET), intramolecular charge shifts (ICT) and chemical reaction system etc., although the sensitivity of these methods is very high, but required instrument and equipment and analysis cost costliness, trivial operations, length consuming time, can not meet the demand of simple and quick detection Trace Hg.Emerging biology sensor method (enzyme inhibition method), in the time detecting mercury ion, have advantage quick, easy, with low cost, but detection limit is higher, and linear response range is narrow.
Electrochemiluminescence (Electrochemiluminescence, ECL) be the coefficient result of chemiluminescence and galvanochemistry, refer to that ground state molecule is by participating in after electrochemical reaction obtains energy transitting to excited state, luminous phenomenon when excited state returns ground state, there is pick-up unit simple, highly sensitive, can control the advantages such as the extent of reaction, but current electrochemical sensor is often lacking selectivity aspect detection mercury ion.DNA biology sensor is using nucleic acid as molecular recognition and detection layers combining and a kind of trace analysis that can carry out fast detecting, monitoring in material molecule level of producing with the transducer of various physics, chemistry.DNA biology sensor is in the advantage of the aspects such as stability, repeatability, rapidity, convenience, sensitivity.It is a very fast research field of development in recent years that electrochemical method is applied to DNA biology sensor.Biomacromolecule DNA and chemotron (being the electrode of current mode or electric potential type) combination can form DNA electrochemica biological sensor.Sensors with auxiliary electrode were has that electrode fabrication is easy, long service life, reproducible, highly sensitive, cost is low, less energy consumption, portable, not damage test sample, be not subject to solution colour to affect, be easy to realize the plurality of advantages such as microminiaturized.
Summary of the invention
The object of the present invention is to provide a kind of rapid sensitive to detect preparation method and the application thereof of the DNA electrochemica biological sensor (being electrode) of trace amount mercury ion in water sample.
On the one hand, the invention provides a kind of preparation method of modified glassy carbon electrode, it is characterized in that, comprise the following steps:
(1) glass-carbon electrode is carried out to pre-service;
(2) tris (bipyridine) ruthenium (Ru (bpy)
3 2+) apply: by Ru (bpy)
3 2+be coated to the described pretreated glass-carbon electrode surface of step (1), form Ru (bpy)
3 2+modified glassy carbon electrode;
(3) golden nanometer particle applies: golden nanometer particle is coated to the Ru (bpy) that step (2) obtains
3 2+the glass-carbon electrode surface of modifying, forming surface coverage has the Ru (bpy) of Au nanoparticles films
3 2+-golden nanometer particle modified glassy carbon electrode;
(4) DNA applies: single stranded DNA is coated to the Ru (bpy) that step (3) obtains
3 2+-golden nanometer particle modified glassy carbon electrode surface, forms Ru (bpy)
3 2+-golden nanometer particle-DNA modification glass-carbon electrode;
(5) ferrocene functionalization graphene applies: ferrocene functionalization graphene is coated to the Ru (bpy) that step (4) obtains
3 2+-golden nanometer particle-DNA modification glass-carbon electrode surface, forms Ru (bpy)
3 2+-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode;
Wherein, described single stranded DNA sequence is rich in base T, in conjunction with Hg
2+after can complementary form stable double-stranded DNA structure, and 5 ' end of described single stranded DNA sequence is connected with SH-(CH
2)
6group.
In a specific embodiment of the present invention, the Ru (bpy) that step (2) is described
3 2+apply and carry out in the following manner: pretreated glass-carbon electrode step (1) Suo Shu is put into 0.1～1.0mMRu (bpy)
3 2+with 0.01～0.1MKNO
3mixed solution in, to carry out potentiostatic scanning through pretreated glass-carbon electrode in the three-electrode system of working electrode, wherein, voltage is 1.8～2.0V, be 5～10min sweep time; Take out after electrode, wash with deionized water; Drying at room temperature.
In a specific embodiment of the present invention, the described golden nanometer particle of step (3) applies and carries out in the following manner: the Ru (bpy) that step (2) is obtained
3 2+the glass-carbon electrode of modifying is put into 0.01～0.1M chlorauric acid solution, with Ru (bpy)
3 2+modified glassy carbon electrode is in the three-electrode system of working electrode, controls current potential at-1.0～1.1V, with chronoamperometry electro-deposition 5～20s; Take out after electrode, wash with deionized water; Drying at room temperature.
In a specific embodiment of the present invention, the described DNA of step (4) applies and carries out in the following manner: the Ru (bpy) that step (3) is obtained
3 2+-golden nanometer particle modified glassy carbon electrode immerses in 5～10 μ MDNA solution and soaks 3～3.5h; Then, in 1～5mM mercaptoethanol solution, process 45～60min; Wash with phosphate buffer.
In a specific embodiment of the present invention, the described ferrocene functionalization graphene of step (5) applies and carries out in the following manner: the Ru (bpy) that step (4) is obtained
3 2+-golden nanometer particle-DNA modification glass-carbon electrode immerses 1～2 mgmL
-145～60 min in ferrocene functionalization graphene solution; Wash with phosphate buffer.
In a specific embodiment of the present invention, the described pretreatment of glassy carbon electrode of step (1) carries out in the following manner: by α-A1 for glass-carbon electrode
2o
3burnishing powder polishing; Use deionized water washes clean; Ultrasonic 10min in deionized water and ethanol respectively.
