CN111518054A - HClO detection microelectrode, and preparation method and application thereof - Google Patents
HClO detection microelectrode, and preparation method and application thereof Download PDFInfo
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- CN111518054A CN111518054A CN202010283834.3A CN202010283834A CN111518054A CN 111518054 A CN111518054 A CN 111518054A CN 202010283834 A CN202010283834 A CN 202010283834A CN 111518054 A CN111518054 A CN 111518054A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
- C07D279/30—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with acyl radicals attached to the ring nitrogen atom
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention discloses a microelectrode CFME/CNT/ABTS + MBS for detecting HClO in trace blood and a preparation method and application thereof, belonging to the technical field of application of organic molecular probes in biosensing. The method firstly synthesizes the electrochemical probe MBS with HClO specificity recognition, and modifies MBS molecules and ABTS molecules with internal reference function on CFME/CNT electrodes through pi-pi bonds to prepare the HClO detection microelectrode CFME/CNT/ABTS + MBS. The microelectrode CFME/CNT/ABTS + MBS has higher selectivity on the response of HClO, and the introduction of the internal reference improves the accuracy and the anti-pollution capability of the actual sample detection. The HClO microelectrode can realize qualitative or quantitative determination of HClO in trace blood samples, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of application of organic probes in biosensing, and relates to a sensor for specific recognition and high-accuracy detection of HClO in trace blood, and a preparation method and application thereof.
Background
HClO plays an important role as one of active oxygen. In daily life, HClO is used for sterilization and disinfection; in the biological system, HClO is an important component of our immune system, especially neutrophils as the first line of host defense against malignancies and invading pathogens. However, an abnormal content of HClO will lead to "oxidative stress", further causing diseases associated with many inflammations, such as neurodegenerative diseases, atherosclerosis, cancer, etc. Therefore, it is necessary to detect the content of HClO in both daily life and physiological systems.
To date, many methods have been developed for the detection of HClO, such as fluorescence, colorimetry, electrochemistry, and the like. Although researchers developed a large number of fluorescent probes for the detection of HClO, exhibiting highly selective cellular imaging, the fluorescence method cannot satisfy its direct detection for blood samples due to its own color and background fluorescence. In contrast, electrochemistry has many advantages, such as high space-time resolution, high sensitivity, and the like. However, to date, electrochemical detection based on HClO has been affected primarily by two factors: (1) HClO is depended on electrochemical oxidation, the oxidation overpotential of HClO is reduced by regulating the characteristics of electrode materials, but unfortunately, common bio-related substances generate interference, and how to realize high-selectivity detection is a great challenge. (2) In order to meet the requirements of practical application and avoid measurement errors caused by complex sample environments or sample dilution, how to realize high-accuracy electrochemical detection is another major challenge.
Disclosure of Invention
In view of the deficiencies of the existing electrochemical sensors, the present invention aims to improve the selectivity and accuracy of the detection of HClO in blood.
In order to realize the purpose of the invention, the invention designs and synthesizes an HClO specific organic probe MBS, and prepares an HClO detection microelectrode CFME/CNT/ABTS + MBS by introducing an internal reference molecule ABTS, thereby realizing the high selectivity, high accuracy and high sensitivity detection of HClO in trace blood.
The HClO recognition electrochemical probe MBS and the commercial internal reference molecule ABTS have the following structures:
r is C3-4 alkyl.
The preparation method of the CFME/CNT/ABTS + MBS comprises the following steps:
(1) HClO recognition electrochemical probe synthesis
(a) Methylene blue was dissolved in aqueous solvent under alkaline conditions followed by addition of organic solvent, then the mixture was stirred well under oxygen-free conditions and reducing agent was added with syringe. After the addition, the mixture is stirred and reacted under anhydrous and oxygen-free conditions.
