CN109307695A - A kind of preparation method and application of Spanon Electrochemiluminescsensor sensor - Google Patents
A kind of preparation method and application of Spanon Electrochemiluminescsensor sensor Download PDFInfo
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- CN109307695A CN109307695A CN201811306537.5A CN201811306537A CN109307695A CN 109307695 A CN109307695 A CN 109307695A CN 201811306537 A CN201811306537 A CN 201811306537A CN 109307695 A CN109307695 A CN 109307695A
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- 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
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Abstract
The invention discloses a kind of preparation methods of Spanon Electrochemiluminescsensor sensor.Belong to Nano-function thin films and biosensory analysis technology field.The present invention is prepared for cobalt nickel bimetal nitride nano chip arrays can disposably throw first on electrode, using its big specific surface area and to the high adsorption activity of amino, and the amido functional group of poly-dopamine, using the method for growth in situ, directly be prepared in succession on cobalt nickel bimetal nitride nano chip arrays in succession poly-dopamine film and in-stiu coating luminol using Spanon as the molecularly imprinted polymer of template molecule, after by template molecule elution, the position of template molecule originally has become hole, that is the molecularly imprinted polymer of eluted template molecule, thus, a kind of Spanon Electrochemiluminescsensor sensor just prepares completion.
Description
Technical field
The present invention relates to a kind of preparation method and applications of Electrochemiluminescsensor sensor.Belong to Nano-function thin films
With biosensory analysis technology field.
Background technique
Spanon is also known as ampicillin, is a kind of beta-lactam antibiotic, is semi-synthetic penbritin, can treat
Various bacteria infection.Indication includes respiratory tract infection, urethral infection, meningitis, salmonella infection disease and the internal membrane of heart
It is scorching.Since its is easy to use, low in cost, it is chiefly used in infectious diseases caused by treating chicken sensitive bacteria, such as Escherichia coli, sramana
Salmonella, Pasteurella, staphylococcus and streptococcal infection etc..On October 27th, 2017, the research of World Health Organization's international cancer
In the carcinogenic substance inventory that mechanism announces, ampicillin is in 3 class carcinogenic substance inventories.Therefore, it develops a kind of quick, highly selective
It is extremely important to publilc health with the method for Sensitive Detection Spanon, and have wide market application prospect.
Electroanalytical Chemistry sensor includes electrochemical sensor, Electrochemiluminescsensor sensor, optical electro-chemistry sensor etc.,
Such sensor has high specific selectivity, excellent stability, excellent reproducibility, wide detection range and floor detection
Limit.Due to the sensor prepare simple, easy to detect, high sensitivity, it is at low cost the advantages that be widely used in chromatographic isolation, film
Point, the fields such as Solid Phase Extraction, medicine controlled releasing, chemical sensitisation.Molecularly imprinted polymer (MIP), also referred to as " plastics antibody ", can
Specific recognition and the specific target molecule of selective absorption (i.e. template molecule).Since molecular imprinting technology has many advantages,
Such as organic reagent corrosion resistance, good stability, heat-resisting quantity and preparation are simple.Therefore, in the past few years, it is based on
The MIP Electroanalytical Chemistry sensor (MIP-ECS) that MIP is combined with Electroanalytical Chemistry sensor causes Electroanalytical Chemistry field
Focus, the especially detection of small molecule contaminants.However, having template point in the preparation process of traditional MIP-ECS
The disadvantages of sub- hardly possible elutes, the thickness of blotting membrane is difficult to control, reproducibility is poor, limits molecular engram film in Electroanalytical Chemistry sensor
In application.These problems, especially molecular engram film thickness are not easy to control cause electrochemical sensor sensitivity decrease and
Molecular engram film easily falls off from electrode surface during elution leads to the technical problem of stability and reproducibility reduction, limits
Therefore the application of MIP_ECS finds the modification side of new molecularly imprinted polymer synthetic method, new molecular engram film electrode
The combination method of method and molecular engram film and base material has important grind to solve preparation and the application problem of MIP-ECS
Study carefully meaning and market value.
