CN113248528B - Three-dimensional Ag (I) complex synthesized based on silver hexafluorosilicate and synthesis method and application thereof - Google Patents
Three-dimensional Ag (I) complex synthesized based on silver hexafluorosilicate and synthesis method and application thereof Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- -1 silver hexafluorosilicate Chemical compound 0.000 title abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229930182555 Penicillin Natural products 0.000 claims abstract description 26
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 claims abstract description 26
- 229940049954 penicillin Drugs 0.000 claims abstract description 26
- 108091023037 Aptamer Proteins 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 21
- 238000001514 detection method Methods 0.000 claims abstract description 14
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- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 150000002343 gold Chemical class 0.000 claims abstract description 8
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
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- 239000002184 metal Substances 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 150000003839 salts Chemical class 0.000 claims description 34
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 33
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- 239000007788 liquid Substances 0.000 claims description 30
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- 239000013078 crystal Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 15
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- 238000000034 method Methods 0.000 claims description 8
- PDGVLYLXTUFIOL-UHFFFAOYSA-N n,n-dipyridin-4-ylpyridin-4-amine Chemical compound C1=NC=CC(N(C=2C=CN=CC=2)C=2C=CN=CC=2)=C1 PDGVLYLXTUFIOL-UHFFFAOYSA-N 0.000 claims description 8
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- 238000003786 synthesis reaction Methods 0.000 claims 1
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- 230000001965 increasing effect Effects 0.000 abstract description 4
- DBQIWTFUWZFCRA-UHFFFAOYSA-N C(C=C1)=CC(C2=CC=NC=C2)=C1N(C1=CC=NC=C1)C1=CC=NC=C1 Chemical compound C(C=C1)=CC(C2=CC=NC=C2)=C1N(C1=CC=NC=C1)C1=CC=NC=C1 DBQIWTFUWZFCRA-UHFFFAOYSA-N 0.000 abstract 1
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- 238000010521 absorption reaction Methods 0.000 description 4
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Abstract
The invention discloses a three-dimensional Ag (I) complex synthesized based on silver hexafluorosilicate and a synthesis method and application thereof, wherein the chemical formula of the three-dimensional Ag (I) complex is [ Ag [ ]2(TPA)2]·SiF6Wherein the TPA is tri (4-pyridyl) aniline. Mixing the three-dimensional Ag (I) complex with water to obtain 1-1.5 mg mL–1And (2) taking 10-20 mu L of the dispersion, placing the dispersion on the surface of a gold electrode, standing in the air for at least 2 hours to obtain a modified gold electrode, placing the modified gold electrode in an aptamer aqueous solution for at least 2 hours to obtain an electrochemical impedance biosensor, detecting penicillin in a solution to be detected by using the electrochemical impedance biosensor, and increasing the impedance of the electrochemical impedance biosensor when the solution to be detected contains penicillin. The synthesis method of the three-dimensional Ag (I) complex has the advantages of simple and easy operation, simple required equipment and good reproducibility, and the prepared three-dimensional Ag (I) complex has the advantages of high yield, good stability and the like, and can be widely applied to the field of detection of electrochemical impedance aptamer sensors.
Description
Technical Field
The invention belongs to the technical field of penicillin detection, and particularly relates to a three-dimensional Ag (I) complex and a synthesis method and application thereof.
Background
In recent years, coordination polymers as a novel class of complexes have been widely studied and applied in a variety of fields, such as heterogeneous catalysis, biomolecule immobilization, drug delivery, fluorescence detection, optical devices, gas capture, and the like. The material contains metal ions or metal clusters and organic ligands containing electron donating groups such as oxygen and nitrogen, and is connected through coordination bonds to form an inorganic-organic hybrid network structure, so that the material has excellent designability and structural property diversity. Coordination polymers are currently of particular interest in the scientific and industrial fields as one of the most promising solid materials.
