CN109053817B - Nickel-antifungal drug functionalized polyacid compound, preparation method and application - Google Patents
Nickel-antifungal drug functionalized polyacid compound, preparation method and application Download PDFInfo
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- CN109053817B CN109053817B CN201810750901.0A CN201810750901A CN109053817B CN 109053817 B CN109053817 B CN 109053817B CN 201810750901 A CN201810750901 A CN 201810750901A CN 109053817 B CN109053817 B CN 109053817B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003429 antifungal agent Substances 0.000 title claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 229960004884 fluconazole Drugs 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910020628 SiW12O40 Inorganic materials 0.000 claims abstract description 14
- RFHAOTPXVQNOHP-UHFFFAOYSA-N fluconazole Chemical compound C1=NC=NN1CC(C=1C(=CC(F)=CC=1)F)(O)CN1C=NC=N1 RFHAOTPXVQNOHP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 229940121375 antifungal agent Drugs 0.000 claims abstract description 9
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910003206 NH4VO3 Inorganic materials 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 13
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- 229940093430 polyethylene glycol 1500 Drugs 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
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- 238000005406 washing Methods 0.000 claims description 3
- 230000001225 therapeutic effect Effects 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 18
- 239000003814 drug Substances 0.000 abstract description 4
- 108010001336 Horseradish Peroxidase Proteins 0.000 abstract description 3
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- 238000006911 enzymatic reaction Methods 0.000 description 9
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- 150000002500 ions Chemical class 0.000 description 7
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- 230000000977 initiatory effect Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
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- 238000002474 experimental method Methods 0.000 description 5
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- 238000000921 elemental analysis Methods 0.000 description 4
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- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
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- 241000282414 Homo sapiens Species 0.000 description 3
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- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- YRNWIFYIFSBPAU-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C1=CC=C(N(C)C)C=C1 YRNWIFYIFSBPAU-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
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- 230000011506 response to oxidative stress Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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Abstract
The invention discloses a nickel-antifungal drug functionalized polyacid compound and a preparation method thereof, wherein the nickel-antifungal drug functionalized polyacid compound comprises the following steps: h is to be4SiW12O40、Ni(NO3)2Fluconazole, NH4VO3Adding a surfactant into distilled water to dissolve to obtain a pre-reaction solution; and (3) placing the pre-reaction liquid in a reaction kettle, and crystallizing at the constant temperature of 170 ℃ for 4 days to obtain the nickel-antifungal medicine functionalized polyacid compound. The invention takes fluconazole as functional molecule and uses coordination bond phase in the presence of nickel ionsThe Keggin type polyacid is sheared, modified or bridged by interaction, and a functionalized polyacid compound is prepared; the compound is used as the imitated horseradish peroxidase pair H to be researched by utilizing an ultraviolet spectrophotometer2O2The result shows that the compound has better H2O2Sensing performance, for H2O2The detection interval of (a) is 0.1-90 [ mu ] mol.L‑1The lowest detection limit is 0.13 mu mol.L‑1。
Description
Technical Field
The invention belongs to the technical field of preparation of novel biosensors, and particularly relates to a nickel-antifungal drug functionalized polyacid compound, a preparation method and application thereof.
Background
The biological micromolecules play a vital role in the metabolism process and even the whole life process in the human body, and the content of the biological micromolecules directly influences the health of the human body. E.g. H in vivo2O2When the dosage exceeds a certain amount, the redox balance in vivo is broken or the oxidation resistance of the organism is low, so that oxidative stress reaction is caused, even certain damage is caused to some tissues, and the damage is accumulated along with the lapse of time, so that serious diseases such as diabetes, arteriosclerosis, cancer and the like are induced. Therefore, the detection of the biological small molecules becomes an important standard for measuring the living environment, physical quality and health condition of human beings.