On the other hand, the present invention also provides and has utilized the made modified glassy carbon electrode of the method for this law in the application that detects mercury ion content in water sample.
In a specific embodiment of the present invention, modified glassy carbon electrode of the present invention comprises the following steps in the application that detects mercury ion in water sample:
1) by Ru (bpy)
3 2+-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode immerses 25～35min in water sample to be detected, then cleans described electrode with phosphate buffer;
2) by Ru (bpy)
3 2+in the three-electrode system of-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode as working electrode, using 0.05～0.1M Tri-n-Propylamine solution, as detecting, liquid carries out galvanochemistry and electrochemiluminescence detects.
The present invention carries out Ru (bpy) on glass-carbon electrode surface
3 2+modify with Jenner's grain of rice, again by carrying out constructed dna electrochemiluminescence biology sensor at modified glassy carbon electrode surface self-organization single stranded DNA and ferrocene functionalization graphene, i.e. Ru (bpy)
3 2+-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode.This DNA electrochemiluminescence biology sensor utilizes single stranded DNA to realize ferrocene (Fc) to Ru (bpy) to the absorption of Graphene uniqueness
3 2+the cancellation of galvanochemistry optical signalling, due to Hg
2+can with single stranded DNA sequence in T-T base-pair generation specific binding form stable T-Hg
2+-T complex structure, thus single stranded DNA occurred conformation is changed, form stable duplex structure, no longer adsorb Graphene, ferrocene Graphene is departed from, Ru in sensor (bpy) from DNA chain
3 2+galvanochemistry optical signalling is recovered, and cancellation and the recovery of the galvanochemistry optical signalling by sensor, realize the trace heavy metal contaminated ion Hg in visual testing environment water quality
2+.Compared with prior art, the DNA electrochemiluminescence biology sensor tool of the present invention's design has the following advantages: 1) have good stability, reappearance, mercury ion is had to very high selectivity; 2) Graphene and golden nanometer particle are modified in electrode surface, the characteristic such as good conduction, high-specific surface area of having utilized Graphene and Jenner's grain of rice to have, thus increase greatly the sensitivity of electrode; 3) simple to operation, can quick and precisely detect the trace amount mercury ion in water sample.Therefore, DNA electrochemiluminescence biology sensor heavy metal ions in testing environment water quality of the present invention's design embodies good development prospect.
Brief description of the drawings
Fig. 1 be modified glassy carbon electrode of the present invention for detection of mercury ion experimental principle figure.
Fig. 2 is the cyclic voltammogram of different glass-carbon electrodes in an embodiment.
Fig. 3 be one embodiment of the invention modified glassy carbon electrode the different modifying stage electrochemical impedance.
Fig. 4 shows Hg
2+the impact of concentration and the binding time electrochemiluminescence intensity on embodiment of the present invention modified glassy carbon electrode.
Fig. 5 shows the impact of pH value and the electrochemiluminescence intensity of salinity on embodiment of the present invention modified glassy carbon electrode.
Fig. 6 is that the modified glassy carbon electrode of one embodiment of the invention is at the electrochemical luminescence signals in different modifying stage.
Fig. 7 is that the modified glassy carbon electrode of one embodiment of the invention detects variable concentrations Hg
2+electrochemical luminescence signals time, electrochemiluminescence intensity and Hg
2+the canonical plotting of concentration.
Fig. 8 is the modified glassy carbon electrode anti-interference test pattern of one embodiment of the invention.
Embodiment
Electrochemiluminescence detects, and is a kind of new analytical approach growing up on chemiluminescent basis, is the product that chemiluminescence and galvanochemistry mutually combine, and has high sensitivity, high selectivity, is easy to realize the features such as automatic continuous analysis.Ru (bpy)
3 2+owing to thering is the good characteristic that is stimulated, be day by day subject to people's attention in electrochemiluminescence field.Ferrocene and derivant thereof are the important object that coordination structure chemistry and inorganic photochemical are studied always, the structure that it is special and to Ru (bpy)
3 2+act in fundamental research significant Deng the cancellation of photosensitizer.
Nanogold particle has unique physics, chemical property and good bio-compatibility, has been widely used in DNA electrochemica biological sensor.The application of golden nanometer particle in electrochemica biological sensor is mainly aspect two: the one, improve can molecular recognition material process for fixation, improve fixed amount; The 2nd, the sensitivity that improves electrochemical signals indicator, thereby the detection sensitivity of DNA electrochemica biological sensor, shorten detection time and improve and detect flux.
Graphene is the crystal of banishing honeycomb crystalline network of the tightly packed formation of monolayer carbon atom, and unique structure makes it have excellent electricity, calorifics, mechanics and chemical property, makes it can be used as novel sensor material.Graphene can adsorb single stranded DNA effectively by pi-pi accumulation effect, but because pi-pi accumulation effect can not occur effectively for the rigid structure of double-stranded DNA itself and the water wettability of outer both sides phosphoric acid skeleton, so Graphene can not adsorb double-stranded DNA effectively.
