CN109187687A - It is conjugated the preparation of organic poromerics modified electrode and the application as peroxynitrite electrochemical sensor - Google Patents

It is conjugated the preparation of organic poromerics modified electrode and the application as peroxynitrite electrochemical sensor Download PDF

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CN109187687A
CN109187687A CN201811230195.3A CN201811230195A CN109187687A CN 109187687 A CN109187687 A CN 109187687A CN 201811230195 A CN201811230195 A CN 201811230195A CN 109187687 A CN109187687 A CN 109187687A
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electrode
modified electrode
onoo
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poromerics
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CN109187687B (en
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刘秀辉
李琳
刘福鑫
张彬雁
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Northwest Normal University
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    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333Ion-selective electrodes or membranes
    • G01N27/3335Ion-selective electrodes or membranes the membrane containing at least one organic component

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Abstract

The present invention provides a kind of preparations of organic poromerics modified electrode (CMP/GCE) of conjugation, it is under the conditions of being protected from light, make solvent with the mixed solution of triethylamine and toluene, 1,3,5- tri- ethynylbenzene and 2- amino -3,5- dibromo pyridine is as substrate, a kind of organic poromerics (CMP) of conjugation is made under given conditions, then CMP is made into dispersant liquid drop and is coated in glassy carbon electrode surface, final modified electrode is made.The modified electrode is to peroxynitrite (ONOO) there is good electrochemical response, with the wide range of linearity to 5 orders of magnitude, low detection limit (1.54 × 10‑9 M), strong anti-interference performance and the features such as stability and favorable reproducibility, can be measured in real time;In addition, the modified electrode electrode is in drug antioxidant for clearing ONOOElectrochemical Detection in have satisfied as a result, showing that the modified electrode has good application prospect, be expected to the detection applied to pharmaceutical properties.