H2O2Is one of the products of metabolism in organisms, and can cause damage to the organism. It has been found that H is present in vivo2O2After the content exceeds the standard, the cell decay can be accelerated, and even the diseases such as diabetes, nerve diseases, tumor and the like can be induced to appear. Relating to fluorescence method and electrochemical method for detecting H2O2Although some reports also exist on the biosensors, most of the detection methods have the defects of complex operation, high price, easy interference of detection elements by external conditions and the like, and the development of biological small molecule detection is seriously hindered. Therefore, the development of new detection methods, new testing techniques and the development of new biological detection materials have become the hot spots of research.
Selecting substances with peroxidase-like activity to catalyze H2O2Generating water and oxygen, the oxygen canThe oxidation of Tetramethylbenzidine (TMB) to a blue product was allowed, and H was inferred from the concentration of the blue solution2O2Concentration, this method has become the focus of current research. The peroxidase-like material has catalytic activity similar to that of enzyme, is low in price and easy to store, so that research on the material becomes a key problem for solving the detection of small biological molecules.
Polyoxometallate (polyacid, POMs) has diversified structural characteristics and unique performances such as optical, electric, magnetic and surface activity, and has wide application prospects in the fields of catalysis, sensors, adsorption, ion exchange, antibiosis, antivirus and the like. The polyacid and the polyacid compound after the function thereof have excellent oxidation-reduction property and abundant structural diversity, and can transfer or transmit electrons in the process of acting with the biological micromolecule, so the detection of the biological micromolecule can be realized. In addition, most polyacid molecules are nano-sized in volume, may have excellent characteristics of nano-materials under certain conditions, and can regulate and control the appearance thereof from the molecular level. Therefore, the polyacid and the polyacid-based hybrid thereof have considerable prospects in the field of biological small molecule detection.
Disclosure of Invention
The invention aims to overcome the defects of the prior method and provides a nickel-antifungal drug functionalized polyacid compound and a preparation method thereof, and the prepared polyacid compound has better H content2O2Sensing performance, for H2O2The detection interval of (a) is 0.1-90 [ mu ] mol.L-1The lowest detection limit is 0.13 mu mol.L-1。
The first object of the present invention is to provide a method for preparing a nickel-antifungal drug-functionalized polyacid complex having the formula [ Ni ]2(fkz)2(SiW12O40)]·[Ni2(fkz)2·(H2O)2]·8H2O, specifically comprising the following steps:
h is to be4SiW12O40、Ni(NO3)2FluconazoleAdding a mineralizer and a surfactant into distilled water in sequence, stirring to dissolve the mineralizer and the surfactant, and stirring for 1 hour after all the mineralizer and the surfactant are dissolved to obtain a pre-reaction solution;
wherein H4SiW12O40、Ni(NO3)2The proportion of fluconazole, mineralizer, surfactant and distilled water is 1 mmol: 3 mmol: 2 mmol: 3 mmol: 0.3 mmol: 100 ml;
adjusting the pH value of the pre-reaction liquid to 2.3-2.8, placing the pre-reaction liquid in a high-pressure reaction kettle, crystallizing at the constant temperature of 170 ℃ for 4d, cooling the reaction liquid to the room temperature after crystallization is finished, filtering to remove filtrate, washing filter residue with water, and drying to obtain green blocky crystals, wherein the crystals are [ Ni ] Ni2(fkz)2(SiW12O40)]·[Ni2(fkz)2·(H2O)2]·8H2O；
Wherein fkz is fluconazole anion.
Preferably, the surfactant is polyethylene glycol 1500.
Preferably, the mineralizer is NH4VO3。
Preferably, the pH value of the pre-reaction liquid is adjusted by using a nitric acid solution with the concentration of 1 mol/L.
The second object of the present invention is to provide a nickel-antifungal drug-functionalized polyacid complex prepared according to the above preparation method.
