CN114907418A - Heteropolyacid salt-organic ligand compound and synthetic method and application thereof - Google Patents

Heteropolyacid salt-organic ligand compound and synthetic method and application thereof Download PDF

Info

Publication number
CN114907418A
CN114907418A CN202210496358.2A CN202210496358A CN114907418A CN 114907418 A CN114907418 A CN 114907418A CN 202210496358 A CN202210496358 A CN 202210496358A CN 114907418 A CN114907418 A CN 114907418A
Authority
CN
China
Prior art keywords
organic ligand
ligand compound
heteropolyacid salt
triazole
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210496358.2A
Other languages
Chinese (zh)
Inventor
倪鲁彬
章瀚之
常文慧
王培森
王牌
王梦尧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yangzhou University
Original Assignee
Yangzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yangzhou University filed Critical Yangzhou University
Priority to CN202210496358.2A priority Critical patent/CN114907418A/en
Publication of CN114907418A publication Critical patent/CN114907418A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses a heteropolyacid salt-organic ligand compound and a synthesis method and application thereof. The method uses a unit { P } 2 W 18 O 184 } 40‑ Based on the basic, 1,2, 4-triazole and transition metal Ag are introduced to synthesize the polyacid compound K through self-assembly 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]. The invention utilizes the structural characteristics of polyoxometallate and the biological effect with antitumor activity, and changes the surface charge and electrode of the POM by introducing organic groups into the POM frameworkThe prepared heteropoly acid salt-organic ligand compound has an inhibition effect on tumor cells, shows strong anti-tumor activity on liver cancer cells, and can be used as an anti-tumor medicament.

Description

Heteropolyacid salt-organic ligand compound and synthetic method and application thereof
Technical Field
The invention belongs to the field of antitumor drugs, and relates to a heteropolyacid salt-organic ligand compound, and a synthesis method and application thereof.
Background
Polyoxometallates (POMs) have biochemical characteristics of resisting tumors, viruses, bacteria and the like, and are considered to be metal medicaments with relatively development prospects. However, their cytotoxicity to normal cells and their interaction with biomolecules prevent their further clinical use. The POMs with more biocompatible organic ligands are expected to improve the biological activity and the biological specificity through a synergistic effect. Studies have shown that the amphiphilic nature of POM hybrids allows the vesicles formed to bind more readily to the cell membrane and then be taken up by the cell, resulting in a significant increase in antitumor activity. The selective organic ligand is adopted to decorate POM, so that a novel POM hybrid medicine with increased biological activity can be obtained.
Document 1(J Liu, W Lu, Y Kai, Z Su, B Zhou, New J. chem.,2015,39,1139) sodium tungstate and sodium arsenite are dissolved in water, then transition metal salts such as nickel chloride, cobalt chloride, manganese chloride are added, 1,2, 4-triazole is finally added, pH is adjusted, after reaction at 80 ℃ for 30 minutes, crystallization is carried out at room temperature, and tungstate { AsW- 9 O 33 Bonding transition metals Mn, Ni and Co with 1,2, 4-triazole to obtain compound Na 6 [{Na(H 2 O)} 3 {Ni(Htaz)} 3 (AsW 9 O 33 ) 2 ]·4H 2 Based on good antiviral and antitumor properties of the arsenic-containing and transition metal-containing compound, the compound achieves an antitumor effect by inhibiting cell proliferation and inducing apoptosis, and shows a strong inhibiting effect on proliferation of HeLa cells.
Disclosure of Invention
The invention aims to provide a heteropolyacid salt-organic ligand compound with high antitumor activity and low toxicityAnd a synthetic method and application thereof. The invention uses { P 8 W 48 O 184 } 40- Based on the introduction of 1,2, 4-triazole (trz) and transition metal, self-assembly is carried out to synthesize the heteropoly acid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]。
The technical solution for realizing the purpose of the invention is as follows:
heteropolyacid salt-organic ligand compound of the formula K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]The crystal data are as follows:
Figure BDA0003633411110000011
Figure BDA0003633411110000021
the preparation method of the heteropolyacid salt-organic ligand compound comprises the following steps:
according to { P 8 W 48 O 184 } 40- (hereinafter abbreviated as { P 8 W 48 }), silver nitrate and 1,2, 4-triazole, wherein the molar ratio of the silver nitrate to the 1,2, 4-triazole is (0.30-0.35): (4.5-5.0): (5.0-5.5), firstly adding { P into a lithium nitrate solution at normal temperature 8 W 48 O 184 } 40- Stirring until the mixture is uniformly mixed, adjusting the pH value to 1.45 by using dilute nitric acid, changing the solution from turbid to clear, adding silver nitrate and 1,2, 4-triazole, after the solution is completely dissolved, carrying out self-assembly, changing the solution from clear to turbid, filtering, collecting clear liquid, volatilizing to obtain the heteropoly acid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]。
Preferably, { P 8 W 48 O 184 } 40- The molar ratio of the silver nitrate to the 1,2, 4-triazole is 0.34: 4.9: 5.1.
preferably, the dilute nitric acid has a concentration of 1M.