The ingenious interaction relationship having utilized between above-mentioned substance of the present invention, designs a kind of Ru (bpy) that detects mercury ion that can be used in
3 2+-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode, the principle of its detection mercury ion as shown in Figure 1.There is no Hg
2+time, single stranded DNA absorption Graphene, thus realize ferrocene to Ru (bpy)
3 2+the cancellation of galvanochemistry optical signalling; There is Hg
2+time, due to Hg
2+can with single stranded DNA sequence in T-T base-pair generation specific binding form stable T-Hg
2+-T complex structure, thus single stranded DNA occurred conformation is changed, form stable duplex structure, no longer adsorb Graphene, ferrocene Graphene is departed from, Ru in sensor (bpy) from double-stranded DNA
3 2+galvanochemistry optical signalling is recovered.By cancellation and the recovery of galvanochemistry optical signalling, and show intensity, can realize trace Hg in water sample
2+detection.
The parameter such as electrode reaction character, mechanism and kinetics of electrode process that detects mercury ion in order to study modified glassy carbon electrode of the present invention, pretreated glass-carbon electrode, before modifying, adopts three-electrode system cyclic voltammetry to detect.In one embodiment, be pretreated glass-carbon electrode by working electrode, be platinum electrode to electrode, contrast electrode is the three-electrode system of Ag/AgCl electrode, in 0.5M sulfuric acid, glass-carbon electrode is carried out to cyclic voltammetry scan, it is-0.2～1.6V that voltage is wherein set, and after detection, uses deionized water rinsing glass-carbon electrode, dry up glass-carbon electrode surface, for subsequent use.Similarly, at DNA electrochemica biological sensor, i.e. Ru (bpy)
3 2+time prepared by-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode, also need to carry out cyclic voltammetry scan, in one embodiment, the modified glassy carbon electrode that preparation is completed is put into 0.05～0.1M Tri-n-Propylamine solution and is carried out cyclic voltammetry scan, wherein voltage range is 0.2～1.3V, and sweep speed is 50～100mVs
-1, photomultiplier high pressure is set to-800～-1000V.
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein, only for description and interpretation the present invention, is not intended to limit the present invention.
embodiment 1
The present invention uses electrochemical workstation and MPI-B type multiparameter chemiluminescence analysis test macro.
1. pretreatment of glassy carbon electrode: glass-carbon electrode is through α-A1 of 0.05 μ m
2o
3after burnishing powder polishing, rinse well with deionized water, and ultrasonic 10 min in deionized water and ethanol respectively.Employing three-electrode system detects, working electrode is glass-carbon electrode, be platinum electrode to electrode, contrast electrode is Ag/AgCl electrode, in 0.5M sulfuric acid, it is-0.2～1.6V that voltage is set, glass-carbon electrode is carried out to cyclic voltammetry scan, after detection, use deionized water rinsing electrode, dry up electrode surface, for subsequent use.
2. the preparation of modified glassy carbon electrode:
1) pre-service rear electrode is put into 0.1mMRu (bpy)
3 2+and 0.01MKNO
3mixed solution in, on electrochemical workstation, control anode potential and process 5min at 1.8V place constant potential, take out electrode, with deionized water washing, drying at room temperature; Electrode is put into 0.01M chlorauric acid solution, on electrochemical workstation, control current potential at-1.0～1.1V chronoamperometry electro-deposition 5s, take out electrode, by deionized water washing, drying at room temperature.
2) modified electrode step 1) being obtained immerses in 10 μ M single stranded DNA solution and soaks 3h, then in 1mM mercaptoethanol solution, processes 60min, cleans modified glassy carbon electrode with phosphate buffer; Just glass-carbon electrode immerses 2 mgmL again
-160min in ferrocene functionalization graphene solution, uses phosphate buffer cleaning electrode, obtains Ru (bpy)
3 2+-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode.
Wherein, the nucleotides sequence of single stranded DNA is classified 5 ' ATTCTTTGTTCTCCCCTGTTCTTTGTT T-3 ' as, is synthesized by biotech firm.In order to strengthen the connection between DNA and golden nanometer particle, in the time of synthesizing single-stranded DNA, be connected with mercapto groups (SH-(CH at its 5 ' end
2)
6), connect DNA and golden nanometer particle by sulfydryl-Au effect.
embodiment 2
1. pretreatment of glassy carbon electrode: glass-carbon electrode is through α-A1 of 0.3 μ m
2o
3after burnishing powder polishing, rinse well with deionized water, and ultrasonic 10min in deionized water and ethanol respectively.Employing three-electrode system detects, working electrode is glass-carbon electrode, be platinum electrode to electrode, contrast electrode is Ag/AgCl electrode, in 0.5M sulfuric acid, it is-0.2～1.6V that voltage is set, glass-carbon electrode is carried out to cyclic voltammetry scan, after detection, use deionized water rinsing electrode, dry up electrode surface, for subsequent use.
2. the preparation of modified glassy carbon electrode:
1) pre-service rear electrode is put into 1.0mMRu (bpy)
3 2+and 0.1MKNO
3mixed solution in, on electrochemical workstation, control anode potential and process 10min at 2.0V place constant potential, take out electrode, with deionized water washing, drying at room temperature; Electrode is put into 0.1M chlorauric acid solution, on electrochemical workstation, control current potential at-1.0～1.1V chronoamperometry electro-deposition 20s, take out electrode, by deionized water washing, drying at room temperature.