Reaction 1 is shown below:
(b) the product of step (a) is not required to be purified, and the organic solvent is quickly separated from the water layer and dried by a drying agent. After removing the drying agent by filtration, the acid chloride solution was quickly added dropwise to the organic phase under alkaline conditions and stirred in an ice-water bath for reaction, then at room temperature until the reaction was complete, and the reaction was monitored by thin layer chromatography. Reaction 2 is shown below:
(c) after the reaction is finished, extracting, drying, filtering, spin-drying the filtrate, and purifying under a proper developing solvent proportion to obtain the product. Namely the HClO specific recognition electrochemical probe Molecule (MBS).
(2) Preparation of HClO detection microelectrode CFME/CNT/ABTS + MBS
(a) Preparing a CFME glass electrode;
(b) immersing the CFME electrode into a carbon nano material (CNT) solution, rotating for a plurality of circles, taking out, and naturally drying to obtain the CFME/CNT electrode;
(c) immersing the CFME/CNT electrode into a mixed solution of MBS and ABTS, and modifying to obtain CFME/CNT/ABTS + MBS;
in the step (1a), the alkaline environment is sodium carbonate, potassium carbonate and cesium carbonate, and sodium carbonate is preferred; the organic solvent is dichloromethane, toluene, ethyl acetate, preferably dichloromethane; the reducing agent is sodium borohydride, sodium hydrosulfite, reduced iron powder and zinc powder, preferably sodium hydrosulfite; the molar ratio of the methylene blue to the alkali to the reducing agent is 1: 1-5, preferably 1:4: 4; the reduction reaction is carried out at the temperature of 20-100 ℃, and preferably at the temperature of 40 ℃; the reaction time is 5-180 min, preferably 30 min; the reaction conditions are preferably in N2Under the protection condition.
In the step (1b), the alkaline environment is sodium carbonate, potassium carbonate, cesium carbonate and triethylamine, preferably triethylamine. The organic solvent is dichloromethane, toluene, ethyl acetate, methanol, ethanol, acetonitrile, preferably dichloromethane. The acyl chloride is propionyl chloride, butyryl chloride, isobutyryl chloride, preferably isobutyryl chloride. The molar ratio of the product, alkali and acid chloride in the step (1a) is 1:5:2, the reaction is carried out in an ice-water bath for 1-12 h, preferably 10h, and the reaction condition is N2Under the conditions.
In the step (1c), the developing solvent is petroleum ether/ethyl acetate, petroleum ether/dichloromethane, dichloromethane/ethyl acetate, and the ratio is 1:1 to 5. Preferably ethyl acetate: petroleum ether is 1: 5;
in the step (2a), the CFMF glass microelectrode is exposed with a CFME tip of 0.5-1mm and the diameter of 7 μm;
in step (2b), the CFMF is put into the CNT solution and rotated for 1-20 turns, preferably 5 turns.
The mol ratio of the MBS molecules to the ABTS molecules in the step (2c) is 1-5: 1; preferably 5: 1. The soaking time is 1-10 hours, preferably 5 hours. The solvent of the solution is methanol, ethanol, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide and water, preferably ethanol; the preparation process is carried out at room temperature.
The principle of the invention is as follows: MBS is taken as HClO specific recognition molecule, and under the existence of HClO, MBS and HClO generate nucleophilic oxidation reaction to generate methylene blue structure, and has good electrochemical signal, which is the basis for realizing HClO high-selection detection. In addition, the ABTS is used as an internal reference, and the electrochemical signal of the ABTS is not changed in the presence of HClO, so that the accuracy of the CFME/CNT/ABTS + MBS prepared by the method for detecting the HClO in the trace blood can be improved.
The CFME/CNT/ABTS + MBS prepared by the invention is a ratio type electrochemical sensor and is used for detecting HClO in blood. The three-electrode system is formed with AgCl/Ag electrode and Pt as counter electrode, and HClO is qualitatively and quantitatively detected by Square Wave Voltammetry (SWV). The sensor can realize high-selectivity detection of HClO and high-accuracy detection of HClO.