Penicillin is the most common antibiotic at present and is mainly used as a feed additive for medicines and livestock. Due to unlimited abuse, a large amount of penicillin remains, and a series of food safety and environmental problems are generated, such as water pollution, enhanced bacterial drug resistance and the like, which can cause the disturbance and imbalance of the microbial environmental balance of human bodies and seriously cause toxic reaction or teratogenesis and disability. Researches show that the allergic symptoms of penicillin-sensitive people can be caused by very low-concentration penicillin residues (about 1ppb), so that the method has important theoretical and practical significance for efficient detection and identification of trace penicillin.
The aptamer is a kind of nucleotide with specificity obtained by in vitro screening through an exponential enrichment ligand phylogeny technology. The aptamer biosensor is a novel aptamer-based biosensor, can continuously and reversibly perform molecular recognition, and can be combined with target molecules with high specificity and high affinity, so that the aptamer biosensor can be used as recognition molecules of the aptamer sensor. The electrochemical sensor, especially the electrochemical impedance sensor, has the advantages of high selectivity, high sensitivity, low cost, easy operation and the like. The modification layer on the surface of the electrode of the electrochemical sensor often has great influence on the final detection result. Electrochemical impedance aptamer sensors based on coordination polymer materials for penicillin detection are not reported at present. Therefore, designing a coordination polymer material with high stability and using the coordination polymer material for efficient electrochemical impedance detection of penicillin has great challenges and practical significance.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a water stable three dimensional ag (i) complex containing tris (4-pyridyl) amine.
The invention also aims to provide a synthesis method of the three-dimensional Ag (I) complex.
The invention also aims to provide an electrochemical impedance biosensor constructed by the three-dimensional Ag (I) complex.
It is another object of the present invention to provide the use of the above electrochemical impedance biosensor for the detection of penicillin in water, which electrochemical impedance biosensor has a significant electrochemical impedance detection effect on penicillin.
The purpose of the invention is realized by the following technical scheme.
A three-dimensional Ag (I) complex with a chemical formula of [ Ag [ ]2(TPA)2]·SiF6Wherein said TPA is tris (4-pyridyl) amine.
In the technical scheme, the TPA has the following structural formula:
in the technical scheme, the crystal of the three-dimensional Ag (I) complex belongs to a cubic system, and the space group is P4332, unit cell parameter of
α＝β＝γ＝90°,
Z＝4。
In the technical scheme, when the temperature is higher than 250 ℃, the three-dimensional Ag (I) complex starts to decompose; when the temperature rises to 800 ℃, the residue is silver oxide.
The synthesis method of the three-dimensional Ag (I) complex comprises the following steps:
firstly, adding an Ag (I) metal salt aqueous solution into a container to be used as a lower layer liquid, then adding ethyl acetate into the container to be used as an intermediate layer liquid, then adding a tri (4-pyridyl) amine methanol solution into the container to be used as an upper layer liquid, standing at the room temperature of 20-25 ℃ until a colorless crystal is obtained to be a three-dimensional Ag (I) complex, wherein,
the preparation method of the methanol solution of the tri (4-pyridyl) amine comprises the following steps: dissolving tri (4-pyridyl) amine in methanol to obtain a tri (4-pyridyl) amine methanol solution;
the preparation method of the aqueous solution of the Ag (I) metal salt comprises the following steps: dissolving Ag (I) metal saltIn water, obtaining Ag (I) metal salt aqueous solution2SiF6；
The ratio of the tri (4-pyridyl) amine in the upper layer liquid to the Ag (I) metal salt in the lower layer liquid is (0.2-0.3): 1.
in the technical scheme, the ratio of the ethyl acetate to the water is (1-2): 2 in parts by volume.
In the technical scheme, the glass is placed at the room temperature of 20-25 ℃ for at least 4 days, 24 hours per day, and preferably 4-6 days.