2) modified electrode step 1) being obtained immerses in 5 μ M single stranded DNA solution and soaks 3.5h, then in 5mM mercaptoethanol solution, processes 60min, cleans modified glassy carbon electrode with phosphate buffer; Just glass-carbon electrode immerses 1mgmL again
-145min in ferrocene functionalization graphene solution, uses phosphate buffer cleaning electrode, obtains Ru (bpy)
3 2+-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode.
Wherein, the nucleotides sequence of single stranded DNA is classified 5 ' ATTCTTTGTTCTCCCCTGTTCTTTGTT T-3 ' as, is synthesized by biotech firm.In order to strengthen the connection between DNA and golden nanometer particle, in the time of synthesizing single-stranded DNA, be connected with mercapto groups (SH-(CH at its 5 ' end
2)
6), connect DNA and golden nanometer particle by sulfydryl-Au effect.
the Performance Detection of modified glassy carbon electrode
1) cyclic voltammetry detects
Fig. 2 is the cyclic voltammogram of different glass-carbon electrodes, and wherein a is glass-carbon electrode bare electrode, and b is gold nano-glass-carbon electrode, and c is Ru (bpy)
3 2+-glass-carbon electrode, d is Ru (bpy)
3 2+-gold nano-glass-carbon electrode.At 0.01 M KNO
3in solution, carry out cyclic voltammetry scan, curve a is very level and smooth, does not have obvious redox peak to occur; After electrode coated with gold nano particle, there is oxidation peak at 0.922 V in curve b, illustrates that golden nanometer particle is modified at glass-carbon electrode surface effectively; Electrode is applied to Ru (bpy)
3 2+after, having there is an obvious oxidation peak at 1.01V in curve c, shows Ru (bpy)
3 2+effectively be modified at glass-carbon electrode surface; Again at Ru (bpy)
3 2+modified electrode coated with gold nano particle, preparation Ru (bpy)
3 2+-golden nanometer particle modified glassy carbon electrode, there is an oxidation peak that signal strengthens at 1.05 V in curve d, this shows that golden nanometer particle can effectively strengthen electronics transmission efficiency, thereby makes Ru (bpy)
3 2+signal peak be enhanced.
2) electrochemical impedance detects
Fig. 3 is the electrochemical impedance of the glass-carbon electrode in different modifying stage.Wherein, curve a is the nyquist plot of blank glass-carbon electrode, as seen from the figure, and at 5.0mM[Fe (CN)
6]
3/4in system, blank glass-carbon electrode has presented very little radian in high frequency region, and the nyquist plot obtaining is almost straight line, and this has showed typical blank electrode surface swift electron transmittance process.Electrode is applied to Ru (bpy)
3 2+after golden nanometer particle, the curve radian of curve b high frequency region obviously increases, and can be interpreted as Ru (bpy)
3 2+thereby cause a non-equal face phase interface of electrode to produce the electron transfer characteristic that has changed electrode surface with golden nanometer particle to the modification of electrode.After single stranded DNA and ferrocene functionalization graphene modified electrode, the conductance property of electrode strengthens to some extent, and as shown in curve c, its high frequency region camber ratio curve b reduces to some extent, illustrates that ferrocene functionalization graphene can effectively promote electronics transmission.As Ru (bpy)
3 2+-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode combines Hg
2+afterwards, curve d high frequency region curve radian increases to some extent, illustrates that ferrocene functionalization graphene has departed from DNA surface.
3) Hg
2+the impact on electrochemiluminescence intensity of concentration and binding time
Fig. 4 is the Ru (bpy) of preparation
3 2+-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode is respectively at the Hg of 0.05nM, 1nM and 100nM
2+the electroluminescence intensity level obtaining during in conjunction with different time in solution, thus draw electrochemiluminescence intensity and binding time, Hg
2+interaction relationship chart between concentration three.As can be seen from Figure 4, electrochemiluminescence intensity and binding time, Hg
2+there is good linear relationship in concentration.
4) impact of water environment on electrochemiluminescence intensity
Fig. 5 has shown that pH value (A) and sodium chloride concentration (B) are to Ru (bpy)
3 2+the impact of-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode.As seen from Figure 5, be that 7.5 left and right and sodium chloride concentration can be realized electrode sensor to Hg while being 0.1M at pH
2+optimum detection.
5) electrode sensor stability study
Fig. 6 shown in 0.1M Tri-n-Propylamine solution Different electrodes carried out to electrochemiluminescence intensity detection, and within a certain period of time, the electrochemiluminescence intensity of sensor does not have considerable influence, more stable, and wherein a is glass-carbon electrode bare electrode; B is Ru (bpy)
3 2+-glass-carbon electrode; C is Ru (bpy)
3 2+-gold nano-single stranded DNA-ferrocene functionalization graphene modified glassy carbon electrode; D is Ru (bpy)
3 2+-gold nano-double-stranded DNA-ferrocene functionalization graphene modified glassy carbon electrode.As seen from Figure 6, in the time that voltage is 1.1～1.2V, there is Ru (bpy)
3 2+galvanochemistry light intensity signal occur.The time of Fig. 6 center section and electrochemiluminescence strength relationship chart show, in 0.1M Tri-n-Propylamine solution, modified electrode is carried out to continuous sweep, its electrochemiluminescence intensity does not have considerable influence, more stable, illustrate that electrode sensor of the present invention has good stability.