Description

It is conjugated the preparation of organic poromerics modified electrode and as peroxynitrite The application of electrochemical sensor
Technical field
The present invention relates to a kind of preparations of peroxynitrite electrochemical sensor, are especially conjugated organic micropore material Expect the preparation method of (CMP) modified electrode;Present invention simultaneously relates to be conjugated detecting for organic poromerics (CMP) modified electrode Peroxynitrite (ONOO in solution-) application.
Background technique
Peroxynitrite (peroxynitrite anion, ONOO-) as most important and most active active nitrogen One of (RNS), it is to be combined rapidly to generate by two kinds of free radicals (nitric oxide and oxygen radical) in organism living. ONOO-And its intermediate derived from takes part in most of oxidations and nitration reaction in organism, is to lead to cellular damage, energy consumption It exhausts and an important factor for cell death and NO generates the important link of pathology damage effect.Therefore, ONOO in organism-'s Accurate detection and quantization have become the key of disease preliminary clinical diagnosis, and attract extensive attention.At the same time, due to intracorporal ONOO-Service life is short, it is active it is high, concentration is low, therefore, establishing efficient, reliable method for qualitative and quantitative detection is still a problem.According to Existing report, ultraviolet-visible spectrophotometry, immunohistochemical method, high performance liquid chromatography etc. are used ONOO-'s Detection.Although the acceptance of these methods is very high, the specificity as necessary to their the complicated pretreatment of needs, shortages, It is time-consuming and at high cost, so can not accomplish the intracorporal real-time monitoring of biology.
Electrochemistry provides direct, the online and real-time measurement about important biomolecule species, it is a kind of sensitive, easy Biochemical analysis method.Therefore, sensitive, convenient and fast ONOO is developed-Electrochemical sensor is just particularly important.From 2007 Since reporting for the first time, as a kind of Space network of polymer skeleton constructed by conjugate unit, it is conjugated organic poromerics or total Yoke microporous polymer (Conjugated Microporous Polymer, CMP) presents excellent porosity, stable bone Frame structure and diversified function, it is shown that in the application value and bright prospects of various fields.It is reported that passing through regulation shape Looks can improve the performance for being conjugated organic poromerics, and being conjugated organic poromerics (CMP) has better electronic conduction ability, There is potential application in the relevant fields such as energy environments, the biological medicines such as photoelectricity, sensing, catalysis in addition to adsorbing separation etc. Value.However, it is seldom in relation to being conjugated report of organic poromerics for sensor at present, it especially has no for peroxide nitrous The report of base anion sensors.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods for being conjugated organic poromerics modified electrode;
The present invention also relates to application of the modified electrode as peroxynitrite electrochemical sensor.
One, it is conjugated the preparation of organic poromerics (CMP)
The present invention is conjugated the preparation method of organic poromerics, is under the conditions of being protected from light, by the mixed solution of triethylamine and toluene (volume ratio of triethylamine and toluene is 1:1 ~ 1:9) is added in anti-reactor as solvent, after magnetic agitation is uniform, in N2It protects Reactant is sequentially added under shield: tri- ethynylbenzene of 1,3,5- and 2- amino -3,5- dibromo pyridine (molar ratio of the two is 1:1 ~ 1: 7);Add catalyst cuprous iodide and the (dosage of the cuprous iodide and four triphenyl phosphorus palladiums respectively reaction of four triphenyl phosphorus palladiums 0.01 ~ 0.08 times, 0.01 ~ 0.06 times of object integral molar quantity), it stirs evenly and is placed in oil bath pan, be to slowly warm up to 60 ~ 90 DEG C, react 50 ~ 100 h;It is cooled to room temperature, resulting polymers are successively washed with chloroform, water, acetone, methanol, most Carry out 24 ~ 96 h of soxhlet extraction in methyl alcohol afterwards, final product must be conjugated organic poromerics CMP through drying, grinding.
Two, it is conjugated the structural characterization of organic poromerics CMP
Fig. 1 A is the SEM figure for being conjugated organic poromerics CMP.From Figure 1A it can be seen that, the material in a tubular form, surface more light Sliding, pipe diameter is about 0.4 ~ 2 μm.
The TEM that Figure 1B is CMP schemes.Figure B shows that the material is hollow pipe-in-pipe structure, the thickness of tube wall 10nm ~ Between the range of 30nm.The bore of inner tube between 80 ~ 120nm, the bore of outer tube 200 ~ 400nm it Between.