Summary of the invention
The purpose of the present invention is to provide a kind of high specificity, prepare simple, easy to detect, high sensitivity, at low cost
The preparation method of Spanon Electrochemiluminescsensor sensor, prepared electrogenerated chemiluminescence sensing electrode, preparation is simple, reappears
Property it is good, stability is strong, can be used as sensor for Spanon quick, Sensitive Detection.Based on this purpose, the present invention is first one
Secondary property, which can be thrown, is prepared for cobalt nickel bimetal nitride nano chip arrays on electrode, using its big specific surface area and to the height of amino
The amido functional group of adsorption activity and poly-dopamine is received in cobalt nickel bimetal nitride in succession using the method for growth in situ
The dividing using Spanon as template molecule of poly-dopamine film and in-stiu coating luminol is directly prepared on rice chip arrays in succession
Sub- imprinted polymer, after by template molecule elution, the position of template molecule originally has become hole, i.e. eluted template point
The molecularly imprinted polymer of son, a kind of Spanon Electrochemiluminescsensor sensor just prepares completion as a result,.When for Spanon
When being detected, Spanon Electrochemiluminescsensor sensor is inserted into solution to be measured, the Spanon in solution to be measured can adsorb
Into the hole of NIP.Spanon concentration in solution to be measured is bigger, and it is more to be adsorbed onto Spanon in the hole of NIP.It is electric when carrying out
When causing chemiluminescence detection, it can be become smaller with increasing for Spanon in the hole of NIP is adsorbed by the current strength of electrode,
Corresponding electrochemiluminescence signal can also become smaller therewith, thus the journey reduced according to the light signal strength of electrogenerated chemiluminescence
Degree is capable of the concentration of Spanon in qualitative, quantitative solution to be measured.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method of Spanon Electrochemiluminescsensor sensor, the Spanon Electrochemiluminescsensor sensor
Gathered by growth in situ on cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-nanoarray without template molecule molecular engram
Close what object NIP was obtained；The molecular engram polymerization that template molecule is free from without template molecule molecularly imprinted polymer NIP
Object；The molecularly imprinted polymer without containing template molecule is by the MIP of molecularly imprinted polymer containing template molecule by washing
Stripper plate molecule obtains；The MIP of molecularly imprinted polymer containing template molecule is that the molecular engram containing template molecule is poly-
Close object；The template molecule is Spanon；
2. the preparation side of the chip arrays electrode of cobalt nickel bimetal nitride nano described in technical solution 1 CoNiN-nanoarray
Method includes following preparation step:
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 1 ~ 3 mmol Ni (NO is weighed3)2With Co (NO3)2Mixture and 3 ~ 9 mmol urea CO (NH2)2, it is put into
In 50 mL beakers, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 100 ~
It is reacted 9 ~ 12 hours at a temperature of 130 DEG C, cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electricity is prepared
Pole；
(4) 5 in the cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode insertion ammonium hydroxide obtained step (3) ~
It is taken out after 30 seconds, under ammonia environment, after being heated to 340 ~ 400 DEG C and being kept for 4 ~ 8 hours, continuation is dropped naturally under ammonia environment
To room temperature, it is then inserted into the phosphate buffer solution PBS containing dopamine and Ammonium Persulfate 98.5, in 20 ~ 40 DEG C of temperature
After lower reaction 4 ~ 6 hours, takes out and embathed 2 ~ 4 times with deionized water, cobalt nickel bimetal nitride nano chip arrays are prepared
Electrode CoNiN-nanoarray；
The described disposable electrode of throwing is selected from one of cycle unit: nickel foam, foam copper, pure nickel piece, pure copper sheet, pure cobalt piece,
Pure silicon piece, conductive carbon cloth；Ni (the NO3)2With Co (NO3)2Mixture in the molar ratio of nickel and cobalt be 1:1；