Furthermore, the invention also provides application of the heteropoly acid salt-organic ligand compound in preparing antitumor drugs.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, by utilizing the structural characteristics of polyoxometallate and the biological effect of antitumor activity, the surface charge, polarity and redox characteristics of the POM are changed by introducing organic groups into the POM frame, so that the functionalized POM with lower toxicity and stronger cell penetration capability is formed;
(2) the heteropolyacid salt-organic ligand compound has low toxicity, has an inhibition effect on tumor cells by inhibiting cell cycle induced apoptosis and inhibiting proliferation of HepG2 cells, is generally stable in an aqueous solution and shows an effect of enhancing biological targeting.
(3) The heteropolyacid salt-organic ligand compound of the present invention binds to DNA by the binding and cleavage action with DNA, and inactivates the active site of DNA, thereby inhibiting the proliferation of tumor cells.
(4) According to the invention, Ag ions with good sterilization and anti-tumor properties are added into the structure, so that the double helix conformation of DNA is changed, and the anti-tumor property of the compound is further enhanced.
Drawings
FIG. 1 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]Experimental and theoretical values of X-ray powder diffraction data of (a).
FIG. 2 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]An infrared spectrum of (1).
FIG. 3 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]Thermogram of (c).
FIG. 4 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]And { P 2 W 18 Plot of cyclic voltammetry spectra.
FIG. 5 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]A raman spectrum of (a).
FIG. 6 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]Nuclear magnetic map of (a).
FIG. 7 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]Ultraviolet-visible spectrum of (a).
FIG. 8 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]The ultraviolet absorption spectrum of (A) is shown as the change of the CT-DNA concentration is increased. .
FIG. 9 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]、{P 8 W 48 }、AgNO 3 And cytotoxicity results of 1,2, 4-triazole to HepG2 and HEK 293T.
FIG. 10 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]、{P 8 W 48 }、AgNO 3 DNA gel electrophoresis picture of 1,2, 4-triazole, wherein channel 1 is DNA, and channel 2 is DNA + { P 8 W 48 O 184 } 40- Channel 3 is DNA + AgNO 3 The channel 4 is DNA +1,2, 4-triazole, and the channel 5 is a DNA + compound.
FIG. 11 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]The polyhedron structure of (1).
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings. In the following test, { P ] was used 8 W 48 O 184 } 40- Synthesized by the existing method, in particular the references [ R Contant, A Tez é, Inorg. chem.1985,24,4610-4614 ].
Example 1
According to { P 8 W 48 O 184 } 40- The molar ratio of the silver nitrate to the 1,2, 4-triazole is 0.34: 4.9: 5.1 adding 0.42g of lithium nitrate into 60ml of water solution under normal temperature condition, stirring uniformly and dissolving completely, adding 0.51g of { P 8 W 48 O 184 } 40- . Stirring until the mixture is uniformly mixed, adjusting the pH value to 1.45 by using 1M dilute nitric acid, changing the solution from turbid to clear, adding 0.0825g of silver nitrate to dissolve, adding 0.035g of 1,2, 4-triazole, uniformly stirring for 5min for self-assembly after complete dissolution, changing the solution from clear to turbid, filtering and collecting clear solution, and volatilizing for about one week to finally obtain yellow blocky single crystal. Wherein { P 8 W 48 Decompose into { P } 2 W 18 The chemical formula of the heteropolyacid salt-organic ligand compound is K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]。
Example 2
This example is essentially the same as example 1, except that { P } 8 W 48 O 184 } 40- The molar ratio of the silver nitrate to the 1,2, 4-triazole is 0.30: 4.5: 5.0.
example 3
This example is essentially the same as example 1, except that { P } 8 W 48 O 184 } 40- The molar ratio of the silver nitrate to the 1,2, 4-triazole is 0.35: 5.0: 5.5.
comparative example 1
{P 8 W 48 O 184 } 40- Silver nitrate and 1,2, 4-trisThe molar ratio of the azole is 1: 1: when the pH of the solution is adjusted to 1.45 at 1, no crystal grows.