Fig. 1 C is the EDX figure for being conjugated organic poromerics.Fig. 1 C shows the strong peak of C, N, O and Br, shows to be conjugated organic (SEM is to carry out on copper mesh, therefore there are the peaks of Cu) is successfully made in poromerics.
Fig. 2 is the nitrogen adsorption desorption figure (BET) for being conjugated organic poromerics (CMP).Figure it is seen that it belongs to TypeType curve, but also there is TypeSome features of type curve, in P/P0 It is stagnant once between=0.4 ~ 0.8 Ring illustrates to exist simultaneously micropore and mesoporous in material.Its specific surface area is 319.115 m2/g.Illustration is internal pore-size distribution Figure, shows most of apertures in 2 nm or so.
Three, the preparation and performance of modified electrode material
1, the preparation of modified electrode material
Disperse the organic poromerics CMP of conjugation of above-mentioned preparation in the mixed solution (percentage by volume of ethyl alcohol of second alcohol and water Be 20 ~ 80%) in be made into the dispersion liquid that concentration is 0.2 ~ 1.0mg/mL, and drop coating is in processed bare glassy carbon electrode, room Temperature is dry, and modified electrode CMP/GCE is made, be conjugated organic poromerics CMP coating with a thickness of 200 ~ 1200 nm.
2, the performance of modified electrode material
Fig. 3 is bare electrode GCE(A), modified electrode CMP/GCE(B) it is being free of (a) and is containing (b) 8.76 × 10-6 The ONOO of M- PBS(pH=7.0 0.2M) in cyclic voltammetry curve, sweep speed be 50 mV/s.As seen from Figure 3, two different modified electrodes Middle each b curve is all higher than corresponding a curve current-responsive, this illustrates ONOO-Electrochemistry can be generated on two kinds of electrodes Signal.In comparison, ONOO-In CMP/GCE(Fig. 3 B b curve) on electrochemical response signal be apparently higher than naked GCE(figure 3A b curve), illustrate the organic poromerics of the conjugation to ONOO-Oxidation have significant facilitation.
Fig. 4 is that CMP/GCE is containing various concentration ONOO-0.2 M PBS(pH 7.0) in chronoamperogram, illustration For corresponding linear relationship chart.By Fig. 4 it can be found that current-responsive can be with ONOO- The increase of concentration and constantly increase.By illustration It is found that working as ONOO- Concentration is 4.62 × 10-9 ~ 9.51×10-5When within the scope of M, response current Ip and ONOO-The logarithm of concentration In good linear relationship, equation of linear regression are as follows: Ip (μ A)=- 0.0622 [ONOO-] -0.1065, R2 = 0.9994.It follows that ONOO- The range of linearity of detection is 4.62 × 10-9 ~9.51×10-5M, detection are limited to 1.54 × 10- 9M。
Fig. 5 is the chronoa mperometric plot figure of modified electrode CMP/GCE at different conditions.(a) add in PBS buffer solution Enter 3 × 10-6 M O2 •−;(b) 3 × 10 are added in the PBS solution of ascorbic acid containing 3mM (AA)-6 M ONOO- ;(c) it is taken off containing 3mM 3 × 10 are added in the PBS solution of melanin (Melatonin)-6 M ONOO- ;(d) reduced glutathione containing 3mM (GSH) 3 × 10 are added in PBS solution-6 M ONOO- , operating potential is 1.0 V.Curve (a) display, by 3 × 10-6M ONOO- It is added In PBS solution, current-responsive is increased rapidly.However, when different antioxidants is first added in PBS solution, (ascorbic acid is moved back black Pigment, reduced glutathione), then add 3 × 10-6 M ONOO- , discovery current-responsive is substantially reduced, such as curve b, c, Shown in d.As a result illustrate the removing ONOO that these three antioxidants have had- Ability.In comparison, drug antioxidant Reduced glutathione (d curve) removes ONOO- Ability it is best.Therefore, modified electrode CMP/GCE can be used for electrochemistry inspection Survey the ability of drug antioxidant for clearing peroxynitrite.
In conclusion the present invention has the advantage that compared with prior art
1, the present invention constructs a kind of ONOO based on CMP using organic poromerics is conjugated- Sensor, the sensor have Detection range is wide, detection limit is low, detection process is simple, high sensitivity.In addition, its preparation process is simple, and it is low in cost, easily grasp Make, can be used for a long time.
2, modified electrode prepared by the present invention is to ONOO- Have a sensitive electrochemical response, strong anti-interference performance, stability and Favorable reproducibility can be measured in real time;
3, modified electrode prepared by the present invention is used for drug antioxidant for clearing ONOO- In the Electrochemical Detection of ability, obtain full Meaning is as a result, show that the modified electrode has good application prospect in biosensor, and be expected to the inspection applied to pharmaceutical properties It surveys.
Detailed description of the invention
