CN114019003A - Electrochemical sensor for UA detection through molecular line regulation and control nano interface and preparation and application thereof - Google Patents
Electrochemical sensor for UA detection through molecular line regulation and control nano interface and preparation and application thereof Download PDFInfo
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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
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- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
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Abstract
The invention discloses a method for electrochemically detecting cerebral uric acid by regulating a nano interface with a molecular line. The invention also discloses a molecular wire and a preparation method thereof, and different types of molecular wires are obtained by reaction in an organic solvent. The molecular wire is modified on the surface of the gold electrode through the interaction of gold and sulfur, and then Ni is modified3HHTP2And obtaining the electrochemical sensor. The method provided by the invention is simple to operate, and the prepared electrochemical sensor is used for detecting the uric acid in the brain of the mouse, has high selectivity, high sensitivity and low detection limit, and has important significance for exploring the behavior of the uric acid in a living body and the relation between the uric acid and the learning and memory abilities.
Description
Technical Field
The invention belongs to the technical field of sensing detection of carbon fiber microelectrodes, and particularly relates to an electrochemical sensor for UA detection by regulating a nano interface by using a molecular wire, and preparation and application thereof.
Background
Most of nervous system diseases are closely related to the deficiency or disorder of neurochemicals, and the in-situ detection of neurochemicals in the brain is an important method for understanding brain science and solving brain diseases. However, the environment in the brain is very complex, many substances with many redox activities exist, and signals overlap, so that the detection of the neurochemical substances in the brain is greatly influenced. Therefore, it is highly desirable to develop an efficient electrochemical sensor, which retains the intrinsic signal of the chemical substance, improves the selectivity, and can realize reversible detection, which is important for long-term dynamic detection of the neurochemical substance.
Wherein, uric acid is used as a natural antioxidant in human body, can remove peroxide, hydroxyl, oxygen free radical and the like, effectively relieves the oxidative damage of free radicals to the body and the damage to blood brain barrier, has strong protection effect on neurons, and plays a role in preventing and treating a plurality of nervous system diseases. However, in the existing electrochemical technology, the problems of low stability, poor selectivity, high detection limit, unidirectional detection and the like of the nano material generally exist, and the challenges make the technology for detecting uric acid in a living body difficult to make a substantial breakthrough.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a novel method for detecting uric acid. The method has the advantages of high selectivity, high sensitivity and low detection limit, and is very beneficial to kinetic detection.
The invention provides a two-dimensional conductive MOF material Ni3HHTP2The structure is as shown in formula (a):
the invention also provides a two-dimensional conductive MOF material Ni3HHTP2In the aqueous solution, 2,3,6,7,10, 11-hexahydroxybenzo and nickel (II) acetate tetrahydrate react to obtain the two-dimensional conductive MOF material Ni3HHTP2。
Wherein the aqueous solution is deionized water.
The invention also discloses three molecular lines, the structures of which are respectively shown as formulas (b), (c) and (d):
the invention also discloses a preparation method of the molecular wire shown in the formula (c), which comprises the following specific steps: adding 4-iodobenzaldehyde and PdCl2(PPh3)2And CuI suspended in 15mL dry THF and 5mL TEA at room temperature; then, 3-ethynylthiophene was added and stirred at 50 ℃; after the 4-iodobenzaldehyde is consumed, continuously stirring for 16 hours to obtain yellow solid, namely the molecular line shown in the formula (c);
wherein, the 4-iodobenzaldehyde and PdCl2(PPh3)2The molar ratio of CuI to 3-ethynylthiophene is 5:20:10: 6.