6) mercury ion detecting
Utilize the modified glassy carbon electrode of preparation to detect mercury ion in water quality, concrete detecting step is as follows:
1) modified glassy carbon electrode is immersed to the Hg of variable concentrations to be detected
2+30min in solution, then uses phosphate buffer cleaning electrode.
2), using modified glassy carbon electrode as working electrode, on electrochemical workstation, use 0.1M Tri-n-Propylamine solution to carry out electrochemiluminescence detection as detecting liquid.(cyclic voltammetry scan voltage range is 0.2～1.25V, and sweep speed is 100mVs
-1, be set to-800V of photomultiplier high pressure).
Fig. 7 has shown the Hg of modified glassy carbon electrode at variable concentrations
2+(Hg in solution
2+concentration sequence is 0.05nm(a), 0.1nm(b), 1nm(c) and, 10nm(d), 20nm(e) and, 50nm(f) and 100nm(g)) cultivate after certain hour the electrochemiluminescence intensity vs time curve in 0.1M Tri-n-Propylamine solution.As seen from the figure, under best experiment condition, work as Hg
2+concentration is between 0.05～100nM time, along with Hg
2+the variation of concentration, electrochemiluminescence intensity has significant change.Detect Hg through calculating
2+linear equation be Δ
i eCL=371 lg
c hg2+ + 4226.6, related coefficient is 0.9968, detects and is limited to 18pM.
7) anti-interference test
For probing into the interference free performance of sensor to other potential interference ions, we have carried out parallel disturbed test experiment to the different ions that may coexist with mercury ion.In the detection shown in Fig. 8, ion concentration of mercury is 10nM, and other ion concentrations are 500nM.As seen from Figure 8, the mercury ion of 50 times of dilutions has produced ten response signals times over interfering ion, illustrates that the sensor of this experimental design has good Hg
2+identification selection.
Finally it should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. a preparation method for modified glassy carbon electrode, is characterized in that, comprises the following steps:
(1) glass-carbon electrode is carried out to pre-service;
(2) Ru (bpy)
3 2+apply: by Ru (bpy)
3 2+be coated to the described pretreated glass-carbon electrode surface of step (1), form Ru (bpy)
3 2+modified glassy carbon electrode;
(3) golden nanometer particle applies: golden nanometer particle is coated to the Ru (bpy) that step (2) obtains
3 2+the glass-carbon electrode surface of modifying, forming surface coverage has the Ru (bpy) of Au nanoparticles films
3 2+-golden nanometer particle modified glassy carbon electrode;
(4) DNA applies: single stranded DNA is coated to the Ru (bpy) that step (3) obtains
3 2+-golden nanometer particle modified glassy carbon electrode surface, forms Ru (bpy)
3 2+-golden nanometer particle-DNA modification glass-carbon electrode;
(5) ferrocene functionalization graphene applies: ferrocene functionalization graphene is coated to the Ru (bpy) that step (4) obtains
3 2+-golden nanometer particle-DNA modification glass-carbon electrode surface, forms Ru (bpy)
3 2+-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode;
Wherein, described single stranded DNA sequence is rich in base T, in conjunction with Hg
2+after can complementary form stable double-stranded DNA structure, and 5 ' end of described single stranded DNA sequence is connected with SH-(CH
2)
6group.
2. the preparation method of modified glassy carbon electrode as claimed in claim 1, the wherein described Ru (bpy) of step (2)
3 2+apply and carry out in the following manner: pretreated glass-carbon electrode step (1) Suo Shu is put into 0.1～1.0mMRu (bpy)
3 2+with 0.01～0.1MKNO
3mixed solution in, to carry out potentiostatic scanning through pretreated glass-carbon electrode in the three-electrode system of working electrode, wherein, voltage is 1.8～2.0V, be 5～10min sweep time; Washing; Dry.
3. the preparation method of modified glassy carbon electrode as claimed in claim 1, wherein the described golden nanometer particle of step (3) applies and carries out in the following manner: the Ru (bpy) that step (2) is obtained
3 2+the glass-carbon electrode of modifying is put into 0.01～0.1M chlorauric acid solution, with Ru (bpy)
3 2+modified glassy carbon electrode is in the three-electrode system of working electrode, controls current potential at-1.0～1.1V, with chronoamperometry electro-deposition 5～20s; Washing; Dry.
4. the preparation method of modified glassy carbon electrode as claimed in claim 1, wherein the described DNA of step (4) applies and carries out in the following manner: the Ru (bpy) that step (3) is obtained
3 2+-golden nanometer particle modified glassy carbon electrode immerses in 5～10 μ MDNA solution and soaks 3～3.5h; Then, in 1～5mM mercaptoethanol solution, process 45～60min; Wash with phosphate buffer.
5. the preparation method of modified glassy carbon electrode as claimed in claim 1, wherein the described ferrocene functionalization graphene of step (5) applies and carries out in the following manner: the Ru (bpy) that step (4) is obtained
3 2+-golden nanometer particle-DNA modification glass-carbon electrode immerses 1～2mgmL
-145～60min in ferrocene functionalization graphene solution; Wash with phosphate buffer.