The invention has the beneficial effects that: (1) according to the invention, MBS is used as the HClO specificity recognition electrochemical probe, so that the detection selectivity is obviously improved, ABTS is used as an internal reference, the detection accuracy is further improved, and errors caused by complex environment or actual sample determination are effectively avoided; (2) the HClO detection micro-electrode has quick response time (less than 10s) to HClO; (3) the HClO prepared by the method has higher selectivity and is not interfered by other electroactive substances, active oxygen, active sulfur, active nitrogen and the like; (4) the MBS and ABTS are modified on the surface of the CNT through pi-pi bonds, and the preparation process is simple and quick. (5) The size of the tip of the HClO detection microelectrode is 500 mu m-1 mm. Can realize qualitative and quantitative determination of trace samples, and has important significance for research on the function of HClO in related diseases.
Drawings
FIG. 1 nuclear magnetic resonance characterization hydrogen spectrum of MBS of the invention.
FIG. 2 is a nuclear magnetic resonance characterization carbon spectrum of MBS in the invention.
FIG. 3 is a high resolution mass spectrum characterization chart of MBS in the invention.
FIG. 4 is an electrochemical characterization diagram of SWV in the CFME/CNT/ABTS + MBS modification process of the present invention, wherein after HClO is added to a-bare CFME, b-CFME/CNT, c-CFME/CNT/MBS, HClO is not added to d-CFME/CNT/ABTS + MBS, and HClO is added to e-CFME/CNT/ABTS + MBS.
FIG. 5 is a graph showing the response kinetics of MBS and HClO according to the present invention.
FIG. 6 is a high resolution mass spectrum representation diagram of MBS of the present invention after reaction with HClO.
FIG. 7 high performance liquid chromatography before and after the reaction of MBS of the present invention with HClO, wherein left-side before the reaction and right-side after the reaction.
FIG. 8 is a SWV response of CFME/CNT/ABTS + MBS of the present invention to different concentrations of HClO (0.5-150. mu.M).
FIG. 9 shows the selectivity of CFME/CNT/ABTS + MBS of the present invention for different biologically relevant active molecules.
FIG. 10 shows CFME/CNT/ABTS + MBS of the present invention after adding 0.5mg mL-1Bovine serum albumin pre-and post-SWV responses, with a-pre-addition and b-post-addition.
FIG. 11 is a SWV response of CFME/CNT/ABTS + MBS of the present invention to actual blood samples, wherein a-is in blank PBS and b-is in blood samples.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings, which are not intended to limit the present invention unless otherwise specifically noted, but are generally known or appreciated by those skilled in the art.
Example 1: preparation method of HClO detection microelectrode CFME/CNT/ABTS + MBS
(1) Synthesis of HClO specific recognition molecular probe
Methylene blue (1.12g, 3.75mmol) and Na were first combined2CO3(1.59g, 15.00mmol) in 5mL of water followed by addition of dichloromethane (10mL) and stirring of the mixture at 40 ℃ under nitrogen. Sodium dithionite (2.61g, 15.00mmol) was then dissolved in 5mL of water and injected directly into the solution using a syringe. After the addition was complete, the mixture was stirred at 40 ℃ under nitrogen until the solution turned yellow (30 min). The dichloromethane layer was separated from the aqueous layer and dried quickly over anhydrous sodium sulfate. After filtration to remove sodium sulfate, the filtrate was quickly washedTriethylamine (0.5mL) was added to the solution, a solution of isobutyryl chloride (3.75mmol) was added dropwise to the mixture in an ice-water bath under nitrogen and stirred, the reaction was monitored by thin layer chromatography until complete after the reaction undissolved material was removed by filtration, then the solution was poured into 200mL of ice-water with stirring and the resulting mixture was extracted with 3 × 100mL of ethyl acetate the combined extracts were washed with brine, dried over anhydrous sodium sulfate and evaporated on a rotary evaporator to give a solid residue which was purified by column chromatography (ethyl acetate/petroleum ether ═ 1/5) to give MBS as a white solid and characterized by nmr, carbon and high resolution mass spectrometry (fig. 1, 2 and 3), thus demonstrating the successful synthesis of specific HClO electrochemical probes.