The invention also discloses a preparation method of the molecular wire shown in the formula (d), which comprises the following specific steps:
step (1): adding 4-iodobenzaldehyde and PdCl2(PPh3)2And CuI to a suspension of 5mL TEA in 15mL dry THF at room temperature, then 1-ethynyl-4-iodobenzene was added and the mixture was stirred at 50 ℃ until 4-iodobenzaldehyde was consumed, then the reaction was stirred for 16h to give an intermediate product;
the 4-iodobenzaldehyde and PdCl2(PPh3)2The molar ratio of CuI to 1-ethynyl-4-iodobenzene is 5:20:10: 6;
step (2): the intermediate was dissolved in 8mL dry THF at room temperature and N2Then 2.8mL of TEA and PdCl are added2(PPh3)2And CuI dissolution; then, 3-ethynylthiophene was added, and the mixture was stirred at 50 ℃ for 16h to obtain a yellow solid, a molecular line represented by formula (d);
the intermediate product, PdCl2(PPh3)2The molar ratio of CuI to 3-ethynylthiophene is 2.80:11:5.6: 3.06.
In one embodiment, the method for preparing the molecular wire represented by the formula (c) comprises the following specific steps: 4-iodobenzaldehyde (5mmol) and PdCl2(PPh3)2(20mmol) and CuI (10mmol) were suspended in 15mL dry THF and 5mL TEA at room temperature. Then, 3-ethynylthiophene (6mmol) was added and stirred at 50 ℃. 4-The reaction was stirred for a further 16h after iodobenzaldehyde consumption. Finally, the crude product was purified by column chromatography (silica gel, petroleum ether/ethyl acetate-9/1) to give a yellow solid.
In one embodiment, the method for preparing the molecular wire represented by the formula (d) comprises the following steps: first, 4-iodobenzaldehyde (5mmol), PdCl2(PPh3)2(20mmol) and CuI (10mmol) were added to a suspension of TEA (5mL) in dry THF (15mL) at room temperature. Next, 1-ethynyl-4-iodobenzene (6mmol) was added and the mixture was stirred at 50 ℃ until 4-iodobenzaldehyde was consumed, then the reaction was stirred for 16 h. Finally, the crude product was purified by column chromatography (silica gel, petroleum ether/ethyl acetate 10/1) to give the product.
The product (2.80mmol) was then dissolved in 8mL dry THF at room temperature and N2Then TEA (2.8mL), PdCl were added2(PPh3)2(11mmol) and CuI (5.6mmol) were dissolved. Thereafter, 3-ethynylthiophene (3.06mmol) was added and the mixture was stirred at 50 ℃ for 16 h. The residue was purified by column chromatography (silica gel, ether/ethyl acetate 10/1) to give a yellow solid.
The reaction schemes of the formula (c) and the formula (d) of the invention are shown as follows:
the invention also provides a preparation method of the electrochemical sensor, which comprises the following specific steps:
(1) preparing a carbon fiber microelectrode: fixing the carbon fiber on the copper wire through silver conductive adhesive, and drying for 1 hour in a drying oven at 60 ℃; then, the above product was inserted into a capillary tube and dried at 60 ℃ for 8 hours to obtain a carbon fiber microelectrode.
(2) Electrodepositing gold nanoparticles on the carbon fiber micro-electrode obtained in the step (1);
(3) modifying molecular lines on the carbon fiber micro-electrode with gold nano-particles electrodeposited in the step (2);
(4) carbon of electrodeposited gold nanoparticles after modification of molecular lines in step (3)On the fiber micro-electrode, modifying the two-dimensional conductive MOF material Ni shown in the formula (a)3HHTP2Obtaining an electrochemical sensor:
in the step (1), the outer diameter of the capillary tube of the carbon fiber microelectrode is 1.0mm-1.5mm, preferably 1.5 mm; the inner diameter is 0.7mm to 1.1mm, preferably 1.1 mm.
In the step (1), the capillary tube is made of a quartz glass capillary tube or a borosilicate glass capillary tube, preferably, a borosilicate glass capillary tube.
In the step (1), the aperture of a capillary tube of the carbon fiber microelectrode is 100-200 μm; preferably 100 μm.
In the step (2), the method for electrodepositing the gold nanoparticles on the carbon fiber electrode is an electrochemical deposition method, the carbon fiber electrode is firstly put into 0.1M NaOH, and electrochemical pretreatment is carried out for 80s by 1.5V; and then the gold nanoparticles are electroplated after the gold nanoparticles are inserted into the chloroauric acid solution.