The third purpose of the invention is to provide the nickel-antifungal drug functionalized polyacid complex at H2O2Use in molecular detection.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a hydrothermal synthesis method, selects antifungal drug fluconazole molecules as functional molecules, shears, modifies or bridges Keggin type polyacid by virtue of coordination bond interaction in the presence of nickel ions, and successfully prepares a nickel-fluconazole functionalized polyacid compound with the assistance of a surfactant and a mineralizer; the molecular formula of the crystal is determined to be [ Ni ] through X-ray single crystal diffraction, elemental analysis, infrared spectrum and the like2(fkz)2(SiW12O40)]·[Ni2(fkz)2·(H2O)2]·8H2O; the polyacid compound is used as the horseradish peroxidase-like pair H to be researched by utilizing an ultraviolet spectrophotometer2O2The result shows that the polyacid compound has better H2O2Sensing performance, for H2O2The detection interval of (a) is 0.1-90 [ mu ] mol.L-1The lowest detection limit is 0.13 mu mol.L-1。
Drawings
FIG. 1 is an infrared spectrum of a polyacid complex prepared in example 1;
FIG. 2 is a structural diagram of the basic unit of the polyacid complex prepared in example 1;
FIG. 3 shows two kinds of subunits Ni having the same structural and steric characteristics in the polyacid complex prepared in example 12(fkz)2The structure of (1);
FIG. 4 shows [ SiW ] in the polyacid complex prepared in example 112O40]4-The one-dimensional chain structure diagram of the complex is obtained after the terminal oxygen atom of the polyacid anion coordinates with Ni1 ion in a subunit { S-Ni1 };
FIG. 5 shows the complex of one-dimensional chain structure in the polyacid complex prepared in example 1, the complex being formed by Ni2 ion in { S-Ni2} subunit and [ SiW ]12O40]4-Connecting terminal oxygen atoms in the polyacid anions to form a two-dimensional network structure diagram of a complex;
FIG. 6 shows the polyacid complex prepared in example 1 in para H2O2Absorbance at 643nm with H in the detection of molecules2O2A linear plot of concentration;
FIG. 7 shows polyacid complex catalysis H prepared in example 12O2Ultraviolet spectrogram of substrate TMB within 0-10 min; wherein the upper panel of FIG. 7 is a color chart of the reaction system at different times;
FIG. 8 shows the polyacid complex pair H prepared in example 12O2A graph of the detection kinetics of the molecule; wherein FIG. 8(a) is the speed of initiation of the enzymatic reaction as a function of TMB concentration profile, the lower right panel of FIG. 8(a) is a plot of reciprocal rate of initiation of the enzymatic reaction as a function of reciprocal TMB concentration; FIG. 8(b) is the rate of initiation of the enzymatic reaction as a function of H2O2Graph of concentration variation, the lower right panel of FIG. 8(b) is the reciprocal of the starting velocity of the enzymatic reaction as a function of H2O2Graph of inverse concentration variation.
Detailed Description
In order that those skilled in the art will better understand that the method embodiments of the present invention may be practiced, the present invention will be further described with reference to the following specific examples and accompanying drawings, which are not intended to be limiting.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A preparation method of a nickel-antifungal drug functionalized polyacid compound specifically comprises the following steps:
accurately weigh 300mg of H on an analytical balance4SiW12O4055mg of Ni (NO)3)260mg of fluconazole, 36mg of NH4VO3And 30mg of polyethylene glycol 1500, adding the weighed raw materials into 10mL of distilled water, stirring at normal temperature to fully dissolve the raw materials, and continuing stirring for 1h after the raw materials are fully dissolved to obtain a pre-reaction solution;
adjusting the pH value of the pre-reaction liquid to 2.5 by using a nitric acid solution with the concentration of 1mol/L, then placing the pre-reaction liquid in a stainless steel high-pressure reaction kettle, crystallizing at the constant temperature of 170 ℃ for 4 days, cooling the reaction liquid to room temperature after crystallization is finished, then filtering to remove filtrate, washing filter residues with water, and naturally drying to obtain green blocky crystals, wherein the crystals are [ Ni ] Ni2(fkz)2(SiW12O40)]·[Ni2(fkz)2·(H2O)2]·8H2O, calculated yield 25% (calculated as W);
wherein fkz is fluconazole anion.