6. the preparation method of modified glassy carbon electrode as claimed in claim 1, wherein the described pretreatment of glassy carbon electrode of step (1) carries out in the following manner: by α-A1 for glass-carbon electrode
2o
3burnishing powder polishing; Washing; Ultrasonic 10min in deionized water and ethanol respectively.
7. the modified glassy carbon electrode that as described in as arbitrary in claim 1～6, method is made is detecting the application of mercury ion content in water sample.
8. application as claimed in claim 7, is characterised in that, comprises the following steps:
1) by described Ru (bpy)
3 2+-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode immerses 25～35min in water sample to be detected, then cleans described electrode with phosphate buffer;
2) by described Ru (bpy)
3 2+in the three-electrode system of-golden nanometer particle-DNA-ferrocene functionalization graphene modified glassy carbon electrode as working electrode, using 0.05～0.1 M Tri-n-Propylamine solution, as detecting, liquid carries out galvanochemistry and electrochemiluminescence detects.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410072153.7A CN103913496B (en) | 2014-02-28 | 2014-02-28 | A kind of preparation method of modified glassy carbon electrode and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410072153.7A CN103913496B (en) | 2014-02-28 | 2014-02-28 | A kind of preparation method of modified glassy carbon electrode and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103913496A true CN103913496A (en) | 2014-07-09 |
| CN103913496B CN103913496B (en) | 2016-05-11 |
Family
ID=51039337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410072153.7A Active CN103913496B (en) | 2014-02-28 | 2014-02-28 | A kind of preparation method of modified glassy carbon electrode and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103913496B (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104198557A (en) * | 2014-09-03 | 2014-12-10 | 大连理工大学 | Enzyme based electrochemical biosensing method applied to detection of trace mercury ions |
| CN104677892A (en) * | 2015-03-27 | 2015-06-03 | 济南大学 | Method for preparing electrochemiluminescence biological sensing interface based on loaded graphite phase carbon nitride and application thereof |
| CN104880456A (en) * | 2015-05-22 | 2015-09-02 | 济南大学 | Preparation method and application of electrochemiluminescence immunosensor constructed on basis of GO/MWCNTs-COOH/Au @ CeO2 |
| CN105044085A (en) * | 2015-09-19 | 2015-11-11 | 陕西师范大学 | Method for detecting mercury ions based on Silica/chitosan/Ru nanoparticle electrochemiluminescence method |
| CN105154063A (en) * | 2015-07-22 | 2015-12-16 | 北京理工大学 | Indium-based metal organic framework wrapped functional positive ion Ru(bpy)32+ fluorescent material and preparation method therefor |
| CN105675590A (en) * | 2016-01-08 | 2016-06-15 | 汕头大学 | Electrochemiluminescent biosensor for detection of endonuclease, preparation and application thereof |
| CN106622396A (en) * | 2015-11-03 | 2017-05-10 | 钟梅 | Preparation method of composite catalyst by graphene modified glass carbon electrode |
| CN107215860A (en) * | 2016-03-21 | 2017-09-29 | 绿琪（北京）生物科技有限公司 | A kind of preparation method of the orderly self-assembled structures of graphene/DNA |
| CN107890866A (en) * | 2017-12-13 | 2018-04-10 | 黑龙江科技大学 | A kind of method using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition |
| CN108690870A (en) * | 2018-05-15 | 2018-10-23 | 北京工业大学 | The preparation method of biosensor is quenched in tris (bipyridine) ruthenium electrochemical luminescence |
| CN109470751A (en) * | 2018-09-13 | 2019-03-15 | 宁波大学 | A kind of preparation method and applications of the electrochemical sensor of binary channels output detection mercury ion |
| CN110006968A (en) * | 2019-03-12 | 2019-07-12 | 宁波大学 | The preparation method and applications of electrochemica biological sensor based on quick scan cycle volt-ampere technology detection mercury ion |
| CN110208346A (en) * | 2019-06-20 | 2019-09-06 | 重庆市人民医院 | The biosensor and its preparation method and application that electrochemical luminescence for CCN1 albumen detects |
| CN110308142A (en) * | 2019-07-25 | 2019-10-08 | 常州大学 | A kind of tetracycline flexibility class goldleaf electrochemical luminescence sensor and preparation method thereof and detection method |
| CN110501406A (en) * | 2019-09-30 | 2019-11-26 | 青岛大学 | A kind of spermidine electrochemical luminescence detection method based on Graphene electrodes |
| CN110823977A (en) * | 2019-10-28 | 2020-02-21 | 江苏大学 | Hg detection method2+Preparation method of self-enhanced electrochemiluminescence aptamer sensor |
| CN112763555A (en) * | 2019-10-21 | 2021-05-07 | 上海交通大学 | Multi-target heavy metal microfluidic electrochemical sensor and preparation and application thereof |
| CN115096971A (en) * | 2022-06-29 | 2022-09-23 | 北部湾大学 | Glassy carbon electrode for detecting mercury ions and preparation method and application thereof |