In the phosphate buffer solution PBS containing dopamine and Ammonium Persulfate 98.5: dopamine concentration is 2 ~ 5 mg/mL, mistake
The concentration of amine sulfate is 3 ~ 8 mg/mL, and the concentration of phosphate buffer solution PBS is 0.1 mol/L, and pH value is 7.2 ~ 8.5；
3. the MIP of molecularly imprinted polymer containing template molecule of CoNiN-nanoarray growth in situ described in technical solution 1
Preparation method include following preparation step:
(1) 0.25 ~ 0.45mmol template molecule and 3 ~ 5 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, are added
Enter 8 ~ 15 mL acetonitriles, 30 min of ultrasound to whole dissolutions；
(2) 15 ~ 25 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound
To being uniformly mixed, precursor mixed solution is obtained；
(3) CoNiN-nanoarray prepared in technical solution 2 is clipped on Stirring device, before being inserted into step (2)
It drives in body mixed solution, in N2At a temperature of environment and 20 ~ 40 DEG C of water-bath, with 5 ~ 200 revolutions per seconds of speed Stirring, simultaneously
1 ~ 3 mL of luminol solution and 1 mmol azo two of 1 mmol/L is added dropwise simultaneously into mixed solution with 1 ~ 20 drop/sec of speed
Isobutyronitrile AIBN carries out initiation polymerization, and the molecular engram containing template molecule that growth in situ is obtained on CoNiN-nanoarray is poly-
Close object MIP；
4. CoNiN-nanoarray growth in situ described in technical solution 1 without template molecule molecularly imprinted polymer NIP
Preparation step are as follows: by obtained in technical solution 3 on CoNiN-nanoarray growth in situ molecule containing template molecule print
Mark polymer MIP is immersed in eluant, eluent, and template molecule is carried out 5 ~ 20 min of elution at room temperature, then takes out, obtains
Without template molecule molecularly imprinted polymer NIP；The eluant, eluent is the mixed liquor of formic acid and methanol, wherein formic acid and methanol
Volume ratio is 9:(1 ~ 5)；
5. the preparation step of Spanon Electrochemiluminescsensor sensor described in technical solution 1 are as follows: will be in technical solution 2 ~ 4
The growth in situ obtained on CoNiN-nanoarray without template molecule molecularly imprinted polymer NIP, embathed with deionized water
It 2 ~ 4 times, dries at room temperature, obtains Spanon Electrochemiluminescsensor sensor；
6. using Spanon Electrochemiluminescsensor sensor prepared by technical solution described in technical solution 1 ~ 5, applied to killing
The detection of worm amidine, including following applying step:
(1) standard solution is prepared: preparing the Spanon standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: being working electrode by Spanon Electrochemiluminescsensor sensor, is prepared in inserting step (1)
The Spanon standard solution of various concentration takes out after hatching 10 min, is embathed 3 times with deionized water；
(3) working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is used as to electrode, with step
(2) the working electrode composition three-electrode system modified, is connected in electrochemiluminescdetection detection equipment；In a cell first
Be added afterwards 15 mL phosphate buffer solution PBS and 1mL 2 mmol/L hydrogen peroxide (H2O2) solution；With double rank Pulse Voltammetries
Method applies cyclical voltage to the working electrode of assembling, detects the light signal strength of electrogenerated chemiluminescence；The response light of blank standard specimen
Signal strength is denoted asA 0, the response light signal strength of the Spanon standard solution containing various concentration is denoted asA i, it is strong to respond optical signal
Spending reduced difference is ΔA = A 0-A i, ΔAWith the mass concentration of Spanon standard solutionCBetween it is linear, draw ΔA?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；Double rank arteries and veins
Rush parameter setting when voltammetry detection are as follows: initial potential is 0 V, and pulse potential is 0.9 V, and the burst length is 0.1 s, pulse
Period is 30 s；
(4) in sample to be tested Spanon detection: the Spanon standard solution in step (1) is replaced with sample to be tested, according to step
Suddenly the method in (2) and (3) is detected, the difference DELTA that light signal strength reduces according to responseAAnd working curve, it obtains to be measured
The content of Spanon in sample.