For illustrating the effect, the invention also provides a comparative example which is as follows:
comparative example 1
The preparation method of the nickel-antifungal drug functionalized polyacid compound is the same as that in example 1, except that the surfactant polyethylene glycol 1500 is not added into the raw materials for preparation.
Comparative example 2
The preparation method of the nickel-antifungal drug functionalized polyacid complex is the same as that of example 1, except that the mineralizer NH is not added to the raw materials4VO3。
Comparative example 3
The preparation method of the nickel-antifungal drug-functionalized polyacid complex is the same as that of example 1, except that the pH of the pre-reaction solution is adjusted to 3.5.
Comparative example 4
The preparation method of the nickel-antifungal drug functionalized polyacid compound is the same as that in example 1, except that the surfactant added in the raw materials for preparation is polyethylene glycol 2000.
The nickel-antifungal drug-functionalized polyacid complexes prepared in example 1 and comparative examples 1 to 4 were tested for their performance and the results are shown in Table 1.
TABLE 1 Effect of surfactants, mineralizers, acidity on polyacid complex preparation
As can be seen from Table 1, compared with comparative examples 1-4, the product state in example 1 is better, and the product amount is larger, which shows that the pH value of the system influences the solubility of solute and the growth rate of crystal, and the structure of growth element in solution can be changed, thereby determining the structure, shape and size of crystal; in comparative example 4, polyethylene glycol 2000 was used as a surfactant, and although the obtained product was crystalline and had a large amount, the crystalline state was poor, which indicates that the surfactant and the mineralizer can affect the interaction between the reactive species, thereby determining whether the crystals are crystallized or not.
The nickel-antifungal drug-functionalized polyacid complex prepared in example 1 is characterized and structurally described below.
1. X-ray single crystal diffraction data analysis
Crystallographic data of the polyacid complex prepared in example 1 were examined by X-ray single crystal diffraction data analysis, wherein the single crystal data of the polyacid complex were collected on a Bruker CCD diffractometer at 293K, Mo-Ka ray
The crystal structure is analyzed by a SHELXTL-97 program by a direct method and is corrected by a full matrix least square method F2; all non-hydrogen atoms are corrected for anisotropy; the position of the hydrogen atom is obtained by adopting a theoretical hydrogenation mode, and specific crystallographic data are shown in a table 2.
TABLE 2 crystallographic data for polyacid complex
2. Infrared spectroscopic analysis
The polyacid compound prepared in example 1 was measured by Alpha Centaurt FT/IR infrared spectrometer in the range of 400--1(KBr pellet), the results of the specific tests are shown in FIG. 1.
As can be seen from FIG. 1, at 1004(m), 964(s), 910(s), 789(s) cm-1The stretching vibration peak positions are characteristic absorption peaks of upsilon (Si-O), upsilon (W-Od) and upsilon (W-Ob/c-W) of Keggin anions; 1620(s), 1539(m), 1449(m), 1153(m)1102(m) cm-1The stretching vibration peak position is the characteristic absorption peak of fluconazole, which indicates that polyacid and fluconazole drug molecules exist in the polyacid compound prepared in example 1, and Keggin polyacid is not decomposed.
3. Elemental analysis
The elemental analysis of C, H and N in the polyacid complex prepared in example 1 was determined using a Perkin-Elmer2400 analyzer. The elemental analysis results (%) were as follows C52H58F8N24Ni4O54SiW12(4504.09), theoretical values C13.85, H1.29, N7.46 (%); found C13.68, H1.34, N7.44 (%). The element analysis result and the theoretical calculation value can be well matched, and are consistent with the result of crystal structure analysis, and the molecular formula and the structure of the polyacid compound are finally verified.