(2) Preparation of CFME/CNT/ABTS + MBS
First, a bare CFME electrode was prepared and washed in ethanol, N2Drying, and rotating the carbon fiber in 5mg/mLCNT ethanol solution for 5 circles to obtain CFME/CNT. And then washing the CFME/CNT in ethanol, drying, immersing in a methanol solution containing 5mM MBS +1mM ABTS for 5h, taking out, and washing with ethanol and distilled water in sequence to obtain the HClO detection microelectrode CFME/CNT/ABTS + MBS.
Example 2: HClO detection microelectrode CFME/CNT/ABTS + MBS determination of HClO
The microelectrode CFME/CNT/ABTS + MBS prepared by the invention is used as a working electrode, Ag/AgCl is used as a reference electrode, a Pt wire is used as a counter electrode, the SWV response before and after 50 mu M HClO is added into 0.1M PBS solution is measured, and the potential window: -0.5-0.8V. As a result, as shown in FIG. 4, when HClO is not present, only one oxidation peak is present at 0.53V, which is attributed to the electrochemical signal of ABTS, and when HClO is added, a new peak appears at about-0.30V, which is mainly due to the electrochemical signal generated by the structure that HClO reacts with MBS to generate methyl blue, wherein ABTS is used as internal reference to improve the accuracy of electrochemical sensing, and MBS is used as a specific recognition molecule of HClO to improve the selectivity of detection. The reaction mechanism shows that MBS has rapid response capability (reaction time) to HClO through ultraviolet visible spectrum time dynamics (figure 5)<10s) and the product after reaction was also verified by high resolution mass spectrometry (fig. 6) and high performance liquid chromatography (fig. 7).The above shows that the CFME/CNT/ABTS + MBS of the invention has feasibility for HClO electrochemical detection. Further, as the HClO concentration increased, the peak current (j) at-0.30VMBS) And current signal (j) generated by ABTSABTS) The ratio of (A) to (B) to (C) is in good linear relation with the HClO concentration (0.5-50 mu M), and the corresponding linear equation is as follows: j is a function ofMBS/jABTS0.1047+0.0438c (hclo) with a detection limit of 0.2 μ M (fig. 8).
Example 3: anti-interference experiment
The interference determination of HClO detection microelectrode CFME/CNT/ABTS + MBS prepared by the invention is carried out by using CHI660E electrochemical workstation. As shown in FIG. 9, the peak current ratio change caused by adding other biological common active molecules (active oxygen, active sulfur, active nitrogen, etc.) into 50 μ M HClO solution is not more than 2.5%, which indicates that the HClO detection micro-electrode prepared by the invention has higher selectivity for HClO detection.
Example 4: evaluation of anti-fouling capability of HClO detection microelectrode
The microelectrode CFME/CNT/ABTS + MBS prepared by the invention is used as a working electrode, AgCl/Ag is used as a reference electrode, a Pt wire is used as a counter electrode, SWV is adopted to record under a potential window of-0.5-0.8V, and 0.1M PBS solution containing 50 MuM HClO is added into 0.5mg mL-1The SWV response before and after Bovine Serum Albumin (BSA) is obtained, and the result shows that the peak current ratio j before and after adding BSA is calculatedMBS/jABTSBasically, the method is not changed (figure 10), which shows that errors caused by protein pollution can be eliminated after the HClO detection microelectrode CFME/CNT/ABTS + MBS prepared by the invention is introduced into an internal reference, and the CFME/CNT/ABTS + MBS can be applied to the detection of complex blood samples.
Example 5: determination of HClO in blood samples
Taking a blood sample from a normal volunteer, directly taking 100 mu L without treatment, directly implanting HClO detection microelectrode CFME/CNT/ABTS + MBS as a working electrode, Ag/AgCl as a reference electrode and Pt wire as a counter electrode into blood, and then measuring under a potential window of-0.5-0.8V by adopting an SWV method (figure 11) to obtain a ratio j of peak current change caused by HClO to current value generated by ABTSMBS/jABTSAccording to the linear relationship in example 2The concentration of HClO in the actual blood sample is calculated. Realizes the qualitative and quantitative determination of HClO in trace blood samples.