In the technical scheme, the ratio of the mass parts of the tri (4-pyridyl) amine to the volume parts of the methanol in the tri (4-pyridyl) amine methanol solution is (5-10): 1.
in the above technical scheme, the ratio of the mass parts of the ag (i) metal salt in the ag (i) metal salt aqueous solution to the volume parts of the water is (25-32.5): 1.
in the above technical scheme, the unit of volume parts is mL, and the unit of quantity parts of the substance is mmol.
In the technical scheme, the crystal is obtained by filtering, washed by ethanol and dried in the air.
The electrochemical impedance biosensor constructed by the three-dimensional Ag (I) complex.
In the technical scheme, the three-dimensional Ag (I) complex is mixed with water to obtain 1-1.5 mg mL–1The method comprises the steps of placing 10-20 mu L of dispersion liquid on the surface of a gold electrode, standing the dispersion liquid in the air for at least 2 hours to obtain a modified gold electrode, and placing the modified gold electrode in an aptamer aqueous solution for at least 2 hours to obtain the electrochemical impedance biosensor, wherein the aptamer aqueous solution is formed by mixing an aptamer corresponding to penicillin and water, and the concentration of the aptamer in the aptamer aqueous solution is 10-20 ng mL–1。
The electrochemical impedance biosensor is applied to the detection of penicillin in water.
In the technical scheme, the electrochemical impedance biosensor is used for detecting penicillin in a solution to be detected, and when the solution to be detected contains penicillin, the impedance of the electrochemical impedance biosensor is increased.
Compared with the prior art, the synthesis method of the three-dimensional Ag (I) complex has the advantages of simple and easy operation, simple required equipment and good reproducibility, and the prepared three-dimensional Ag (I) complex has the advantages of high yield, good stability and the like, and can be widely applied to the field of detection of electrochemical impedance aptamer sensors.
Drawings
FIG. 1 is a diagram of coordination environment of Ag (I) in a three-dimensional Ag (I) complex according to the present invention;
FIG. 2 is a schematic diagram of the coordination mode of tris (4-pyridyl) amine in a three-dimensional Ag (I) complex according to the present invention;
FIG. 3 is a three-dimensional structure diagram of the three-dimensional Ag (I) complex of the present invention;
FIG. 4 is a comparison of an experimental pattern (synthetic sample) and a theoretical pattern (simulation) of X-ray powder diffraction (PXRD) of a three-dimensional Ag (I) complex of the present invention;
FIG. 5 is a graph comparing X-ray powder diffraction (PXRD) experimental patterns (synthetic samples) of a three-dimensional Ag (I) complex of the present invention with those after 1 week of immersion in water;
FIG. 6 is a thermogravimetric analysis plot of a three-dimensional Ag (I) complex of the present invention;
FIG. 7 shows the impedance detection of penicillin by the electrochemical impedance biosensor constructed by the three-dimensional Ag (I) complex of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
Silver hexafluorosilicate, penicillin, methanol, and ethyl acetate used in the following examples were all purchased from Sigma-Aldrich Sigma Aldrich (shanghai) trade company, inc. All drugs and reagents were used directly.
The sequence order of the aptamer is 5' -NH2CTG AAT TGG ATC TCT CTT CTT GAG CGA TCT CCA CA-3' purchased from Biotechnology engineering (Shanghai) Ltd.
Tris (4-pyridyl) amine was synthesized according to the following references: F.Bures, D.Cvejn, K.Melanova, L.Benes, J.Svoboda, V.Zima, O.Pytela, T.Mikysek, Z.Ruzickova, I.V.Kityk, A.Wojciechowski, N.Al Zayed, J.Mater.chem.C,2016,4, 468-478.
Gold electrodes were purchased from Tianjin Aida constant technologies, Inc., type: and Au 130.
Examples the following three-dimensional Ag (I) complexes have the formula [ Ag2(TPA)2]·SiF6Wherein, the TPA has the following structural formula:
volume parts are in mL and parts of material are in mmol.