Wherein the concentration of the chloroauric acid solution is 5mM-50 mM; preferably, it is 10 mM.
Wherein the voltage of the electrodeposition is-0.1V to-0.2V; preferably, it is 0.2V.
Wherein the time of electrodeposition is 30-100 s; preferably 40 s.
In the step (3), the method for modifying the molecular wire on the carbon fiber micro-electrode with the electrodeposited gold nano-particles comprises the following steps: and (3) immersing the gold-plated carbon fiber microelectrode into the molecular wire solution, taking out, washing off the free molecular wire solution, and airing at room temperature.
Wherein, the molecular line solution specifically means that the molecular lines shown in formulas (b), (c) and (d) are dissolved in THF solution.
Wherein the concentration of the molecular line is 1mM-2 mM; preferably, it is 2 mM.
Wherein the time for immersing the molecular line is 8-12 h; preferably 12 h.
Wherein the molecular wire has the structure shown in the formulas (b), (c) and (d).
In the step (4), the two-dimensional conductive MOF material Ni shown in the modified formula (a)3HHTP2Before, Ni is added3HHTP2Is dispersed in H2In O to obtain Ni3HHTP2-H2O dispersion liquid; then immersing the carbon fiber microelectrode of the electrodeposited gold nano particle modified by the molecular line in the step (3) into Ni3HHTP2-H2And (4) dispersing in the O dispersion liquid for a period of time to obtain the electrochemical sensor.
Wherein the concentration of the dispersion liquid is 1 mg/mL-5 mg/mL; preferably, it is 1 mg/mL.
Wherein the time for immersing into the dispersion liquid is 1-5 h; preferably, it is 5 h.
The invention also provides an electrochemical sensor prepared by the method.
The invention also provides application of the electrochemical sensor in detecting uric acid.
The invention also provides a method for detecting in vitro uric acid by using the electrochemical sensor through an electrochemical analysis method.
The invention also provides an application of the electrochemical sensor in detecting uric acid in mouse brain by an electrochemical analysis method.
The invention utilizes the interaction between gold and sulfur to modify molecular lines on a gold-plated electrode and then modify a two-dimensional conductive MOF material. On one hand, the synthesized MOF has large specific surface area, high porosity and many active sites, and effectively enriches molecules and simultaneously drives the oxidation process; on the other hand, the rigid molecules are connected with the electrode surface and the MOF material, so that the transfer of electrons from the MOF material to the electrode surface is more orderly, the internal energy consumption is reduced, the electron transfer rate is increased, and the analysis performance of the electrochemical sensor is improved. The electrochemical sensor has high selectivity, high sensitivity, low detection limit and excellent performance on the recognition of uric acid.
Specifically, the method for detecting uric acid in vitro by using the electrochemical sensor comprises the following steps:
(1) gold is electroplated on the carbon fiber electrode, and the concentration of the chloroauric acid solution is 5mM-50mM, preferably 10 mM.
Wherein the voltage of the electrodeposition is-0.1V to-0.2V, preferably 0.2V.
Wherein the time of electrodeposition is 30s-100s, preferably 40 s.
(2) And (2) modifying a molecular wire on the gold-plated carbon fiber electrode obtained in the step (1). Taking out, washing off free molecular line solution, and air drying at normal temperature.
Wherein the concentration of the molecular line is 1mM-2mM, preferably 2 mM.
Wherein the time for immersing the molecular line is 8h-24h, preferably 12 h.
(3) Modifying two-dimensional conductive MOF material Ni on the gold-plated carbon fiber electrode of the modified rigid molecule obtained in the step (2)3HHTP2And obtaining the electrochemical sensor, namely the required electrode.
(4) Building a three-electrode working system: and (3) building a three-electrode working system in an electrochemical workstation, taking the electrode obtained in the step (3) as a working electrode, taking an Ag/AgCl electrode as a reference electrode, and taking a Pt electrode as a counter electrode. The voltage recording range was 0V-0.8V, and the voltage step amplitude was 80 mV.
(5) Making a standard curve:
recording differential pulse voltammetry curves of uric acid with different concentrations on the electrochemical workstation set up in the step (4), and then making a relation curve of peak current and uric acid concentration to obtain a linear range of 0.2-150 mu M;
(6) determining uric acid content in sample
And measuring uric acid in the sample in the electrochemical workstation, and calculating the uric acid content in the sample according to the standard curve.
The invention also provides a method for detecting the content of uric acid in the brain of a mouse by using the prepared carbon fiber microelectrode, which comprises the following steps:
(1) preparing a needed carbon fiber microelectrode;
(2) measurement of uric acid in hippocampal tissues in hyperuricemic and normal mice.
And (3) measuring the peak current, and calculating to obtain the content of uric acid in the brain according to the standard curve.
The invention has the beneficial effects that the modification state of the two-dimensional conductive MOF material on the electrode interface is effectively regulated and controlled through the molecular line, and the high-efficiency sensor for detecting the uric acid is developed. The electrochemical sensor has good selectivity and low detection limit, the linear range of the electrochemical sensor is 0.2-150 mu M, the lowest detection line is 80nM (S/N is 3), the detection of uric acid in vitro or in vivo can be well met, and the electrochemical sensor has important significance for disease diagnosis, drug treatment and other basic researches.
Drawings
FIG. 1: scanning electron microscope SEM images and transmission electron microscope TEM images of the two-dimensional conductive MOF materials synthesized by the present invention. Wherein, A is SEM picture of MOF material, B and C are TEM picture and corresponding XRD picture of MOF, which shows Ni element; pattern D is an XRD pattern. The successful synthesis of two-dimensional conductive MOF materials can be demonstrated by combining the above four figures.
FIG. 2: characterization diagrams of scanning electron microscopes SEM of different modification steps of the carbon fiber microelectrode prepared by the invention. Wherein, A is the SEM picture of a pure gold-plated carbon fiber microelectrode, B and C are the SEM pictures of modified molecular lines and two-dimensional conductive MOF materials, and D is the corresponding XRD picture, further showing that the two-dimensional conductive MOF is successfully modified on the surface of the carbon fiber microelectrode.
FIG. 3: the electrochemical sensor designed by the invention detects the differential pulse voltammogram of uric acid and the linear relation graph of the uric acid concentration and the peak current. Wherein, FIG. A, E is a DPV graph of a pure gold-plated electrode and a corresponding linear relationship graph, with a detection limit of 1.0 μ M and no linearity; FIG. B, F is a DPV graph and a corresponding linear relationship graph obtained after modification of a flexible molecule FP1 represented by formula (b) on a gold-plated electrode, with a detection limit of 5.0. mu.M, and no linearity; FIG. C, G is a DPV graph obtained by modifying short-chain rigid molecule RP1 represented by formula (c) on a gold-plated electrode and a corresponding linear relationship graph, with a detection limit of 0.5. mu.M and a linear range of 0.5. mu.M-150.0. mu.M; FIG. D, H is a DPV graph obtained by modifying a long-chain rigid molecule RP2 represented by formula (d) on a gold-plated electrode, and the corresponding linear relationship graph, with a detection limit of 0.2. mu.M and a linear range of 0.2. mu.M to 150.0. mu.M. The experimental result shows that the probe modified with the long-chain rigid molecule has the optimal analysis performance, so the probe is selected as the target probe.
FIG. 4: the electrochemical sensor implemented by the invention detects the selectivity and the competitive experiment chart of UA. The selectivity and competitive experiment chart (A-D) of amino, neurochemical, metal ion and active oxygen on 10 mu M UA, which are common in organisms. Wherein A is amino acid, B is neurochemical substance, C is metal ion, and D is active oxygen.
FIG. 5: the electrochemical sensor implemented by the invention detects the reproducibility experimental diagram of UA.
FIG. 6: the electrochemical sensor implemented by the invention detects UA in the brain of a normal mouse and a hyperuricemia mouse and the learning and memory behaviors of the normal mouse and the hyperuricemia mouse. As can be seen from the figure, the learning and memory ability of the hyperuricemia mice is obviously inferior to that of the normal mice, and the method can be further used for researching the influence of the hyperuricemia on the cognitive dysfunction.
FIG. 7 shows the assembly of rigid molecular wire RP2 and two-dimensional conductive MOF material Ni on the gold interface3HHTP2Schematic representation of (a).
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1: two-dimensional conductive MOF material Ni3HHTP2Synthesis of (2)
200mg of 2,3,6,7,10, 11-hexahydroxybenzo (HHTP) and 456mg of nickel (II) acetate tetrahydrate are added to 28mL of deionized water and subjected to ultrasonic treatment for 10 min. Subsequently, it was heated and refluxed at 85 ℃ for 24 h. After cooling to room temperature, the product was washed with deionized water (3X 50mL) and acetone (3X 50 mL). Finally, the product was collected after drying in a vacuum oven at 49 ℃ for 24 h. FIG. 2 is Ni3HHTP2The morphology characterization of the Ni-based catalyst is a nano rod-shaped structure with the diameter of about 50nm, and an XRD (X-ray diffraction) pattern further shows that the Ni is successfully prepared by the method3HHTP2。
Example 2: preparation of electrochemical sensor
(1) Gold was electroplated on the carbon fiber electrode, the concentration of the chloroauric acid solution being 10 mM.
(2) Modifying molecules FP1, RP1 or RP2 on the gold-plated carbon fiber electrode obtained in the step (1). Taking out, washing off free molecular solution, and air drying at normal temperature.
(3) Modifying the two-dimensional conductive MOF material Ni prepared in the embodiment 1 on the gold-plated carbon fiber electrode modified with the rigid molecules obtained in the step (2)3HHTP2Then, modifying Ni on the gold-plated carbon fiber electrode3HHTP2And drying at normal temperature to obtain the electrochemical sensor, namely the required electrode. The SEM image of the electrode morphology is shown in FIG. 3, the gold-plated carbon fiber electrode is decorated with Ni3HHTP2。
Example 3: electrochemical sensor UA (user agent) in-vitro detection designed by molecular line regulation nano interface
A three-electrode working system is built in an electrochemical workstation, the electrode obtained in the embodiment 2 of the invention is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, and a Pt electrode is used as a counter electrode. The voltage recording range was 0V-0.8V, and the voltage step amplitude was 80 mV. In a three-electrode system, the DPV curve is swept in UA solutions with different concentrations to obtain the curve relation between the peak current and the concentration, and the linear range of 0.2-150.0 muM is obtained (figure 3). Wherein, FIG. 3A is a control, unmodified molecule, detection limit of 1.0 μ M, no linearity; FIG. 3B modified flexible molecule FP1 with a detection limit of 5.0. mu.M, which is not linear; FIG. 3C modifies short-chain rigid molecule RP1 with a detection limit of 0.5 μ M and a linear range of 0.5 μ M to 150.0 μ M; FIG. 3D modifies the long-chain rigid molecule RP2 with a detection limit of 0.2. mu.M and a linear range of 0.2. mu.M to 150.0. mu.M. As can be seen from the figure, the electrode modified with the long-chain rigid molecule RP2 is used for detecting UA, and has lower detection limit and higher sensitivity.
Example 4: the selectivity and the competitiveness of different amino acids, neurochemicals, metal ions and active oxygen on UA are measured by adopting a DPV method, as shown in figure 4, the electrode prepared in the embodiment 2 of the invention has better selectivity for detecting UA.
Example 5: the reproducibility of the electrode modified with MOF and RP2 was tested by DPV method, as shown in fig. 5, indicating that the electrode prepared in example 2 of the present invention has good stability.