Beneficial achievement of the invention
(1) Spanon Electrochemiluminescsensor sensor preparation of the present invention is simple, easy to operate, realizes to the fast of sample
Fast, sensitive, highly selective detection, and it is at low cost, it can be applied to portable inspectiont, there is market development prospect；
(2) growth in situ divides the present invention on cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-nanoarray for the first time
On the one hand sub- imprinted polymer can grow molecule more, more evenly using the big specific surface area of CoNiN-nanoarray and print
Mark polymer, and CoNiN-nanoarray has excellent electron transmission ability, to greatly improve detection sensitivity；Separately
On the one hand, CoNiN-nanoarray has electro catalytic activity to hydrogen peroxide, may not need and horseradish peroxidase is added
Luminol-stabilization of hydrogen peroxide electrogenerated chemiluminescence system, highly effective reaction is realized, so that prepared sensor is without considering
Biological enzyme deactivation prob so that the use and storage of sensor can more stable and condition it is loose, thus into one
While step reduces signal background, improves detection sensitivity, greatly reduces testing cost and reduce environmental pollution；
(3) present invention specific surface area and dopamine big using high adsorption activity and nano-array electrode of the nitride to amino
It combines, so that dopamine in cobalt nickel bimetal nitride nano chip arrays in situ Polymerization, is forming sufficiently thin gather
While dopamine film, on uniform fold to cobalt nickel bimetal nitride nano chip arrays, thus to be more more preferable in next step
Polymerizable molecular imprinted polymer carry out place mat；Later using poly-dopamine to the strong of the amino being rich on molecularly imprinted polymer
Absorption connection function, then dexterously use CoNiN-nanoarray as blender, in molecular engram precursor mixed solution
In carry out immersion stirring, by control mixing speed, initiators for polymerization rate of addition and polymeric reaction temperature,
The surface CoNiN-nanoarray direct in-situ grows the molecularly imprinted polymer that can control film thickness, on the one hand makes
CoNiN-nanoarray can securely supporting molecular imprinted polymer and luminol, to significantly improve prepared electrochemistry
The stability and reproducibility of sensor；On the other hand molecularly imprinted polymer can effectively be controlled in electrode surface into film thickness
Degree, solve be unable to control molecular engram film be unable to control in electrode surface film forming thickness it is difficult so as to cause the technology of poor reproducibility
Topic；It, can be in addition, more coated due to preparation method of the invention to effective control of film forming thickness and the in situ quantitation of luminol
The sensitivity and detection limit for sufficiently improving the electrochemical sensor based on molecular engram have important scientific meaning and application
Value.
Specific embodiment
The preparation of 1 CoNiN-nanoarray of embodiment
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 1 mmol Ni (NO is weighed3)2With Co (NO3)2Mixture and 3 mmol urea CO (NH2)2, it is put into 50
In mL beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 100
It is reacted 12 hours at a temperature of DEG C, cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode insertion that step (3) obtains is contained into DOPA
In the phosphate buffer solution PBS of amine and Ammonium Persulfate 98.5,20 DEG C at a temperature of reaction 4 hours after, take out and use deionized water
It embathes 2 times, cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-nanoarray is prepared；
The electrode therein that can disposably throw is nickel foam；Ni (the NO3)2With Co (NO3)2Mixture in nickel and cobalt rub
You are than being 1:1；Dopamine concentration is 2 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 3 mg/mL, the concentration of phosphate buffer solution PBS
For 0.1 mol/L, pH value 7.2.
The preparation of 2 CoNiN-nanoarray of embodiment
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 2 mmol Ni (NO are weighed3)2With Co (NO3)2Mixture and 6 mmol urea CO (NH2)2, it is put into 50
In mL beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 110
It is reacted 11 hours at a temperature of DEG C, cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode insertion that step (3) obtains is contained into DOPA
In the phosphate buffer solution PBS of amine and Ammonium Persulfate 98.5,30 DEG C at a temperature of reaction 5 hours after, take out and use deionized water
It embathes 3 times, cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-nanoarray is prepared；
The electrode therein that can disposably throw is pure copper sheet；Ni (the NO3)2With Co (NO3)2Mixture in nickel and cobalt rub
You are than being 1:1；Dopamine concentration is 3.5 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 6.2 mg/mL, phosphate buffer solution PBS's
Concentration is 0.1 mol/L, pH value 8.0.
The preparation of 3 CoNiN-nanoarray of embodiment
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 3 mmol Ni (NO are weighed3)2With Co (NO3)2Mixture and 9 mmol urea CO (NH2)2, it is put into 50
In mL beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 130
It is reacted 9 hours at a temperature of DEG C, cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the cobalt nickel bimetal nitride nano chip arrays presoma electrode insertion obtained step (3) contains dopamine and mistake
In the phosphate buffer solution PBS of amine sulfate, 40 DEG C at a temperature of reaction 6 hours after, take out simultaneously embathe 4 with deionized water
It is secondary, cobalt nickel bimetal layered hydroxide nano-chip arrays electrode CoNiN-nanoarray is prepared；
The electrode therein that can disposably throw is conductive carbon cloth；Ni (the NO3)2With Co (NO3)2Mixture in nickel and cobalt
Molar ratio is 1:1；Dopamine concentration is 5 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 8 mg/mL, and phosphate buffer solution PBS's is dense
Degree is 0.1 mol/L, pH value 8.5.
The preparation method of 4 Spanon Electrochemiluminescsensor sensor of embodiment
(1) 0.25 mmol template molecule and 3 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 8 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 15 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) CoNiN-nanoarray prepared in embodiment 1 is clipped on Stirring device, the forerunner being inserted into step (2)
In body mixed solution, in N2At a temperature of environment and 20 DEG C of water-bath, with 200 revolutions per seconds of speed Stirring, while with 1 drop/
1 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN of 1 mmol/L is added dropwise into mixed solution simultaneously for the speed of second
Initiation polymerization is carried out, the MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on CoNiN-nanoarray；
(4) molecularly imprinted polymer containing template molecule of growth in situ on CoNiN-nanoarray for obtaining step (3)
MIP is immersed in eluant, eluent, and template molecule is carried out 5 min of elution at room temperature, is then taken out, no template molecule point is obtained
Sub- imprinted polymer NIP；Continue to be embathed 2 times with deionized water, dry at room temperature, obtains Spanon electrogenerated chemiluminescence sensing
Device；
Eluant, eluent therein is the mixed liquor of formic acid and methanol, and wherein the volume ratio of formic acid and methanol is 9:1.
The preparation method of 5 Spanon Electrochemiluminescsensor sensor of embodiment
(1) 0.35mmol template molecule and 4 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 12 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 18 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) CoNiN-nanoarray prepared in technical solution 2 is clipped on Stirring device, before being inserted into step (2)
It drives in body mixed solution, in N2At a temperature of environment and 30 DEG C of water-bath, with 60 revolutions per seconds of speed Stirring, while with 10 drops/
2 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN of 1 mmol/L is added dropwise into mixed solution simultaneously for the speed of second
Initiation polymerization is carried out, the MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on CoNiN-nanoarray；
(4) molecularly imprinted polymer containing template molecule of growth in situ on CoNiN-nanoarray for obtaining step (3)
MIP is immersed in eluant, eluent, and template molecule is carried out 10 min of elution at room temperature, then takes out, obtains no template molecule
Molecularly imprinted polymer NIP；Continue to be embathed 3 times with deionized water, dry at room temperature, obtains Spanon electrogenerated chemiluminescence biography
Sensor；
Eluant, eluent therein is the mixed liquor of formic acid and methanol, and wherein the volume ratio of formic acid and methanol is 9:3.
The preparation method of 6 Spanon Electrochemiluminescsensor sensor of embodiment
(1) 0.45mmol template molecule and 5 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 15 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 25 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) CoNiN-nanoarray prepared in technical solution 2 is clipped on Stirring device, before being inserted into step (2)
It drives in body mixed solution, in N2At a temperature of environment and 40 DEG C of water-bath, with 5 revolutions per seconds of speed Stirring, while with 20 drops/
3 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN of 1 mmol/L is added dropwise into mixed solution simultaneously for the speed of second
Initiation polymerization is carried out, the MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on CoNiN-nanoarray；
(4) molecularly imprinted polymer containing template molecule of growth in situ on CoNiN-nanoarray for obtaining step (3)
MIP is immersed in eluant, eluent, and template molecule is carried out 20 min of elution at room temperature, then takes out, obtains no template molecule
Molecularly imprinted polymer NIP；Continue to be embathed 4 times with deionized water, dry at room temperature, obtains Spanon electrogenerated chemiluminescence biography
Sensor；
Eluant, eluent therein is the mixed liquor of formic acid and methanol, and wherein the volume ratio of formic acid and methanol is 9:5.
The Spanon Electrochemiluminescsensor sensor of 7 embodiment 1 ~ 6 of embodiment preparation, applied to the detection of Spanon,
Steps are as follows:
(1) standard solution is prepared: preparing the Spanon standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: being working electrode by Spanon Electrochemiluminescsensor sensor, is prepared in inserting step (1)
The Spanon standard solution of various concentration takes out after hatching 10 min, is embathed 3 times with deionized water；
(3) working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is used as to electrode, with step
(2) the working electrode composition three-electrode system modified, is connected in electrochemiluminescdetection detection equipment；In a cell first
Be added afterwards 15 mL phosphate buffer solution PBS and 1mL 2 mmol/L hydrogen peroxide (H2O2) solution；With double rank Pulse Voltammetries
Method applies cyclical voltage to the working electrode of assembling, detects the light signal strength of electrogenerated chemiluminescence；The response light of blank standard specimen
Signal strength is denoted asA 0, the response light signal strength of the Spanon standard solution containing various concentration is denoted asA i, it is strong to respond optical signal
Spending reduced difference is ΔA = A 0-A i, ΔAWith the mass concentration of Spanon standard solutionCBetween it is linear, draw ΔA?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；Double rank arteries and veins
Rush parameter setting when voltammetry detection are as follows: initial potential is 0 V, and pulse potential is 0.9 V, and the burst length is 0.1 s, pulse
Period is 30 s；
(4) in sample to be tested Spanon detection: the Spanon standard solution in step (1) is replaced with sample to be tested, according to step
Suddenly the method in (2) and (3) is detected, the difference DELTA that light signal strength reduces according to responseAAnd working curve, it obtains to be measured
The content of Spanon in sample.
The Spanon Electrochemiluminescsensor sensor of 8 embodiment 1 ~ 6 of embodiment preparation is walked according to the detection of embodiment 7
The rapid detection for being applied to Spanon, the range of linearity are 4.0 × 10-5~ 1000 mmol/L, detection are limited to 2.0 nmol/L.
The detection of Spanon in 9 water sample of embodiment
Environmental water sample is accurately pipetted, the Spanon standard solution of certain mass concentration is added, is so that the water sample of Spanon not to be added
Blank carries out recovery testu, with Spanon Electrochemiluminescsensor sensor prepared by embodiment 1 ~ 6, according to embodiment 7
Step is detected, and the rate of recovery of Spanon in water sample is measured, and testing result is shown in Table 1:
The testing result of Spanon in 1 water sample of table
1 testing result of table it is found that the relative standard deviation (RSD) of result less than 3.1 %, average recovery rate is 98.0 ~
101.4%, show that the present invention can be used for the detection of Spanon in water sample, as a result the high sensitivity of method, high specificity accurately may be used
It leans on.
Claims (6)
1. a kind of preparation method of Spanon Electrochemiluminescsensor sensor, which is characterized in that the electroluminescent chemistry of the Spanon
Luminescence sensor is by growth in situ on cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-nanoarray without template molecule
Molecularly imprinted polymer NIP is obtained；Point that template molecule is free from without template molecule molecularly imprinted polymer NIP
Sub- imprinted polymer；The molecularly imprinted polymer without containing template molecule is by molecularly imprinted polymer containing template molecule
What MIP was obtained by eluted template molecule；The MIP of molecularly imprinted polymer containing template molecule is point containing template molecule
Sub- imprinted polymer；The template molecule is Spanon.
2. cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-nanoarray as described in claim 1, feature exist
In the preparation method of the CoNiN-nanoarray includes following preparation step:
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 1 ~ 3 mmol Ni (NO is weighed3)2With Fe (NO3)3Mixture and 3 ~ 9 mmol urea CO (NH2)2, it is put into
In 50 mL beakers, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 100 ~
It is reacted 9 ~ 12 hours at a temperature of 130 DEG C, cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electricity is prepared
Pole；
(4) 5 in the cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode insertion ammonium hydroxide obtained step (3) ~
It is taken out after 30 seconds, under ammonia environment, after being heated to 340 ~ 400 DEG C and being kept for 4 ~ 8 hours, continuation is dropped naturally under ammonia environment
To room temperature, it is then inserted into the phosphate buffer solution PBS containing dopamine and Ammonium Persulfate 98.5, in 20 ~ 40 DEG C of temperature
After lower reaction 4 ~ 6 hours, takes out and embathed 2 ~ 4 times with deionized water, cobalt nickel bimetal nitride nano chip arrays are prepared
Electrode CoNiN-nanoarray；
The described disposable electrode of throwing is selected from one of cycle unit: nickel foam, foam copper, pure nickel piece, pure copper sheet, pure cobalt piece,
Pure silicon piece, conductive carbon cloth；Ni (the NO3)2With Fe (NO3)3Mixture in the molar ratio of nickel and cobalt be 1:1；
In the phosphate buffer solution PBS containing dopamine and Ammonium Persulfate 98.5: dopamine concentration is 2 ~ 5 mg/mL, mistake
The concentration of amine sulfate is 3 ~ 8 mg/mL, and the concentration of phosphate buffer solution PBS is 0.1 mol/L, and pH value is 7.2 ~ 8.5.
3. the MIP of molecularly imprinted polymer containing template molecule as described in claim 1, which is characterized in that described containing template point
Sub- molecularly imprinted polymer MIP is that direct in-situ is grown on CoNiN-nanoarray, and preparation method includes following preparation step
It is rapid:
(1) 0.25 ~ 0.45mmol template molecule and 3 ~ 5 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, are added
Enter 8 ~ 15 mL acetonitriles, 30 min of ultrasound to whole dissolutions；
(2) 15 ~ 25 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound
To being uniformly mixed, precursor mixed solution is obtained；
(3) CoNiN-nanoarray is clipped on Stirring device, is inserted into the precursor mixed solution in step (2),
N2At a temperature of environment and 20 ~ 40 DEG C of water-bath, with 5 ~ 200 revolutions per seconds of speed Stirring, while with 1 ~ 20 drop/sec of speed
1 ~ 3 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN that 1 mmol/L is added dropwise simultaneously into mixed solution are drawn
Hair polymerization, obtains the MIP of molecularly imprinted polymer containing template molecule of growth in situ on CoNiN-nanoarray.
4. as described in claim 1 without template molecule molecularly imprinted polymer NIP, it is characterised in that the no template point
The preparation step of sub- molecularly imprinted polymer NIP are as follows: will be given birth in situ on CoNiN-nanoarray obtained in claim 3
The long MIP of molecularly imprinted polymer containing template molecule is immersed in eluant, eluent, and template molecule is carried out elution 5 ~ 20 at room temperature
Min then takes out, and obtains no template molecule molecularly imprinted polymer NIP；The eluant, eluent is the mixing of formic acid and methanol
Liquid, wherein the volume ratio of formic acid and methanol is 9:(1 ~ 5).
5. the preparation step of Spanon Electrochemiluminescsensor sensor as described in claim 1 are as follows: will be made in claim 2 ~ 4
On CoNiN-nanoarray growth in situ without template molecule molecularly imprinted polymer NIP, embathe 2 with deionized water ~
It 4 times, dries at room temperature, obtains Spanon Electrochemiluminescsensor sensor.
6. using Spanon Electrochemiluminescsensor sensor prepared by preparation method described in claim 1 ~ 5, applied to killing
The detection of worm amidine, which is characterized in that the detecting step is as follows:
(1) standard solution is prepared: preparing the Spanon standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: being working electrode by Spanon Electrochemiluminescsensor sensor, is prepared in inserting step (1)
The Spanon standard solution of various concentration takes out after hatching 10 min, is embathed 3 times with deionized water；
(3) working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is used as to electrode, with step
(2) the working electrode composition three-electrode system modified, is connected in electrochemiluminescdetection detection equipment；In a cell first
Be added afterwards 15 mL phosphate buffer solution PBS and 1mL 2 mmol/L hydrogen peroxide (H2O2) solution；With double rank Pulse Voltammetries
Method applies cyclical voltage to the working electrode of assembling, detects the light signal strength of electrogenerated chemiluminescence；The response light of blank standard specimen
Signal strength is denoted asA 0, the response light signal strength of the Spanon standard solution containing various concentration is denoted asA i, it is strong to respond optical signal
Spending reduced difference is ΔA = A 0-A i, ΔAWith the mass concentration of Spanon standard solutionCBetween it is linear, draw ΔA?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；Double rank arteries and veins
Rush parameter setting when voltammetry detection are as follows: initial potential is 0 V, and pulse potential is 0.9 V, and the burst length is 0.1 s, pulse
Period is 30 s；
(4) in sample to be tested Spanon detection: the Spanon standard solution in step (1) is replaced with sample to be tested, according to step
Suddenly the method in (2) and (3) is detected, the difference DELTA that light signal strength reduces according to responseAAnd working curve, it obtains to be measured
The content of Spanon in sample.
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