Comparative example 2
{P 8 W 48 O 184 } 40- The molar ratio of the silver nitrate to the 1,2, 4-triazole is 0.5: 2: when the pH of the solution was adjusted to 1.45 at 2, crystals grew, but the crystal quality was not good. And crystal growth occurs only at a pH of 1.45.
FIG. 1 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]Experimental and theoretical values of X-ray powder diffraction data of (a). As can be seen from FIG. 1, the X-ray powder diffraction experimental value of the crystal is consistent with the peak position of the theoretical value, which shows that the crystal structure is accurately resolved, and the synthesized crystal has high purity. FIG. 2 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]An infrared spectrum of (1). From 400 to l000cm in the low wavenumber region of FIG. 2 -1 The vibration peak can be seen in the range of 950cm -1 And 910cm -1 The splitting of the vibration peak is caused by the fact that the chemical environment where the double bond of W ═ O is located is different, so that the bond length of W ═ O is different. Vibration peak 881cm -1 Is the characteristic peak of the common edge bridge oxygen, and the vibration peak is 750cm -1 Is a characteristic peak of the coplanar bridging oxygens. Vibration peak 3632cm -1 、3144cm -1 Representing characteristic peaks of nitrogen hydrogen and carbon hydrogen in triazole. Vibration peak 1513cm -1 Represents the characteristic peak of the carbon-nitrogen bond in the triazole. According to the infrared spectrum of the compound, the characteristic vibration absorption peak of the 1,2, 4-triazole ligand is contained, which shows that the heteropoly acid salt-organic ligand compound really contains the 1,2, 4-triazole. FIG. 3 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]The thermogravimetric graph shows that the weight of the compound is reduced by 2.45% within the range of 45-210 ℃, solvent water molecules and coordination water molecules are correspondingly lost, and the error range is within the error range compared with the theoretical value of 2.45%(ii) a The weight loss of the second stage is within the range of 210-460 ℃, 4.86% of the weight loss corresponds to the loss of four 1,2, 4-triazole ligands, and the theoretical value is 5.35%. The results are consistent with single crystal structure resolution. FIG. 4 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]It can be seen that the redox signal is weakened and finally completely disappeared due to protonation. The quasi-reversible peak between 0.02 and-0.75V corresponds to W VI The oxidation-reduction process at the center, and the oxidation-reduction peak around 0.75V is metal Ag + The redox process of (1). FIG. 5 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]The Raman spectrogram shows that the compound contains the characteristic vibration absorption peak of the 1,2, 4-triazole ligand, which indicates that the compound does contain the 1,2, 4-triazole. FIG. 6 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]Nuclear magnetic pattern in DMSO-d6, in DMSO-d6 1 H NMR has a strong signal peak at 8.45ppm, and the signal is attributed to the chemical shift of the hydrogen atom on the nitrogen in the 1,2, 4-triazole ligand. With pure 1,2, 4-triazole 1 H NMR shifts the proton signal [ Δδ (H): 0.17ppm]. FIG. 7 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]Uv-vis spectra in PBS buffered solution at pH 7.4, measured every 5 minutes, showed no change in the uv absorbance peak of the compound after 6h, indicating that the compound was relatively stable in the buffered solution.
Test example 1 pharmacodynamic test
In vitro experiments: MTT method for detecting inhibition effect of drug on tumor cells
1. Experimental Material
Tumor cell HepG2
Normal cell HEK293T
DMEM culture solution containing 10% calf serum
2. Experimental procedure
Recovering cells by conventional method, regulating cell concentration to 5 × 10 when cell growth state is good 5 cells/mL, 3X 10 cells per well 3 200 μ L of each suspension was placed in a 96-well plate at 37 ℃ with 5% CO 2 After 24h of culture, the experimental group was set with 6 concentrations, each concentration was set with five multiple wells, each well was added with 10. mu.L of the drug solution, and a positive control and a negative control (untreated cancer cell group) were set. 37 ℃ and 5% CO 2 Continuously culturing for 48h in the incubator, adding 20 mu L0.5mg/mLMTT into each hole for 4h before the experiment is finished, continuously culturing for 4h, removing the supernatant, dissolving the MTT precipitate by DMSO, shaking and uniformly mixing, and measuring the OD value at 480nm of the microplate reader. The inhibition ratio was calculated from the measured OD value by the following formula. Obtaining half inhibition concentration IC by statistical processing of different inhibition rates obtained by different concentrations of the same sample 50 ，
The inhibition ratio was ((1-experimental OD value)/control OD value) × 100%.