Example 6: method for detecting UA in mouse brain by using electrochemical sensor modified with long-chain rigid molecules RP2 and MOF
The content of uric acid in hippocampal regions of normal mice and hyperuricemic mice was measured by needle (fig. 6A). Hyperuricemia mice and control mice walk the Morris water maze and the learning ability and memory ability of the mice are judged. The time for the mouse to find the underwater platform is recorded through a positioning navigation test: the duration of five days is five days, normal rats and hyperuricemia rats are respectively placed into water from four water entry points (the water pool is divided into four quadrants of south, east, west and north, the four water entry points are respectively arranged, a platform is placed in the center of one quadrant), the time for the rats to find the platform hidden under the water surface is recorded, the rats are trained for four times every day, and the average value is recorded (fig. 6B). The UA content in the hippocampal region of normal mice was about 1.3. mu.M, and the UA concentration in the hippocampal region of hyperuricemia mice was about 5.0. mu.M. In addition, the maze-walking time decreased after the next day for normal mice and hyperuricemic mice, but the maze-walking time was slower for hyperuricemic mice than for normal mice.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
Claims (11)
2. a method of making an electrochemical sensor, comprising the steps of:
(1) preparing a carbon fiber microelectrode;
(2) electrodepositing gold nanoparticles on the carbon fiber micro-electrode prepared in the step (1);
(3) modifying molecular lines on the carbon fiber micro-electrode with gold nano-particles electrodeposited in the step (2);
(4) modifying the two-dimensional conductive MOF material Ni shown in the formula (a) on the carbon fiber micro-electrode of the electrodeposited gold nano particles after the molecular line is modified in the step (3)3HHTP2Obtaining an electrochemical sensor;
3. the method according to claim 2, wherein in the step (1), the outer diameter of the glass capillary of the carbon fiber microelectrode is 1.0mm to 1.5 mm; the inner diameter is 0.7 mm-1.1 mm;
in the step (2), the specific steps of electrodepositing the gold nanoparticles on the carbon fiber micro-electrode are as follows: firstly, putting a carbon fiber electrode into 0.1M NaOH, and carrying out electrochemical pretreatment for 80s by using 1.5V; and then the gold nanoparticles are electroplated after the gold nanoparticles are inserted into the chloroauric acid solution.
4. The method of claim 3, wherein the concentration of the chloroauric acid solution is 5mM to 50 mM; and/or the voltage of the electrodeposition is-0.1V to-0.2V; and/or the electrodeposition time is 30s-100 s.
6. the method of claim 2, wherein in step (4), the two-dimensional conductive MOF material Ni of formula (a) is modified3HHTP2Before, Ni is added3HHTP2Is dispersed in H2In O to obtain Ni3HHTP2-H2O dispersion liquid; wherein said Ni3HHTP2-H2The concentration of the O dispersion is 1mg/mL-2 mg/mL.
7. An electrochemical sensor prepared by the method of any one of claims 2 to 6.
8. Use of the electrochemical sensor of claim 7 for detecting UA.
9. The application of claim 8, wherein the method of detecting UA comprises the steps of:
detecting different concentrations of UA using the electrochemical sensor of claim 7, establishing a UA concentration-peak current linear relationship by measuring peak current.
10. A method for preparing a molecular thread represented by formula (c) in claim 1, comprising the following steps: adding 4-iodobenzaldehyde and PdCl2(PPh3)2And CuI suspended in 15mL dry THF and 5mLTEA at room temperature; then, 3-ethynylthiophene was added and stirred at 50 ℃; after the 4-iodobenzaldehyde is consumed, continuously stirring for 16 hours to obtain yellow solid, namely the molecular line shown in the formula (c);
wherein, the 4-iodobenzaldehyde and PdCl2(PPh3)2The molar ratio of CuI to 3-ethynylthiophene is 5:20:10: 6.
11. A method for preparing a molecular thread represented by formula (d) in claim 1, comprising the following steps:
step (1): adding 4-iodobenzaldehyde and PdCl2(PPh3)2And CuI 5mL in 15mL dry THF at room temperatureAdding 1-ethynyl-4-iodobenzene into the TEA suspension, stirring the mixture at 50 ℃ until 4-iodobenzaldehyde is consumed, and then stirring for reacting for 16h to obtain an intermediate product;
the 4-iodobenzaldehyde and PdCl2(PPh3)2The molar ratio of CuI to 1-ethynyl-4-iodobenzene is 5:20:10: 6;
step (2): the intermediate was dissolved in 8mL dry THF at room temperature and N22.8ml of LTEA and PdCl are used for the treatment of the above-mentioned diseases2(PPh3)2And CuI dissolution; then, 3-ethynylthiophene was added, and the mixture was stirred at 50 ℃ for 16h to obtain a yellow solid, a molecular line represented by formula (d);
the intermediate product, PdCl2(PPh3)2The molar ratio of CuI to 3-ethynylthiophene is 2.80:11:5.6: 3.06.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060096870A1 (en) * | 2004-11-10 | 2006-05-11 | Fwu-Shan Sheu | Detection of biological molecules |
CN107525834A (en) * | 2017-07-18 | 2017-12-29 | 济南大学 | A kind of DNA aptamer sensors of Cu MOF marks are used for the method for detecting Acetamiprid |
CN108760861A (en) * | 2018-08-30 | 2018-11-06 | 哈尔滨理工大学 | A kind of Ni-MOF based electrochemical sensors for detecting uric acid |
KR102160358B1 (en) * | 2019-04-15 | 2020-09-28 | 인천대학교 산학협력단 | Electrochemical sensor detecting dopamine using nitrogen-doped carbon sphere having au-ag alloy nanodots and platinum and method of the same |
CN112649482A (en) * | 2019-10-11 | 2021-04-13 | 天津大学 | Enzyme-free electrochemical urea sensor based on Ni-MOFs composite material and preparation method and application thereof |
US20210262970A1 (en) * | 2018-06-21 | 2021-08-26 | Trustees Of Dartmouth College | Metal-organic frameworks for electrochemical detection of analytes |
-
2021
- 2021-10-15 CN CN202111202357.4A patent/CN114019003B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060096870A1 (en) * | 2004-11-10 | 2006-05-11 | Fwu-Shan Sheu | Detection of biological molecules |
CN107525834A (en) * | 2017-07-18 | 2017-12-29 | 济南大学 | A kind of DNA aptamer sensors of Cu MOF marks are used for the method for detecting Acetamiprid |
US20210262970A1 (en) * | 2018-06-21 | 2021-08-26 | Trustees Of Dartmouth College | Metal-organic frameworks for electrochemical detection of analytes |
CN108760861A (en) * | 2018-08-30 | 2018-11-06 | 哈尔滨理工大学 | A kind of Ni-MOF based electrochemical sensors for detecting uric acid |
KR102160358B1 (en) * | 2019-04-15 | 2020-09-28 | 인천대학교 산학협력단 | Electrochemical sensor detecting dopamine using nitrogen-doped carbon sphere having au-ag alloy nanodots and platinum and method of the same |
CN112649482A (en) * | 2019-10-11 | 2021-04-13 | 天津大学 | Enzyme-free electrochemical urea sensor based on Ni-MOFs composite material and preparation method and application thereof |
Non-Patent Citations (3)
Title |
---|
YUE WANG ET AL.: "Conductive Metal−Organic Framework Microelectrodes Regulated by Conjugated Molecular Wires for Monitoring of Dopamine in the Mouse Brain", J. AM. CHEM.SOC., vol. 145, no. 5, pages 2118 - 2126 * |
YU-TING HUNG ET AL.: "Catalytic Sonogashira couplings mediated by an amido pincer complex of palladium", INORG. CHEM. FRONT, vol. 1, pages 405 - 413 * |
数据库REGISTRY(在线): "Aurora Fine Chemicals等提供的产品目录", 数据库REGISTRY(在线), pages 2574266 - 41 * |
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