Fig. 1 is transmission electron microscope picture (SEM), transmission electron microscope picture (TEM) and the energy color of modified electrode surfacing of the present invention It dissipates X ray picture (EDX).
Fig. 2 is the nitrogen adsorption desorption figure (BET) for being conjugated organic poromerics, and illustration is its grain size distribution.
Fig. 3 is that different modifying electrode is being free of (a) and is containing (b) 8.76 × 10-6 M ONOO- 0.2M PBS (pH= 7.0) cyclic voltammetry curve in.
Fig. 4 is ONOO of the CMP/GCE to various concentration- The chronoamperogram and ONOO of detection- Concentration and its electric current ring Linear relationship chart (illustration) between answering.
Fig. 5 is in the PBS buffer solution without or with different antioxidants, and CMP/GCE is to ONOO- Chrono-amperometric Curve graph.
Specific embodiment
The preparation of modified electrode CMP/GCE of the present invention and application are described further below by specific embodiment.
1, it is conjugated the preparation of organic poromerics CMP: taking 4 ml of triethylamine, 4 ml of toluene, sequentially add three mouthfuls of 50mL Bottle, magnetic agitation at room temperature, then in N2Sequentially add 1,3,5- tri- ethynylbenzenes (0.25 mol) under protection, amino -3 2-, 5- dibromo pyridine (0.051 mol), cuprous iodide (0.0088 mol), four triphenyl phosphorus palladiums (0.0015 mol) stir evenly It is placed in oil bath pan, is to slowly warm up to 80 DEG C of reaction 72h, entire reaction process is being protected from light lower progress.It cools down after reaction To room temperature, resulting polymers successively use chloroform, water, acetone, then methanol washing carries out soxhlet extraction 72 in methyl alcohol H, final product must be conjugated organic poromerics CMP through drying, grinding;
2, the preparation of modified electrode CMP/GCE
(1) pretreatment of glass-carbon electrode: glass-carbon electrode is successively polished to the aluminum oxide suspension of 0.30 μm, 0.05 μm Mirror surface, then successively after ethyl alcohol that volume fraction is 95 %, secondary distilled water ultrasonic cleaning, the glass-carbon electrode that obtains that treated; Then it is three-electrode system to electrode, saturated calomel electrode for reference electrode by working electrode, platinum column of glass-carbon electrode, is containing Have in the 0.1M potassium chloride electrolyte solution of 1.0mM potassium ferricyanide probe molecule, carrying out cyclic voltammetry scan, (sweeping speed is 50mV/ S), finally electrode is taken out and is rinsed and dried up with secondary distilled water;
(2) preparation of modified electrode CMP/GCE: organic 0.002 g of poromerics CMP of conjugation prepared by Example 1, dispersion In the mixed solution of 2 ml second alcohol and waters (ethyl alcohol 1ml, water 1ml), being made into concentration is 1.0 mgmL-1Dispersion liquid, and drip It is coated in above-mentioned processed bare glassy carbon electrode, drying at room temperature, modified electrode CMP/GCE is made.
3, modified electrode CMP/GCE is for detecting drug antioxidant for clearing ONOO- Ability
3 × 10 are added in the PBS solution containing drug antioxidant-6 M ONOO- , to be conjugated organic poromerics modification electricity It is in the three-electrode system of reference electrode composition that extremely working electrode, platinum column, which are to electrode, saturated calomel electrode, and operating potential is 1.0 V are detected with chronoamperometry;Current-responsive after obtaining drug antioxidant for clearing peroxynitrite Chrono-amperometric, more, the drug antioxidant for clearing ONOO that the chrono-amperometric of current-responsive reduces- Ability it is stronger.
Instrument used in implementation process of the present invention and drug:
CHI 660C electrochemical workstation (Shanghai Chen Hua instrument company) is used to carry out the experiment of cyclic voltammetric, chrono-amperometric, stone Automatically dual pure water distiller (1810B, Asian-Pacific Glass-Tech. Co., Shanghai City) is used to steam ultrapure water English pipe heated type.Electronic balance (Beijing Sai Duolisi Instrument Ltd.), for weighing drug.Ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.). Aluminum oxide polishing powder (Shanghai Chen Hua instrument reagent company) is for handling glass-carbon electrode.Saturated calomel reference electrode, platinum pair Electrode, potassium chloride, sodium dihydrogen phosphate, disodium hydrogen phosphate (Xi'an chemical reagent factory);Tri- ethynylbenzene of 1,3,5- (Hebei lark prestige Fine materials Co., Ltd);Triethylamine (three factory of Tianjin chemical reagent), toluene, chloroform (Beijing Chemical Plant);Iodate is sub- Copper (upper marine Qin's chemical reagent Co., Ltd);Four triphenyl phosphorus palladiums, 2- amino -3,5- dibromo pyridine (Sa grace chemical technology (on Sea) Co., Ltd);Acetone, methanol (Li Anlongbohua (Tianjin) medical chemistry Co., Ltd).