| CN115211995A (en) * | 2022-07-18 | 2022-10-21 | 天津大学 | Flexible intelligent sensing tooth socket |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007089550A2 (en) * | 2006-01-26 | 2007-08-09 | Nanoselect, Inc. | Cnt-based sensors: devices, processes and uses thereof |
| CN102520036A (en) * | 2011-12-30 | 2012-06-27 | 汕头大学 | Method for fixing terpyridyl ruthenium on surface of electrochemical electrode |
| CN103230794A (en) * | 2012-06-18 | 2013-08-07 | 天津大学 | Graphene-oxide-loaded double-metal nano-particles used in methanol and ethanol fuel cells and in catalytic reactions, and preparation method thereof |
| CN103245656A (en) * | 2013-04-25 | 2013-08-14 | 济南大学 | Preparation and application of alpha fetoprotein and carcino-embryonic antigen electrochemiluminescence sensor |
-
2014
- 2014-02-28 CN CN201410072153.7A patent/CN103913496B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007089550A2 (en) * | 2006-01-26 | 2007-08-09 | Nanoselect, Inc. | Cnt-based sensors: devices, processes and uses thereof |
| CN102520036A (en) * | 2011-12-30 | 2012-06-27 | 汕头大学 | Method for fixing terpyridyl ruthenium on surface of electrochemical electrode |
| CN103230794A (en) * | 2012-06-18 | 2013-08-07 | 天津大学 | Graphene-oxide-loaded double-metal nano-particles used in methanol and ethanol fuel cells and in catalytic reactions, and preparation method thereof |
| CN103245656A (en) * | 2013-04-25 | 2013-08-14 | 济南大学 | Preparation and application of alpha fetoprotein and carcino-embryonic antigen electrochemiluminescence sensor |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104198557A (en) * | 2014-09-03 | 2014-12-10 | 大连理工大学 | Enzyme based electrochemical biosensing method applied to detection of trace mercury ions |
| CN104677892A (en) * | 2015-03-27 | 2015-06-03 | 济南大学 | Method for preparing electrochemiluminescence biological sensing interface based on loaded graphite phase carbon nitride and application thereof |
| CN104880456A (en) * | 2015-05-22 | 2015-09-02 | 济南大学 | Preparation method and application of electrochemiluminescence immunosensor constructed on basis of GO/MWCNTs-COOH/Au @ CeO2 |
| CN105154063A (en) * | 2015-07-22 | 2015-12-16 | 北京理工大学 | Indium-based metal organic framework wrapped functional positive ion Ru(bpy)32+ fluorescent material and preparation method therefor |
| CN105044085B (en) * | 2015-09-19 | 2018-05-08 | 陕西师范大学 | A kind of method based on Silica/chitosan/Ru nano-particles Electrochemiluminescince detection mercury ion |
| CN105044085A (en) * | 2015-09-19 | 2015-11-11 | 陕西师范大学 | Method for detecting mercury ions based on Silica/chitosan/Ru nanoparticle electrochemiluminescence method |
| CN106622396A (en) * | 2015-11-03 | 2017-05-10 | 钟梅 | Preparation method of composite catalyst by graphene modified glass carbon electrode |
| CN105675590A (en) * | 2016-01-08 | 2016-06-15 | 汕头大学 | Electrochemiluminescent biosensor for detection of endonuclease, preparation and application thereof |
| CN105675590B (en) * | 2016-01-08 | 2018-05-25 | 汕头大学 | A kind of electrochemical luminescence biosensor for detecting restriction endonuclease and its preparation and application |
| CN107215860B (en) * | 2016-03-21 | 2020-07-24 | 绿琪（北京）生物科技有限公司 | Preparation method of graphene/DNA ordered self-assembly structure |
| CN107215860A (en) * | 2016-03-21 | 2017-09-29 | 绿琪（北京）生物科技有限公司 | A kind of preparation method of the orderly self-assembled structures of graphene/DNA |
| CN107890866A (en) * | 2017-12-13 | 2018-04-10 | 黑龙江科技大学 | A kind of method using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition |
| CN107890866B (en) * | 2017-12-13 | 2020-07-31 | 黑龙江科技大学 | Method for preparing platinum catalyst by electrodeposition with hydantoin derivative as complexing agent |
| CN108690870A (en) * | 2018-05-15 | 2018-10-23 | 北京工业大学 | The preparation method of biosensor is quenched in tris (bipyridine) ruthenium electrochemical luminescence |
| CN109470751A (en) * | 2018-09-13 | 2019-03-15 | 宁波大学 | A kind of preparation method and applications of the electrochemical sensor of binary channels output detection mercury ion |
| CN109470751B (en) * | 2018-09-13 | 2020-10-30 | 宁波大学 | Preparation method and application of electrochemical sensor for detecting mercury ions through dual-channel output |
| CN110006968A (en) * | 2019-03-12 | 2019-07-12 | 宁波大学 | The preparation method and applications of electrochemica biological sensor based on quick scan cycle volt-ampere technology detection mercury ion |
| CN110006968B (en) * | 2019-03-12 | 2021-03-09 | 宁波大学 | Preparation method and application of electrochemical biosensor for detecting mercury ions based on rapid scanning cyclic voltammetry technology |
| CN110208346A (en) * | 2019-06-20 | 2019-09-06 | 重庆市人民医院 | The biosensor and its preparation method and application that electrochemical luminescence for CCN1 albumen detects |
| CN110208346B (en) * | 2019-06-20 | 2021-09-10 | 重庆市人民医院 | Biosensor for electrochemiluminescence detection of CCN1 protein and preparation method and application thereof |