4. Description of the construction
The X-ray single crystal diffraction structure analysis shows that the unit cell in the polyacid compound is composed of 1 [ SiW12O40]4-Polyacid anion, 4 Ni ions, 4 fluconazole drug molecules, 2 coordinated water molecules and 8 crystal water molecules, as shown in figure 2. In the polyacid complex, 2 Ni1 ions and 2 Ni2 ions respectively form two subunits Ni with the same structure and spatial characteristics with 4 fluconazole drug molecules2(fkz)2(labeled S-Ni1 and S-Ni 2) as shown in FIG. 3; further [ SiW12O40]4-The polyacid anion coordinates with Ni1 ions in a subunit { S-Ni1} through a terminal oxygen atom (O14) of the polyacid anion to form a one-dimensional chain structure (-POMs- { S-Ni1} -POMs- { S-Ni1 }) as shown in FIG. 4; finally, adjacent one-dimensional-POMs- { S-Ni1} -POMs- { S-Ni1} -chains are doped with Ni2 ions in { S-Ni2} subunits and [ SiW ]12O40]4-The terminal oxygen atoms (O2) in the polyacid anion are linked to form a two-dimensional network of complexes, as shown in fig. 5.
The nickel-antifungal drug-functionalized polyacid complex prepared in example 1 is described below in H2O2The application in molecular detection is illustrated.
1. To H2O2Detection of molecules
Polyacid complex pair H prepared in example 12O2The molecular detection is carried out by adopting Shimadzu UV-2550 ultraviolet spectrophotometer, and the detection wavelength range is 350-800 nm.
1) 3mL of NaAc-HAc buffer solution and 2mL of TMB are mixed uniformly, 2mg of the polyacid compound crystal prepared in example 1 is added, the mixture is shaken to form a suspension, and then a pipette is used for adding 1 mu L of dilute H2O2And (5) rapidly shaking to make the mixture fully react, timing and observing color change. By changing the pH value of the HAc-NaAc buffer solution, the ultraviolet spectrum (more than 600 peaks at 800nm at 350-.
2) Under the condition that the pH value is 5.5, different temperatures are controlled by water bath, experiments are carried out, the ultraviolet spectrum (350-.
3) The experiment was carried out at 35 ℃ and pH 5.5, and the ultraviolet spectra at 0min, 2min, 4min, 6min, 8min, and 10min were measured.
4) Preparing diluted H with different concentrations2O2(1, 3, 5, 10, 15, 30, 50, 60, 70, 80, 100, 150, 250, 500, 1000. mu.M), the above experiment was performed to obtain absorbance, a plot was made to obtain a detection range, and a linear regression was performed to obtain a linear equation. The 10 experiments were performed on a blank without added crystals and the standard deviation S0 was calculated and the limit of detection was calculated from LOD ═ KS 0/S. (n-10, K-3; S is the slope of the linear equation).
5) Preparing TMB solution (0.01, 0.03, 0.05, 0.0750.1, 0.15mM) and diluted H at different concentrations2O2(0.05, 0.06, 0.08, 0.10, 0.15, 0.2, 0.3mM), control H2O2The concentration of TMB was varied in the order of 0.01, 0.03, 0.05, 0.1 and 0.15mM at a concentration of 0.1mM, and the absorbance was measured; further, the concentration of TMB was controlled to 0.05mM, and the concentration of TMB was changed to 0.05mM, 0.10 mM, 0.15mM, 0.2 mM, and 0.3mM in this order to measure the absorbance. The kinetics were studied by calculation and mapping using the michaelis equation, and the results are shown in fig. 6.
From FIG. 6, H can be obtained2O2The linear range of detection is 1-90 mu mol.L-1The lowest detection Limit (LOD) is 0.13. mu. mol. L-1(LOD 3S0/S, S0 is the standard deviation of the blank (s.d.), S is the slope of the calibration curve).