Example 1
The synthesis method of the three-dimensional Ag (I) complex comprises the following steps:
firstly, putting an Ag (I) metal salt aqueous solution into a test tube as a lower layer liquid, then putting 1mL ethyl acetate into the test tube as an intermediate layer liquid, then slowly adding a tri (4-pyridyl) amine methanol solution into the test tube as an upper layer liquid, standing for 4 days at the room temperature of 20-25 ℃ until colorless crystals appear (24 hours per day), wherein the crystals are three-dimensional Ag (I) complexes, filtering to obtain crystals, washing by using ethanol, and drying for 1 day at the room temperature of 20-25 ℃ in the air. The yield of the three-dimensional Ag (I) complex is tested to be 64%.
Wherein,
the preparation method of the methanol solution of the tri (4-pyridyl) amine comprises the following steps: dissolving 10mmol of tri (4-pyridyl) amine in 2mL of methanol to obtain a methanol solution of tri (4-pyridyl) amine, wherein the ratio of the mass parts of the tri (4-pyridyl) amine to the volume parts of the methanol is 5: 1.
the preparation method of the aqueous solution of the Ag (I) metal salt comprises the following steps: preparation of Ag2SiF6As Ag (I) metal salt, 50mmol of Ag (I) metal salt was dissolved in 2mL of water to obtain Ag (I) metal salt aqueous solution, and the ratio of mass parts of Ag (I) metal salt to volume parts of water was 25: 1.
the ratio of the tri (4-pyridyl) amine in the upper layer liquid to the Ag (I) metal salt in the lower layer liquid is 0.2: 1.
example 1 preparation of major infrared absorption peaks (cm) of three-dimensional Ag (I) complexes–1)：3442br,3045m,2978s,2897s,1634s,1582s,1490s,1422s,1347s,1291s,1215s,1091s,1048s,955s,937s,880s,825s,741s,627s,525m,482s,423s。
Example 2
The synthesis method of the three-dimensional Ag (I) complex comprises the following steps:
firstly, putting an Ag (I) metal salt aqueous solution into a test tube as a lower layer liquid, then putting 1mL ethyl acetate into the test tube as an intermediate layer liquid, then slowly adding a tri (4-pyridyl) amine methanol solution into the test tube as an upper layer liquid, standing for 5 days at the room temperature of 20-25 ℃ until colorless crystals appear (24 hours per day), wherein the crystals are three-dimensional Ag (I) complexes, filtering to obtain crystals, washing by using ethanol, and drying for 1 day at the room temperature of 20-25 ℃ in the air. The yield of the three-dimensional Ag (I) complex was tested to be 67%.
Wherein,
the preparation method of the tri (4-pyridyl) amine methanol solution comprises the following steps: dissolving 15mmol of tri (4-pyridyl) amine in 2mL of methanol to obtain a methanol solution of tri (4-pyridyl) amine, wherein the ratio of the mass fraction of the tri (4-pyridyl) amine to the volume fraction of the methanol is 7.5: 1.
the preparation method of the aqueous solution of the Ag (I) metal salt comprises the following steps: preparing Ag2SiF6As Ag (I) metal salt, 60mmol of Ag (I) metal salt was dissolved in 2mL of water to obtain Ag (I) metal salt aqueous solution, and the ratio of the mass parts of Ag (I) metal salt to the volume parts of water was 30: 1.
the ratio of the tri (4-pyridyl) amine in the upper layer liquid to the Ag (I) metal salt in the lower layer liquid is 0.25: 1.