| CN110308142A (en) * | 2019-07-25 | 2019-10-08 | 常州大学 | A kind of tetracycline flexibility class goldleaf electrochemical luminescence sensor and preparation method thereof and detection method |
| CN110308142B (en) * | 2019-07-25 | 2021-07-27 | 常州大学 | Tetracycline flexible gold-like foil electrochemical luminescence sensor and preparation method and detection method thereof |
| CN110501406A (en) * | 2019-09-30 | 2019-11-26 | 青岛大学 | A kind of spermidine electrochemical luminescence detection method based on Graphene electrodes |
| CN112763555A (en) * | 2019-10-21 | 2021-05-07 | 上海交通大学 | Multi-target heavy metal microfluidic electrochemical sensor and preparation and application thereof |
| CN110823977A (en) * | 2019-10-28 | 2020-02-21 | 江苏大学 | Hg detection method2+Preparation method of self-enhanced electrochemiluminescence aptamer sensor |
| CN115096971A (en) * | 2022-06-29 | 2022-09-23 | 北部湾大学 | Glassy carbon electrode for detecting mercury ions and preparation method and application thereof |
| CN115211995A (en) * | 2022-07-18 | 2022-10-21 | 天津大学 | Flexible intelligent sensing tooth socket |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103913496B (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103913496B (en) | A kind of preparation method of modified glassy carbon electrode and application thereof | |
| Hasanjani et al. | An electrochemical sensor for attomolar determination of mercury (II) using DNA/poly-L-methionine-gold nanoparticles/pencil graphite electrode | |
| Ensafi et al. | A new non-enzymatic glucose sensor based on copper/porous silicon nanocomposite | |
| Wei et al. | Stripping voltammetry study of ultra-trace toxic metal ions on highly selectively adsorptive porous magnesium oxide nanoflowers | |
| Zhang et al. | A novel electrochemical sensor for formaldehyde based on palladium nanowire arrays electrode in alkaline media | |
| Khan et al. | Electrochemical determination of uric acid in the presence of ascorbic acid on electrochemically reduced graphene oxide modified electrode | |
| He et al. | Poly (glycine)/graphene oxide modified glassy carbon electrode: Preparation, characterization and simultaneous electrochemical determination of dopamine, uric acid, guanine and adenine | |
| CN103983681B (en) | A kind of for electrochemical sensor detecting heavy metal and its preparation method and application | |
| Sheng et al. | Electrodeposition of Prussian blue nanoparticles on polyaniline coated halloysite nanotubes for nonenzymatic hydrogen peroxide sensing | |
| Hosseini et al. | A novel bioelectrochemical sensing platform based on covalently attachment of cobalt phthalocyanine to graphene oxide | |
| Wen et al. | Simultaneous analysis of uric acid, xanthine and hypoxanthine using voltammetric sensor based on nanocomposite of palygorskite and nitrogen doped graphene | |
| Cao et al. | Developing an electrochemical sensor for the detection of tert-butylhydroquinone | |
| Wang et al. | An electrochemical aptasensor based on a TiO 2/three-dimensional reduced graphene oxide/PPy nanocomposite for the sensitive detection of lysozyme | |
| CN108279262A (en) | A kind of electrochemical sensor and preparation method for Sensitive Detection dopamine and uric acid simultaneously | |
| Schebeliski et al. | Preparation and characterization of a carbon nanotube-based ceramic electrode and its potential application at detecting sulfonamide drugs | |
| Ensafi et al. | Development of a voltammetric procedure based on DNA interaction for sensitive monitoring of chrysoidine, a banned dye, in foods and textile effluents | |
| Moreno-Baron et al. | Graphite-epoxy composite as an alternative material to design mercury free working electrodes for stripping voltammetry | |
| Xu et al. | Simultaneous determination of ascorbic acid, dopamine, and uric acid based on double-walled carbon nanotubes/choline-modified electrode | |
| Babaei et al. | A multi-walled carbon nano-tube and nickel hydroxide nano-particle composite-modified glassy carbon electrode as a new sensor for the sensitive simultaneous determination of ascorbic acid, dopamine and uric acid | |
| CN108680636A (en) | Preparation method, product and the method for detecting tert-butyl hydroquinone of multi-walled carbon nanotube/l-methionine modified electrode | |
| En-Nakra et al. | Voltammetric determination of rutin in fruit juice samples using a 2 mercaptobenzothiazole coated pencil graphite electrode | |
| CN108802121B (en) | Photocurrent dissolved oxygen sensor | |
| Manikandan et al. | Anodized screen-printed electrode modified with poly (5-amino-4H-1, 2, 4-triazole-3-thiol) film for ultrasensitive detection of Hg2+ in fish samples | |
| CN111272843B (en) | Nano material with FeCo network structure constructed by nano wires and preparation method and application thereof | |
| CN103940882B (en) | Trace copper ion sensor and construction method in a kind of water sample |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |