CN103866367A - Preparation method and application of tri-(2, 3-dibromopropyl) isocyanurate sensor - Google Patents
Preparation method and application of tri-(2, 3-dibromopropyl) isocyanurate sensor Download PDFInfo
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- CN103866367A CN103866367A CN201410127572.6A CN201410127572A CN103866367A CN 103866367 A CN103866367 A CN 103866367A CN 201410127572 A CN201410127572 A CN 201410127572A CN 103866367 A CN103866367 A CN 103866367A
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Abstract
The invention relates to a preparation method of a sensor capable of identifying tri-(2,3-dibromopropyl) isocyanurate. Tri-(2,3-dibromopropyl) isocyanurate is quickly determined by using the sensor. The preparation method comprises the following steps: firstly, polishing, cleaning and electrochemically activating a working electrode to obtain a pre-treated working electrode; adding a functional body solution and an imprinted molecule tri-(2, 3-dibromopropyl) isocyanurate solution into an electrolytic tank for electrochemical polymerization, and eluting to obtain an imprinted sensor with a functional body polymer membrane on the surface; and by taking the imprinted sensor as the working electrode and potassium ferricyanide as a testing base solution, adding the tri-(2, 3-dibromopropyl) isocyanurate solution, recording the peak current change condition of potassium ferricyanide to quickly test the content of tri-(2,3-dibromopropyl) isocyanurate. The imprinted sensor prepared by the invention is simple in method, and indirectly and quickly tests TBC by taking potassium ferricyanide (K2[Fe(CN)6]) as a probe molecule.
Description
Technical field
The present invention relates to one and can identify three-(2,3-dibromopropyl) the sensor preparation field of isocyanuric acid ester, be specifically related to one and can identify three-(2,3-dibromopropyl) preparation method of imprinted polymer sensor of isocyanuric acid ester, utilize the imprinted polymer sensor of invention preparation to carry out the application of Fast Measurement to three-(2,3-dibromopropyl) isocyanuric acid esters.
Background technology
Three-(2,3-dibromopropyl) isocyanuric acid ester (Tris (2,3-dibromopropyl) isocyanurate, be called for short TBC) be a kind of novel brominated flame-retardant, there is good flame retardation effect, volatility is low, consistency good, the characteristic such as durable and water-fast, be widely used in plastics, rubber and synthon.And research in recent years shows, TBC has potential endocrine disrupting.This class heterocycle brominated flame-retardant needs further to pay close attention to the harm of environment.At present, mainly contain Electrochemiluminescince, Ultra Performance Liquid Chromatography tandem mass spectrometry about the mensuration of TBC.Electrochemiluminescince selectivity is low, and Liquid Chromatography-Tandem Mass Spectrometry method instrument costliness, therefore, is necessary to find a kind of highly selective, quick and cheap detection method.
Molecular imprinting more and more receives people's concern with its structure effect precordainment, specific recognition and extensive practicality, all represent in a lot of fields good application prospect, as fields such as the separating of enantiomorph in chromatogram and positional isomers, chemobionics sensor, Solid-Phase Extraction, clinical medicine analysis, mimetic enzyme catalysis, membrane separation techniques.Wherein, especially concerned is that molecularly imprinted polymer replaces material molecule as recognition component in sensor, development tolerance by force, molecular imprinting sensor cheaply.Therefore, preparation TBC trace sensor is significant to the fast monitored of TBC.
The present invention adopts the method for electrochemical polymerization, utilizes TBC to make microsphere, has prepared the trace sensor that can identify TBC.And with the Tripotassium iron hexacyanide (K
3[Fe (CN)
6]) be probe molecule, realize indirect, Fast Measurement to TBC.The detection linearity range of this trace sensor is 1.4 × 10
-10-6.7 × 10
-10mol/L, detects and is limited to 6.64 × 10
-12mol/L, the time of response short (about 30s), has obtained comparatively desirable result.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of three-(2,3-dibromopropyl) isocyanuric acid ester (TBC) molecular imprinting sensor.
Another object of the present invention is also to provide the application on Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester (TBC) of three-(2,3-dibromopropyl) isocyanuric acid ester (TBC) molecular imprinting sensor based on preparation.
The object of the invention is to be achieved by the following scheme:
1, the pre-treatment of working electrode: be that on the oxidation aluminium paste of 0.3 μ m and 0.05 μ m, sanding and polishing becomes minute surface at particle diameter respectively by working electrode, then use successively rare HNO
3, dehydrated alcohol, distilled water ultrasonic cleaning, repeat 2～3 times, each 3min, finally carries out electrochemical activation processing, obtains pretreated working electrode.
2, the preparation of trace sensor:
0.01～0.05g functive is dissolved in 0.1mol/L solvent and is mixed with functive solution, then in electrolyzer, add functive solution and microsphere three-(2,3-dibromopropyl) isocyanuric acid ester solution 8～15mL;
Adopt working electrode, supporting electrode and reference electrode three-electrode system by functive and three-(2; 3-dibromopropyl) isocyanuric acid ester carries out electrochemical polymerization: with cyclic voltammetry scanning 25～30 times, working electrode is prepared into surface band the sensor of functive polymeric film;
After completing, sensor is soaked to 12h with eluent, to remove the microsphere three-(2 in polymeric film, 3-dibromopropyl) isocyanuric acid ester, make three of molecular configuration hole-(2,3-dibromopropyl) the trace sensor of isocyanuric acid ester molecule, and adopt differential pulse method to carry out trace Effect Evaluation to this trace sensor and circulation ratio is measured.
The application of 3, Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester: taking trace sensor as working electrode, the Tripotassium iron hexacyanide [(K of platinum wire electrode as supporting electrode, saturated Ag/AgCl electrode as reference electrode, 5mmol/L
3fe (CN)
6)] for test end liquid, adopt timing Amperometric, at room temperature, by the liquid Tripotassium iron hexacyanide [(K at the bottom of the test of trace sensor immersion 8mL
3fe (CN)
6)] in, when background current reach stable after, in end liquid, add three of 0.10mL-(2 every 60s, 3-dibromopropyl) isocyanuric acid ester solution formation mixing solutions, record the peak current situation over time of the Tripotassium iron hexacyanide in mixing solutions, obtain the linear relationship between isocyanuric acid ester strength of solution, realize the content of Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester.
Rare HNO of the present invention
3, its concentration expressed in percentage by volume is 50%.
Electrochemical activation processing of the present invention is the H at 0.5mol/L
2sO
4in carry out cyclic voltammetry scan in-0.3～1.5V.
Functive of the present invention refers to o-aminophenol, near amino thiophenols, 2-mercaptobenzimidazole, tetrabutylammonium perchlorate.
Solvent of the present invention, refers to HClO
4or C
2h
5oH.
The present invention is preparing in the step of trace sensor, described microsphere three-(2,3-dibromopropyl) isocyanuric acid ester solution, and its concentration range is 1.0 × 10
-3～1.0 × 10
-4mol/L.
Eluent of the present invention, refers to sulfuric acid, nitric acid, Hydrogen bromide or hydrochloric acid, and its volumetric molar concentration is 0.5～1.0mol/L.
Working electrode of the present invention is glass-carbon electrode, platinum disk electrode or gold electrode.
Supporting electrode of the present invention is that platinum is to electrode.
Reference electrode of the present invention is silver/silver chloride electrode or mercurous chloride electrode.
The present invention in the step of the application of Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester, three-(2,3-dibromopropyl) described isocyanuric acid ester solutions, its concentration is 1.0 × 10
-8mol/L.
The present invention's functive used forms fine and close polymeric film through electrochemical polymerization in electrode surface polyreaction.The C=O of the function Ji Tuan – NH existing in functive easily and in microsphere three-(2,3-dibromopropyl) isocyanuric acid ester forms hydrogen bond.When wash-out, in strongly acidic solution, hydrogen bond action in trace sensor film is by destroyed, cause microsphere three-(2,3-dibromopropyl) isocyanuric acid ester overflows from sensor film, thereby in trace sensor film, formed the hole matching with microsphere, microsphere is preferentially identified in this hole.At the K of 5mmol/L
3[Fe (CN)
6] in test soln, three-(2,3-dibromopropyl) isocyanuric acid ester molecules enter in molecular imprinting sensor by hydrogen bond action, cause K
3[Fe (CN)
6] response of peak current changing value.
The present invention adopts differential pulse method (potential range :-0.2～0.6V, current potential increment: 0.005V, amplitude: 0.05V, pulse width: 0.1s, sampling width: 0.02s) to carry out trace Effect Evaluation to trace sensor.At the K of 5mmol/L
3[Fe (CN)
6] in solution, add different concns (1.0 × 10
-10, 1.0 × 10
-9, 1.0 × 10
-8mol/L) microsphere three-(2,3-dibromopropyl) isocyanuric acid ester.Because the film of gained after molecular imprinting remains with the three-dimensional cavity that can identify microsphere three-(2,3-dibromopropyl) isocyanuric acid ester, [Fe (CN)
6]
3-molecule diffuses to sensor surface by hole, and electrochemical reaction occurs; When three-(2,3-dibromopropyl) isocyanuric acid ester molecules in solution enter behind trace hole, hole sealing, [Fe (CN)
6]
3-diffusion hindered, [the Fe (CN) of sensor surface
6]
3-concentration reduces, thereby electric current is declined, and when three-(2,3-dibromopropyl) isocyanuric acid ester concentrations in solution are larger, hole sealing is more, [the Fe (CN) of sensor surface
6]
3-concentration is lower, and peak point current reduces according to the increase of microsphere three-(2,3-dibromopropyl) isocyanuric acid ester concentration.
The present invention also utilizes the circulation ratio of differential pulse method determination sensor, is specially: the H by used sensor at 0.50mol/L
2sO
4in solution, ultrasonic concussion washing 2h, can make sensor substantially return to the state before response with after distilled water drip washing.Applying this sensor, adopt differential pulse method, is 1.0 × 10 at three-(2,3-dibromopropyl) isocyanuric acid ester concentrations
-8when mol/L, (in test fluid, contain the K of 5mmol/L
3[Fe (CN)
6], under room temperature condition, carry out) repeat 3 parallel laboratory tests, the results are shown in following table.
Current-responsive changing value (Δ I) average out to 49.6 μ Α, relative standard deviation RSD is 1.76%.This sensor has good circulation ratio.
The present invention utilizes timing Amperometric to make detectability and the response performance of I-T curve to trace sensor and tests, detailed process is as follows: taking 5mmol/L potassium ferricyanide solution as background solution, after background current is stable, in background solution, add three of same volume same concentration-(2 continuously successively, 3-dibromopropyl) isocyanuric acid ester acetonitrile solution, records the peak current situation over time of the Tripotassium iron hexacyanide.Along with adding gradually of three-(2,3-dibromopropyl) isocyanuric acid esters, K
3[Fe (CN)
6] reduction peak current reduce gradually, can there is a platform in each concentration stage, in 30s, tend towards stability, show that TBC trace sensor has the time of response faster.Be 1.4 × 10 in concentration
-10～6.7 × 10
-10within the scope of mol/L, K
3[Fe (CN)
6] the concentration of peak current changing value and three-(2,3-dibromopropyl) isocyanuric acid ester be linear increase relation, concentration is greater than 6.7 × 10
-10when mol/L, because recognition site is tending towards saturated, affect detected result.The peak current changing value Δ I of the Tripotassium iron hexacyanide sees the following form:
In his-and-hers watches, result is made the linear regression graph of electric current and concentration, obtains linear equation to be: y=-3.27577x+0.01441, wherein slope is its sensitivity m, show that sensitivity is 3.28 × 10
4μ A/ (μ mol/L); Detection that must this trace sensor by detection limit calculation formula 3 × SD/m is limited to 6.64 × 10
-12mol/L.
Brief description of the drawings
Fig. 1 is electrochemical polymerization cyclic voltammogram.
Fig. 2 is the trace effect figure of trace sensor to different concns TBC in the embodiment of the present invention 1.
Fig. 3 is the I-T graphic representation of trace sensor in the embodiment of the present invention 1.
Fig. 4 is electric current in the embodiment of the present invention 1 and the linear regression graph of concentration.
Embodiment
Below in conjunction with embodiment, the present invention is described in more detail.
Working electrode pre-treatment:
Glass-carbon electrode is polished respectively on particle diameter is the oxidation aluminium paste of 0.3 μ m and 0.05 μ m, until there is smooth minute surface, then use successively rare HNO
3(volume ratio is 1:1), dehydrated alcohol, distilled water ultrasonic cleaning, repeat 3 times, each 3min.Then carry out electrochemical activation processing [at the H of 0.5mol/L
2sO
4in carry out cyclic voltammetry scan in-0.3～1.5V], until obtain stable cyclic voltammetric response curve.
The preparation of trace sensor:
0.0136g o-aminophenol is dissolved in to 0.1mol/L HClO
4in, regulate pH value to be slightly acidic with 0.4mol/L NaOH, be settled to 50mL.In electrolyzer, add 20mL o-aminophenol solution and 10mL1.0 × 10
-4mol/L tri--(2,3-dibromopropyl) isocyanuric acid ester solution.Taking glass-carbon electrode after treatment as working electrode, platinum wire electrode is supporting electrode, saturated Ag/AgCl electrode is reference electrode, adopt traditional three-electrode system to carry out electrochemical polymerization: to utilize cyclic voltammetry, be under the condition of 100mV/s, scanning potential range-0.2～1.0V in scanning speed, scan 30 times, obtain poly-o-aminophenol film sensors in the polymerization of glass-carbon electrode surface electrical.After completing, with the sulfuric acid immersion sensor 12h of 0.5mol/L, to remove three in polymeric film-(2,3-dibromopropyl) isocyanuric acid ester, make the molecular imprinting sensor that remains with three-(2,3-dibromopropyl) isocyanuric acid ester molecular configuration holes.Its electrochemical polymerization cyclic voltammogram as shown in Figure 1.Adopt differential pulse method to carry out trace Effect Evaluation (the results are shown in Figure 2) and circulation ratio mensuration to sensor.
The application of Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester:
Taking trace sensor as working electrode, the Tripotassium iron hexacyanide [(K of platinum wire electrode as supporting electrode, saturated Ag/AgCl electrode as reference electrode, 5mmol/L
3fe (CN)
6)] for test end liquid, adopt timing Amperometric, at room temperature, by the liquid Tripotassium iron hexacyanide [(K at the bottom of the test of trace sensor immersion 8mL
3fe (CN)
6)], when background current reach stable after, in end liquid, add 0.10mL1.0 × 10 every 60s
-8three of mol/L-(2,3-dibromopropyl) isocyanuric acid ester solution, record the peak current situation over time of the Tripotassium iron hexacyanide in mixing solutions, obtain I-T curve (as shown in Figure 3), calculate Tripotassium iron hexacyanide reduction current value and three-(2 in mixing solutions according to I-T opisometer, 3-dibromopropyl) linear relationship (as shown in Figure 4) between isocyanuric acid ester strength of solution, realizes the content of Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester.
Working electrode pre-treatment:
Gold electrode, containing the 5min that polishes on the chamois leather of alumina slurry that particle diameter is 0.03 μ m, is then put in to V
30%H2O2: V
dense H2SO4in the solution of=1:3, soak 10min, use respectively the each supersound washing 5min of redistilled water and dehydrated alcohol, to remove aluminum oxide and other impurity of electrode surface absorption, then at 1.0mol/L H
2sO
4in solution, in the potential range of-0.20～+ 1.40V, carry out cyclic voltammetry scan, until obtain stable cyclic voltammetric response.
The preparation of trace sensor:
To contain 0.0500g2-mercaptobenzimidazole and be dissolved in 30mL ethanol, this solution and 8mL1.0 × 10
-3mol/L tri--(2,3-dibromopropyl) isocyanuric acid ester solution mixes, logical nitrogen deoxygenation 5min.Taking gold electrode after treatment as working electrode, platinum wire electrode is supporting electrode, saturated Ag/AgCl electrode is reference electrode, adopt traditional three-electrode system to carry out electrochemical polymerization: to utilize cyclic voltammetry, be that 100mV/s, scanning potential range are under the condition of-0.6～+ 1.3V in scanning speed, scan 28 times, make poly-2-mercaptobenzimidazole polymeric film sensor in gold electrode surfaces polymerization.After polymerization completes, Hydrogen bromide supersound washing 3min by sensor at 0.8mol/L, wrap into three in polymeric film-(2 with wash-out, 3-dibromopropyl) isocyanuric acid ester, make and remain with three-(2,3-dibromopropyl) the molecular imprinting sensor in isocyanuric acid ester molecular configuration hole, and adopt differential pulse method to carry out trace Effect Evaluation to this trace sensor and circulation ratio is measured.
The application of Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester:
Taking trace sensor as working electrode, the Tripotassium iron hexacyanide [(K of platinum wire electrode as supporting electrode, saturated Ag/AgCl electrode as reference electrode, 5mmol/L
3fe (CN)
6)] for test end liquid, adopt timing Amperometric, at room temperature, by the liquid Tripotassium iron hexacyanide [(K at the bottom of the test of trace sensor immersion 8mL
3fe (CN)
6)], when background current reach stable after, in end liquid, add 0.10mL1.0 × 10 every 60s
-9three of mol/L-(2,3-dibromopropyl) isocyanuric acid ester solution, record the peak current situation over time of the Tripotassium iron hexacyanide in mixing solutions, obtain I-T curve, calculate Tripotassium iron hexacyanide reduction current value and three-(2 in mixing solutions according to I-T opisometer, 3-dibromopropyl) linear relationship between isocyanuric acid ester strength of solution, realizes the content of Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester.
Working electrode pre-treatment:
Glass-carbon electrode is polished respectively on particle diameter is the oxidation aluminium paste of 0.3 μ m and 0.05 μ m, until there is smooth minute surface, then use successively rare HNO
3(volume ratio is 1:1), dehydrated alcohol, distilled water ultrasonic cleaning, repeat 3 times, each 3min.Then carry out electrochemical activation processing [at the H of 0.5mol/L
2sO
4in carry out cyclic voltammetry scan in-0.3～1.5V], until obtain stable cyclic voltammetric response curve.
The preparation of trace sensor:
The logical 99% nitrogen deoxygenation 5min of mixed solution by 30mL containing 0.0117g tetrabutylammonium perchlorate and 0.0324g o-amino thiophenol, by pretreated glass-carbon electrode self-assembly 4h in this solution.Then, in this solution, add 15mL0.5 × 10
- 3mol/L tri--(2,3-dibromopropyl) isocyanuric acid ester solution, makes polymer fluid.Taking glass-carbon electrode after treatment as working electrode, platinum wire electrode is supporting electrode, saturated Ag/AgCl electrode is reference electrode, adopt traditional three-electrode system to carry out electrochemical polymerization: to utilize cyclic voltammetry, be 100mV/s in sweep velocity, potential range is under the condition of-0.40～+ 1.40V, and scan round 30 times obtain o-amino thiophenol polymeric membrane sensor at glass-carbon electrode surface aggregate.By sensor ultrasonic 4min in the hydrochloric acid soln of 1.0mol/L, wrap into three in polymeric film-(2 with wash-out, 3-dibromopropyl) isocyanuric acid ester, make and remain with three-(2,3-dibromopropyl) the molecular imprinting sensor in isocyanuric acid ester molecular configuration hole, and adopt differential pulse method to carry out trace Effect Evaluation to this trace sensor and circulation ratio is measured.
The application of Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester:
Taking trace sensor as working electrode, the Tripotassium iron hexacyanide [(K of platinum wire electrode as supporting electrode, saturated Ag/AgCl electrode as reference electrode, 5mmol/L
3fe (CN)
6)] for test end liquid, adopt timing Amperometric, at room temperature, by the liquid Tripotassium iron hexacyanide [(K at the bottom of the test of trace sensor immersion 8mL
3fe (CN)
6)], when background current reach stable after, in end liquid, add 0.10mL1.0 × 10 every 60s
-10three of mol/L-(2,3-dibromopropyl) isocyanuric acid ester solution, record the peak current situation over time of the Tripotassium iron hexacyanide in mixing solutions, obtain I-T curve, calculate Tripotassium iron hexacyanide reduction current value and three-(2 in mixing solutions according to I-T opisometer, 3-dibromopropyl) linear relationship between isocyanuric acid ester strength of solution, realizes the content of Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester.
Embodiment 4
Working electrode pre-treatment:
Platinum disk electrode is polished respectively on particle diameter is the oxidation aluminium paste of 0.3 μ m and 0.05 μ m, until there is smooth minute surface, then use successively rare HNO
3(volume ratio is 1:1), dehydrated alcohol, distilled water ultrasonic cleaning, repeat 3 times, each 3min.Then carry out electrochemical activation processing [at the H of 0.5mol/L
2sO
4in carry out cyclic voltammetry scan in-0.3～1.5V], until obtain stable cyclic voltammetric response curve.
The preparation of trace sensor:
0.0209g o-aminophenol is dissolved in to 0.1mol/L HClO
4in, regulate pH value to be slightly acidic with 0.4mol/L NaOH, be settled to 50mL.In electrolyzer, add 20mL o-aminophenol solution and 15mL1.0 × 10
-4mol/L TBC solution.Taking platinum disk electrode after treatment as working electrode, platinum wire electrode is supporting electrode, saturated calomel electrode is reference electrode, adopt traditional three-electrode system to carry out electrochemical polymerization: to utilize cyclic voltammetry, be under the condition of 100mV/s, scanning potential range-0.2～1.0V in scanning speed, scan 25 times, obtain poly-o-aminophenol film sensors in the polymerization of platinum disk electrode surface electrical.After completing, with the sulfuric acid immersion sensor 12h of 0.8mol/L, to remove three-(2 in polymeric film, 3-dibromopropyl) isocyanuric acid ester, make and remain with three-(2,3-dibromopropyl) the molecular imprinting sensor in isocyanuric acid ester molecular configuration hole, and adopt differential pulse method to carry out trace Effect Evaluation to this trace sensor and circulation ratio is measured.
The application of Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester:
Taking trace sensor as working electrode, the Tripotassium iron hexacyanide [(K of platinum wire electrode as supporting electrode, saturated Ag/AgCl electrode as reference electrode, 5mmol/L
3fe (CN)
6)] for test end liquid, adopt timing Amperometric, at room temperature, by the liquid Tripotassium iron hexacyanide [(K at the bottom of the test of trace sensor immersion 8mL
3fe (CN)
6)], when background current reach stable after, in end liquid, add 0.10mL1.0 × 10 every 60s
-9three of mol/L-(2,3-dibromopropyl) isocyanuric acid ester solution, record the peak current situation over time of the Tripotassium iron hexacyanide in mixing solutions, obtain I-T curve, calculate Tripotassium iron hexacyanide reduction current value and three-(2 in mixing solutions according to I-T opisometer, 3-dibromopropyl) linear relationship between isocyanuric acid ester strength of solution, realizes the content of Fast Measurement three-(2,3-dibromopropyl) isocyanuric acid ester.