2. To H2O2Molecular detectionStudy of Activity
2mg of the polyacid complex prepared in example 1 was added to 1. mu. L H2O2And 2mL of TMB, and 3mL of HAc-NaAc buffer solution was added to the mixture to adjust the H content in the whole reaction system2O2The concentration was 97.8. mu. mol. L-1The concentration of the polyacid complex is 0.4 mg/mL-1TMB concentration of 83. mu. mol. L-1. The solution was monitored using an ultraviolet spectrophotometer and the results are shown in figure 7. As can be seen from FIG. 7, in the reaction system, the absorbance at 643nm of the characteristic peak of TMB in an oxidized state in the mixed solution gradually increases with the passage of time. The absorbance value reached 0.69 at 10 min. The results show that the polyacid compound prepared in example 1 has a better catalytic effect.
3. To H2O2Detection kinetics study of molecules
Since the polyacid complex prepared in example 1 is active like a natural enzyme, it will be at a high concentration of H2O2Under these conditions, we used the Michaelis Menten model to study the activity of the polyacid complex. The Michaelis Menten model is based on a certain H2O2The concentration range is obtained by a Lineweaver-Burk mapping method by adopting the following formula:
ν＝Vmax×[S]/(Km+[S])
wherein, ν is the initial speed of enzymatic reaction, Vmax is the maximum reaction rate, [ S ] is the concentration of reaction substrate, and Km is the Michaelis constant.
Corresponding kinetic parameters in the respective changes of TMB and H2O2Is obtained, see in particular fig. 8, fig. 8 is a graph of the polyacid complex pair H prepared in example 12O2A detection kinetic profile of the molecule, wherein FIG. 8(a) is a graph of the initiation rate of the enzymatic reaction as a function of the concentration of TMB, and the lower right panel of FIG. 8(a) is a graph of the reciprocal of the initiation rate of the enzymatic reaction as a function of the reciprocal of the concentration of TMB; FIG. 8(b) is the rate of initiation of the enzymatic reaction as a function of H2O2Graph of concentration variation, the lower right panel of FIG. 8(b) is the reciprocal of the starting velocity of the enzymatic reaction as a function of H2O2Graph of inverse concentration variation.
The specific test results are shown in Table 3.
Table 3 example 1 comparison of kinetic parameters of polyacid complexes and other mimetic enzymes
As shown in Table 3, when TMB was used as a substrate, the corresponding Km values were lower than those of horseradish peroxidase and PW12, confirming that the polyacid complex of example 1 has a higher binding ability to TMB. At the same time, with H2O2The Km value for the substrate is also lower than that of horseradish peroxidase and PW12, also demonstrating the polyacid complex pair H of example 12O2Has higher binding capacity.
It should be noted that the present invention has been described in terms of preferred embodiments, but that additional variations and modifications may be made to these embodiments by those of ordinary skill in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Thus, it is intended that such modifications and variations be included within the scope of the present invention as set forth in the claims and the equivalents thereof.
Claims (4)
1. A method for preparing a nickel-antifungal drug functionalized polyacid compound, wherein the molecular formula of the nickel-antifungal drug functionalized polyacid compound is [ Ni2(fkz)2(SiW12O40)]·[Ni2(fkz)2·(H2O)2]·8H2O, which is characterized by comprising the following steps:
h is to be4SiW12O40、Ni(NO3)2Sequentially adding fluconazole, a mineralizer and a surfactant into distilled water, stirring to dissolve the fluconazole, the mineralizer and the surfactant, and stirring for 1h after the fluconazole, the mineralizer and the surfactant are completely dissolved to obtain a pre-reaction solution;
wherein H4SiW12O40、Ni(NO3)2The proportion of fluconazole, mineralizer, surfactant and distilled water is 1 mmol: 3 mmol: 2 mmol: 3 mmol: 0.3 mmol: 100 ml;
adjusting the pH value of the pre-reaction liquid to 2.3-2.8, placing the pre-reaction liquid in a high-pressure reaction kettle, crystallizing at the constant temperature of 170 ℃ for 4 days, cooling the reaction liquid to the room temperature after crystallization is finished, filtering to remove filtrate, washing filter residue with water, and drying to obtain green blocky crystals, wherein the crystals are [ Ni ] Ni2(fkz)2(SiW12O40)]·[Ni2(fkz)2·(H2O)2]·8H2O；
Wherein fkz is fluconazole anion;
the surfactant is polyethylene glycol 1500, and the mineralizer is NH4VO3。
2. The method of functionalizing a polyacid complex with a nickel-antifungal drug as claimed in claim 1, wherein the pH of the pre-reaction solution is adjusted with a nitric acid solution having a concentration of 1 mol/L.