Claims (8)
1. An electrochemical probe molecule for specifically recognizing HClO, which is characterized by having the following structural formula:
2. A method for synthesizing an electrochemical probe for HClO specific recognition according to claim 1, comprising the steps of:
(a) dissolving methylene blue in an aqueous phase solvent under an alkaline condition, adding an organic solvent, and stirring the mixture uniformly under an oxygen-free condition; then adding a reducing agent by using an injector, and stirring the mixture to react under anhydrous and anaerobic conditions after the addition is finished;
(b) the product of step (a) is not required to be purified, and the organic solvent is quickly separated from the water layer and dried by a drying agent; filtering to remove a drying agent, quickly dropwise adding the acyl chloride solution into the organic phase under an alkaline condition, stirring in an ice-water bath, then stirring at room temperature until the reaction is finished, and monitoring the reaction by thin-layer chromatography;
(c) after the reaction is finished, extracting, drying, filtering, spin-drying the filtrate, and purifying under a proper developing solvent proportion to obtain the HClO specific recognition Molecule (MBS).
3. The method for synthesizing an electrochemical probe for specifically recognizing HClO according to claim 2, wherein the basic conditions used in the step (a) are sodium carbonate, potassium carbonate or cesium carbonate; the organic solvent is dichloromethane, toluene and ethyl acetate; the reducing agent is sodium borohydride, sodium hydrosulfite, reduced iron powder or zinc powder; the molar ratio of the methylene blue to the alkali to the reducing agent is 1: 1-5.
4. The method for synthesizing an electrochemical probe for specifically recognizing HClO according to claim 2, wherein the basic conditions used in the step (b) are sodium carbonate, potassium carbonate, cesium carbonate or triethylamine; the organic solvent is dichloromethane, toluene, ethyl acetate, methanol, ethanol or acetonitrile; the acyl chloride is propionyl chloride, butyryl chloride or isobutyryl chloride; the molar ratio of the product in the step (1), alkali and acid chloride is 1: 1-10: 1-5.
5. A microelectrode CFME/CNT/ABTS + MBS for detecting HClO is characterized by being prepared by the following steps:
(1) preparing a CFME electrode;
(2) immersing the CFME electrode prepared in the step (1) into a carbon nano material (CNT) solution, taking out after rotating for several circles and drying to obtain a CFME/CNT electrode;
(3) and (3) soaking the CFME/CNT electrode prepared in the step (2) in a solution of an HClO specific recognition molecule MBS and an internal reference molecule ABTS to obtain the HClO detection microelectrode CFME/CNT/ABTS + MBS.
6. The microelectrode CFME/CNT/ABTS + MBS for detecting HClO of claim 5, wherein the carbon fiber of step (1) has an exposed tip of 500 μm to 1mm and a diameter of 7 μm; in the step (2), the CFME electrode is fixed in one direction and rotates for 5-20 circles.
7. The microelectrode CFME/CNT/ABTS + MBS for detecting HClO of claim 5, wherein the molar ratio of the HClO-specific recognition molecule to the reference molecule in step (3) is 1: 0-0: 1; the solvent of the solution is methanol, ethanol, acetonitrile, dimethyl sulfoxide, N-dimethylformamide or water.
8. Use of micro-electrodes CFME/CNT/ABTS + MBS for detecting HClO according to any one of claims 5 to 7, characterized in that the micro-electrodes CFME/CNT/ABTS + MBS for detecting HClO are used as working electrodes, Ag/AgCl is used as reference electrode, Pt wire is used as counter electrode, and the micro-electrodes are directly implanted into blood, and the qualitative or quantitative analysis of HClO in the trace blood is carried out by SWV method.
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