Claims (10)

1. a kind of preparation method for being conjugated organic poromerics modified electrode, comprises the following steps that:
(1) it is conjugated the preparation of organic poromerics: under the conditions of being protected from light, the mixed solution of triethylamine and toluene being added as solvent Enter in anti-reactor, after magnetic agitation is uniform, in N2Tri- ethynylbenzene of reactant 1,3,5- and amino -3 2- are sequentially added under protection, 5- dibromo pyridine adds catalyst cuprous iodide and four triphenyl phosphorus palladiums, stirs evenly and be placed in oil bath pan, slowly heats up To 60 ~ 90 DEG C, 50 ~ 100h is reacted;It is cooled to room temperature, resulting polymers are successively washed with chloroform, water, acetone, methanol It washs, finally carries out 24 ~ 96h of soxhlet extraction in methyl alcohol, final product must be conjugated organic poromerics through drying, grinding CMP;
(2) preparation of modified electrode CMP/GCE: second alcohol and water is dispersed by the organic poromerics of conjugation of step (1) preparation In mixed solution, being made into concentration is 0.2 ~ 2.0mgmL-1Dispersion liquid, and drop coating is in pretreated bare glassy carbon electrode, room The lower drying of temperature, is made modified electrode CMP/GCE.
2. the preparation method of the modified electrode of the organic poromerics of conjugation described in claim 1, it is characterised in that: step (1) In the mixed solution of triethylamine and toluene, the volume ratio of triethylamine and toluene is 1:1 ~ 1:9.
3. the preparation method of the modified electrode of the organic poromerics of conjugation described in claim 1, it is characterised in that: in step (1), The molar ratio of tri- ethynylbenzene of reactant 1,3,5- and 2- amino -3,5- dibromo pyridine is 1:1 ~ 1:7.
4. the preparation method of the modified electrode of the organic poromerics of conjugation described in claim 1, it is characterised in that: in step (1), Catalyst cuprous iodide, four triphenyl phosphorus palladiums dosage be respectively 0.01 ~ 0.08 times of reactant integral molar quantity, 0.01 ~ 0.06 times.
5. the preparation method of the modified electrode of the organic poromerics of conjugation described in claim 1, it is characterised in that: step (2) In the mixed solution of second alcohol and water, the percentage by volume of ethyl alcohol is 20 ~ 80%.
6. the preparation method of the modified electrode of the organic poromerics of conjugation described in claim 1, it is characterised in that: step (2) On modified electrode CMP/GCE, be conjugated organic poromerics coating with a thickness of 200 ~ 1200 nm.
7. the organic poromerics modified electrode of conjugation of method preparation as described in claim 1 is as electrochemical sensor for examining Survey ONOO in solutionConcentration.
8. the modified electrode for being conjugated organic poromerics as claimed in claim 7 is used to detect in solution as electrochemical sensor ONOOConcentration, it is characterised in that: using be conjugated organic poromerics modified electrode as working electrode, platinum column be to electrode, saturation Calomel electrode is reference electrode, three-electrode system is formed, to contain ONOO- PH=7.0 0.2M phosphate buffer solution make Cyclic voltammetry scan is carried out with chronoamperometry in the case where operating potential is 1.0V for electrolyte;Work as ONOO-Concentration 4.62 × 10-9 ~ 9.51×10-5When within the scope of M, response current Ip and ONOO- The logarithm of concentration is in good linear relationship, and is responded Electric current Ip and ONOO-The equation of linear regression of log concentration are as follows:
Ip (μA) = - 0.0622 [ONOO-] (μM) -0.1065, R2 = 0.9994。
9. the organic poromerics modified electrode of conjugation of method preparation as described in claim 1 is used for Electrochemical Detection drug antioxygen The ability of agent removing peroxynitrite.
10. being conjugated organic poromerics modified electrode as claimed in claim 9 for Electrochemical Detection drug antioxidant for clearing The ability of peroxynitrite, it is characterised in that: 1 × 10 is added in the PBS solution containing drug antioxidant-5 M ONOO-, to be conjugated organic poromerics modified electrode as working electrode, platinum column to be to electrode, saturated calomel electrode be reference electricity In the three-electrode system of pole composition, operating potential is that 1.0 V are detected with chronoamperometry;It is clear to obtain drug antioxidant Except ONOO-The chrono-amperometric of current-responsive afterwards, the chrono-amperometric of current-responsive reduce more, oxidation of drug agent removing ONOO- Ability it is stronger.
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CN114759196A (en) * 2022-05-07 2022-07-15 青岛大学 Conjugated microporous polymer electrocatalyst loaded with metal nanoparticles and preparation method and application thereof
CN114759196B (en) * 2022-05-07 2023-08-29 青岛大学 Conjugated microporous polymer electrocatalyst loaded with metal nano particles and preparation method and application thereof

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