3. A nickel-antifungal drug-functionalized polyacid complex prepared by the preparation method of any one of claims 1-2.
4. The nickel-antifungal drug-functionalized polyacid complex of claim 3 in H2O2Use of the molecule for detection of non-therapeutic or diagnostic purposes.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597115A (en) * | 2004-03-26 | 2005-03-23 | 郑州大学 | Fluoro comzole coordination polymer, preparation method and use |
| CN107698624A (en) * | 2017-08-30 | 2018-02-16 | 渤海大学 | A kind of application of multi-functional nickel complex based on organic ligand and its method and carbon paste electrode for synthesizing carbon paste electrode |
-
2018
- 2018-07-10 CN CN201810750901.0A patent/CN109053817B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597115A (en) * | 2004-03-26 | 2005-03-23 | 郑州大学 | Fluoro comzole coordination polymer, preparation method and use |
| CN107698624A (en) * | 2017-08-30 | 2018-02-16 | 渤海大学 | A kind of application of multi-functional nickel complex based on organic ligand and its method and carbon paste electrode for synthesizing carbon paste electrode |
Non-Patent Citations (9)
| Title |
|---|
| A Stable Polyoxometalate-Pillared Metal-Organic Framework for Proton-Conducting and Colorimetric Biosensing;En-LongZhou等，;《Chem.Eur.J.》;20150714;第11894-11898页 * |
| Combination of POMs and deliberately designed macrocations：a rational approach for synthesis of POM-pillared metal-organic framework;Ya-Qian Lan等，;《Dalton Trans.》;20081216;第940-947页 * |
| Construction of different dimensional inorganic-organic hybrid materials based on polyoxometalates and metal-organic units via changing metal ions:from non-covalent interactions to covalent connections;Ya-Qian Lan等，;《Dalton Trans.》;20080613;第3824-3835页 * |
| Fast and Sensitive Colorimetric Detection of H2O2 and Glucose：A Strategy Based on Polyoxometalate Clusters;Sen Liu等，;《ChemPlusChem》;20120430;第541-544页 * |
| Inorganic-organic hybrid materials with different dimensions constructed from copper-fluconazole metal-organic units and Keggin polyanion clusters;Shun-Li Li等，;《Dalton Trans.》;20080218;第2015-2025页 * |
| Polyoxometalates as peroxidase mimetics and their applications in H2O2 and glucose detection;Jingjing Wang等，;《Biosensors and Bioelectronics》;20120410;第18-21页 * |
| Synthesis and characterization of metal(II)-fluconazole complexes:Chain-like structure and photoluminescence;Yun Gong等，;《Journal of Molecular Structure》;20061115;第48-57页 * |
| Synthesis and polypyrrole-loading study of antifungal medicine fluconazole functionalized Keggin polyoxotungstates;Fei Xie等，;《Journal of Coordination Chemistry》;20180214;第1-11页 * |
| 不同金属-氧簇构筑的配合物的合成、结构和性质研究;李顺利，;《东北师范大学博士学位论文》;20081115;全文 * |
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