example 2 preparation of major Infrared absorption Peak (cm) of three-dimensional Ag (I) Complex–1)：3443br,3044m,2976s,2898s,1634s,1582s,1489s,1422s,1346s,1291s,1215s,1090s,1048s,956s,937s,881s,825s,741s,627s,524m,482s,424s。
Example 3
The synthesis method of the three-dimensional Ag (I) complex comprises the following steps:
firstly, putting an Ag (I) metal salt aqueous solution into a test tube as a lower layer liquid, then putting 1mL ethyl acetate into the test tube as an intermediate layer liquid, then slowly adding a tri (4-pyridyl) amine methanol solution into the test tube as an upper layer liquid, standing for 6 days at the room temperature of 20-25 ℃ until colorless crystals appear (24 hours per day), wherein the crystals are three-dimensional Ag (I) complexes, filtering to obtain crystals, washing by using ethanol, and drying in the air at the room temperature of 20-25 ℃ for 1 day. The yield of the three-dimensional Ag (I) complex is 69 percent.
Wherein,
the preparation method of the methanol solution of the tri (4-pyridyl) amine comprises the following steps: dissolving 18mmol of tri (4-pyridyl) amine in 2mL of methanol to obtain a methanol solution of tri (4-pyridyl) amine, wherein the ratio of the mass parts of the tri (4-pyridyl) amine to the volume parts of the methanol is 9: 1.
the preparation method of the aqueous solution of the Ag (I) metal salt comprises the following steps: preparation of Ag2SiF6As Ag (I) metal salt, 65mmol of Ag (I) metal salt was dissolved in 2mL of water to obtain Ag (I) metal salt aqueous solution, and the ratio of mass parts of Ag (I) metal salt to volume parts of water was 32.5: 1.
the ratio of the tri (4-pyridyl) amine in the upper layer liquid to the Ag (I) metal salt in the lower layer liquid is 0.277: 1.
example 3 preparation of major Infrared absorption Peak (cm) of three-dimensional Ag (I) Complex–1)：3441br,3043m,2975s,2897s,1634s,1582s,1488s,1422s,1345s,1290s,1215s,1090s,1047s,956s,936s,881s,824s,741s,627s,524m,483s,424s。
The three-dimensional Ag (I) complex obtained in example 1 was further characterized as follows:
(1) determination of Crystal Structure
Selecting single crystal with proper size under microscope, and monochromating Mo-Ka ray with graphite on Bruker APEX II CCD diffractometer
To be provided with
Diffraction data were collected at room temperature. All diffraction data were corrected for semi-empirical absorption by the SADABS software using the multi-scan method. The unit cell parameters were determined using the least squares method. Data reduction and structure resolution were done using SAINT and SHELXL packages, respectively. All non-hydrogen atoms were anisotropically refined using full matrix least squares. The crystallographic data of the three-dimensional Ag (I) complex obtained in example 1 are shown in Table 1. The crystal structure is shown in fig. 1, fig. 2 and fig. 3.
TABLE 1 Main crystallographic data and refinement parameters of three-dimensional Ag (I) complexes
aR1＝Σ(||Fo|-|Fc||)/Σ|Fo|.bwR2＝[Σw(|Fo|2-|Fc|2)2/Σw(Fo 2)2]1/2
As can be seen from the above characterization results, the three-dimensional Ag (I) complex of the invention belongs to the cubic system, and the space group is P4332, unit cell parameter of
α＝β＝γ＝90°,
Z＝4。
Each Ag (I) in the three-dimensional Ag (I) complex adopts a penta-coordination mode, namely one Ag (I) is connected with 2 fluorine atoms and 3 nitrogen atoms, wherein the three nitrogen atoms are respectively from three crystallographically independent tri (4-pyridyl) amine (ligand), and the two fluorine atoms are from two different SiFs6 2–Ions (fig. 1). Meanwhile, each tris (4-pyridyl) amine is linked to three crystallographically independent ag (i) ions (fig. 2) and the three ag (i) ions are linked to the nitrogen of the tris (4-pyridyl) amine on the benzene ring, respectively. Each SiF6 2–To which 3 Ag (I) bonds. Three (4-Pyridyl) amine and ag (i) are connected to each other by coordination bonds to form a crystalline material having a three-dimensional network structure (fig. 3).
(2) Powder diffraction measurement
Powder diffraction data were collected and measured on a Bruker D8 ADVANCE diffractometer (synthetic samples in the figure). The instrument was operated at 40 kilowatts and 40 milliamps. A graphite monochromatized Cu target X-ray was used. The width of the divergent slit is 0.6mm, the width of the anti-divergent slit is 6mm, and the width of the Soller slit is 4 degrees; data collection was done using a 2 theta/theta scan pattern with continuous scanning in the range of 5 degrees to 50 degrees, with a scan speed of 0.1 degrees/second and a step size of 0.02 degrees.
The results of the powder X-ray diffraction simulated theoretically (simulated in the figure) were obtained by simulation of the X-ray single crystal structure using the Mercury 1.4.1 software package.
As shown in fig. 4, the powder diffraction result of the three-dimensional ag (i) complex obtained in example 1 shows that the powder diffraction peak (synthesized sample) of the macro-prepared crystalline product is the same as the theoretically simulated diffraction pattern (simulation), which indicates that the crystalline product has reliable phase purity and consistency with the crystal structure, and provides guarantee for the application of the crystalline product as an electrode modification material.
The powder diffraction peak of the three-dimensional Ag (I) complex after being soaked in water for one week at room temperature (in the figure, the water is soaked for one week) is the same as that of the originally synthesized three-dimensional Ag (I) complex (synthetic sample), and the three-dimensional Ag (I) complex provided by the invention has excellent water stability (in the figure 5).
(3) Thermogravimetric analysis determination
The thermogravimetric analysis experiments were performed on a thermogravimetric analyzer of Shimadzu simultaneous DTG-60A, measured by heating from room temperature to 800 ℃ at a rate of 10 ℃/min in air. The measurement results are shown in fig. 6, and the three-dimensional ag (i) complex obtained in example 1 can stably exist before 250 ℃. After the temperature continued to rise, the complex began to decompose, leaving a residue of silver oxide.
(4) Electrochemical impedance biosensor construction based on three-dimensional Ag (I) complex and penicillin detection
Mixing the three-dimensional Ag (I) complex with water to obtain 1mg mL–1The dispersion of (a) is,placing 10 mu L of dispersion liquid on the surface of a gold electrode, standing in the air for 2 hours to obtain a modified gold electrode, and placing the modified gold electrode in an aptamer aqueous solution (5mL) for 2 hours to obtain the electrochemical impedance biosensor, wherein the aptamer aqueous solution is formed by mixing an aptamer corresponding to penicillin and water, and the concentration of the aptamer in the aptamer aqueous solution is 10ng mL–1。
Electrochemical impedance biosensors were placed in different concentrations (0.001, 0.005, 0.01, 0.05, 0.1, 0.5ng mL)–1) In the penicillin aqueous solution, the impedance change of the electrochemical impedance biosensor is detected by using a Shanghai Chenghua electrochemical workstation. The experimental results show that: the impedance of the electrochemical impedance biosensor is further increased along with the increase of the concentration of the penicillin, and the results show that the three-dimensional Ag (I) complex has a remarkable electrochemical impedance increasing effect on the specific penicillin and can be used for efficient electrochemical impedance detection of trace penicillin (figure 7).
The three-dimensional Ag (I) complexes obtained in examples 2 and 3 all have the same technical effects as those obtained in example 1.
Statement regarding sponsoring research or development
The invention is applied to obtain the subsidies of the national science foundation project (foundation number: 21801187) of the youth science foundation and the innovative team culture plan (foundation number: TD13-5074) of the high school in Tianjin city.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (9)
1. A three-dimensional Ag (I) complex is characterized in that the chemical formula is [ Ag [ ]2(TPA)2]·SiF6The molecular formula of the three-dimensional Ag (I) complex is C45H36F12N12Si2Ag3The molecular weight of the three-dimensional Ag (I) complex is 1352.62, wherein the TPA is tri (4-pyridyl) amineThe TPA has the following structural formula:
the crystal of the three-dimensional Ag (I) complex belongs to a cubic crystal system, and the space group is P4332, unit cell parameter of
α＝β＝γ＝90°,
Z＝4。
2. The method of synthesizing the three-dimensional ag (i) complex of claim 1, comprising the steps of:
firstly, adding an Ag (I) metal salt aqueous solution into a container to be used as a lower layer liquid, then adding ethyl acetate into the container to be used as an intermediate layer liquid, then adding a tri (4-pyridyl) amine methanol solution into the container to be used as an upper layer liquid, standing at the room temperature of 20-25 ℃ until a colorless crystal is obtained to be a three-dimensional Ag (I) complex, wherein,
the preparation method of the methanol solution of the tri (4-pyridyl) amine comprises the following steps: dissolving tri (4-pyridyl) amine in methanol to obtain a methanol solution of tri (4-pyridyl) amine;
the preparation method of the aqueous solution of the Ag (I) metal salt comprises the following steps: dissolving Ag (I) metal salt in water to obtain Ag (I) metal salt aqueous solution2SiF6；
The ratio of the tri (4-pyridyl) amine in the upper layer liquid to the Ag (I) metal salt in the lower layer liquid is (0.2-0.3): 1.
3. the synthesis method according to claim 2, wherein the ratio of the ethyl acetate to the water is (1-2): 2 in parts by volume.
4. The method of claim 3, wherein the composition is allowed to stand at room temperature of 20-25 ℃ for at least 4 days and 24 hours per day.
5. The synthesis method according to claim 4, wherein the ratio of the mass fraction of tris (4-pyridyl) amine to the volume fraction of methanol in the tris (4-pyridyl) amine methanol solution is (5-10): 1;
the ratio of the parts by weight of the Ag (I) metal salt in the Ag (I) metal salt aqueous solution to the parts by volume of the water is (25-32.5): 1;
the volume parts are in units of mL, and the quantity parts of the substances are in units of mmol.
6. The synthesis process according to claim 5, characterized in that the crystals are obtained by filtration, washed with ethanol and dried in air.
7. An electrochemical impedance biosensor constructed by one of the three-dimensional Ag (I) complex as defined in claim 1 and the three-dimensional Ag (I) complex obtained by the synthesis method as defined in claims 2-6.
8. The electrochemical impedance biosensor of claim 7, wherein the three-dimensional Ag (I) complex is mixed with water to obtain 1-1.5 mg mL–1The method comprises the steps of placing 10-20 mu L of dispersion liquid on the surface of a gold electrode, standing the dispersion liquid in the air for at least 2 hours to obtain a modified gold electrode, and placing the modified gold electrode in an aptamer aqueous solution for at least 2 hours to obtain the electrochemical impedance biosensor, wherein the aptamer aqueous solution is formed by mixing an aptamer corresponding to penicillin and water, and the concentration of the aptamer in the aptamer aqueous solution is 10-20 ng mL–1。
9. Use of the electrochemical impedance biosensor as defined in claim 7 or 8 for the detection of penicillin in water.
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| KR101554680B1 (en) * | 2012-03-16 | 2015-09-21 | 단국대학교 산학협력단 | Aromatic amine compound and organic electroluminescent device including the same |
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| KR101554680B1 (en) * | 2012-03-16 | 2015-09-21 | 단국대학교 산학협력단 | Aromatic amine compound and organic electroluminescent device including the same |
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| Self-assembly of two Ag(I) metal-organic frameworks based on tri(pyridin-4-yl)amine: Crystal structures, anion-directed effect, and Cr2O2-7 capture behaviour;Miao Chaolin 等;《Inorganic Chemistry Communications》;20191231;第112卷;第1387-7003页 * |
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