Claims (5)
1. can identify the preparation method of three-(2,3-dibromopropyl) isocyanuric acid ester (TBC) molecular imprinting sensor sensing film for one kind, it is characterized in that:
1) processing of working electrode: before masking, by working electrode polishing, supersound washing 2 ~ 5 min respectively in redistilled water and dehydrated alcohol, repeat 3 times, then carries out electrochemical activation processing [at the H of 0.5 mol/L
2sO
4in carry out cyclic voltammetry scan in-0.3 ~ 1.5 V], until obtain stable cyclic voltammetric response curve.
2) preparation of TBC trace sensor: electrochemical polymerization adopts traditional three-electrode system (working electrode, supporting electrode and reference electrode).0.01 ~ 0.05 g functive is dissolved in 30 ~ 50 solvents, then adds 8 ~ 15 mL 1 ' 10
-4~ 1 ' 10
-3mol/L microsphere TBC solution, the polymerization of electricity consumption polymerization.After electropolymerization completes, soak 12 h with eluent, and be aided with ultrasonic wash-out, to remove the TBC in polymeric matrix, to make the molecular imprinting polymeric sensing membrane device that remains with TBC molecular configuration hole.At room temperature, with 5mmol/L K
3[Fe (CN)
6] be test end liquid, adopt the molecular imprinting effect of differential pulse method TBC trace sensor.
3) measuring method: utilize three electrode inspectors, the trace sensor of above-mentioned preparation is working electrode, and platinum wire electrode is supporting electrode, and saturated Ag/AgCl electrode is reference electrode.Trace electrode is immersed to 8 ml 5mmol/L K
3[Fe (CN)
6] in Tripotassium iron hexacyanide background solution, when background current reach stable after, inject wherein TBC acetonitrile solution to be measured every 60 s.Under agitation condition, under+0.12 V voltage, record the variation of Tripotassium iron hexacyanide reduction current with timing Amperometric, thereby calculate the relation between Tripotassium iron hexacyanide reduction current value and TBC strength of solution, the content of indirect measurement TBC.
2. according to claim 1ly identify three-(2,3-dibromopropyl) preparation method of isocyanuric acid ester (TBC) molecular imprinting sensor sensing film, it is characterized in that described functive material refers to o-aminophenol, near amino thiophenols, 2-mercaptobenzimidazole, tetrabutylammonium perchlorate.
3. according to claim 1ly identify three-(2,3-dibromopropyl) preparation method of isocyanuric acid ester (TBC) molecular imprinting sensor sensing film, it is characterized in that the working electrode described in summary of the invention 1 and 2 is glass-carbon electrode, platinum disk electrode and gold electrode.
4. according to claim 1ly identify three-(2,3-dibromopropyl) preparation method of isocyanuric acid ester (TBC) molecular imprinting sensor sensing film, it is characterized in that described supporting electrode be platinum to electrode, described reference electrode is silver/silver chloride electrode and mercurous chloride electrode.
5. the preparation method who identifies three-(2,3-dibromopropyl) isocyanuric acid ester (TBC) molecular imprinting sensor sensing film according to claim 1, is characterized in that described solvent is perchloric acid and ethanol.
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| CN111551604A (en) * | 2020-07-02 | 2020-08-18 | 盐城工学院 | Preparation method of flumorph molecular imprinting electrochemical sensor |
| CN111900381A (en) * | 2019-05-05 | 2020-11-06 | 香港城市大学深圳研究院 | Method for activating iron ferricyanide and zinc ion battery prepared thereby |
| CN112007382A (en) * | 2020-09-03 | 2020-12-01 | 湖北医药学院 | Solid phase micro-extraction column and preparation and application method thereof |
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