The inhibitory activities of the heteropolyacid salt-organic ligand compounds at 0. mu.M, 6.25. mu.M, 12.5. mu.M, 25. mu.M, 50. mu.M and 100. mu.M on the above two tumor cells were investigated, respectively. IC of heteropolyacid salt-organic ligand Compound on HepG2 50 The value of (D) was 130.85. + -. 0.55. mu.M, as shown in Table 1. Simultaneously setting a comparison group, namely, a synthetic raw material { P 8 W 48 And (3) inhibition activity experiments of 1,2, 4-triazole (trz) and silver nitrate on liver cancer cells HepG2 and normal cells HEK 293T.
TABLE 1 heteropolyacid salt-organic ligand Compound, trz, { P 8 W 48 },AgNO 3 IC cytotoxic to HepG2 and HEK293T 50
Figure BDA0003633411110000061
Heteropoly acid salt-organic ligand compound, { P 8 W 48 }、trz、AgNO 3 The cytotoxicity effect on HepG2, HEK293T is shown in FIG. 9, where a simple building block { P }can be seen 8 W 48 The toxicity to HepG2, HEK293T cells was significantly lower than that of the compound.
Experimental example 2 agarose gel electrophoresis experiment
1. Preparing a solution:
(1) preparation of electrophoresis buffer solution
242g of tris (hydroxymethyl) aminomethane and Na were weighed 2 EDTA 2H 2 Measuring glacial acetic acid by 57.1mL to obtain 94g, double-distilling deionized water to about 950mL, adjusting the pH value to 8.5 by using the glacial acetic acid, and then using newly prepared double-distilled deionized water to reach the constant volume of 1000 mL.
(2) Preparation of reaction buffer
Weighing 3.025g of Tris (hydroxymethyl) aminomethane and 1.461g of sodium chloride, adding 450mL of newly prepared double-distilled deionized water, adjusting the pH value to 7.2 by hydrochloric acid, and then using the newly prepared double-distilled deionized water to reach 500mL to obtain 50mM Tris-HCl/50mM NaCl reaction buffer solution.
(3) Preparation of agarose gel
0.25g of agarose was weighed, 50mL of the electrophoresis buffer solution was added, and the agarose was completely dissolved by heating. Adding 1mg/L ethidium bromide into the solution, injecting 1 mu L of the solution into a mould, and cooling for 30min to obtain the product.
2. The experimental steps are as follows:
preparation of 40. mu.M of the heteropolyacid salt-organic ligand Compound and its ligand { P } Using the reaction buffer 8 W 48 }、 AgNO 3 1,2, 4-triazole, and respectively mixing the plasmid supercoiled DNA and hydrogen peroxide with heteropoly acid salt-organic ligand compound and { P 8 W 48 }、AgNO 3 And 1,2, 4-triazole are mixed with each other, all react for a certain time in a constant-temperature water bath at 37 ℃, and 10X padding Buffer is added to terminate the reaction. The sample was added to the agarose gel recess using a pipette, run at 180V at 100mA, run for 0.5h, and finally the gel products were analyzed using a Universal hood II gel analysis imaging system.
FIG. 10 shows a heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]、{P 8 W 48 }、AgNO 3 And 1,2, 4-triazole, as shown in the figure, the channel 2, the channel 3 and the channel 4 have no obvious change relatively compared with the channel 1,indicating that all ligands were unable to cleave DNA. The increased open loop structure of channel 5 compared to channel 1 indicates that the compound is effective in cleaving DNA. Different cleavage efficiencies may be attributed to the binding affinity of different substances to DNA. Since the compound can efficiently cleave DNA, the compound inhibits the growth of cancer cells by cleaving the genome.
Test example 3
DNA binding experiments
1. Preparing a solution:
(1) preparation of buffer solution
0.6057g Tris (Tris hydroxymethyl aminomethane) was weighed into a 100ml volumetric flask and the pH was adjusted to 7.4 with 1M HCl to obtain 5mM Tris buffer.
(2) Preparation of calf thymus DNA (CT-DNA)
0.0044g of CT-DNA was weighed, dissolved in 10ml of the above buffer solution, and stored overnight in a refrigerator at 4 ℃.
(3) Preparation of the Compounds
0.0011g of the heteropolyacid salt-organic ligand compound is weighed out and dissolved in 10ml of the above-mentioned buffer.
2. The experimental steps are as follows:
the concentration was measured by ultraviolet absorption spectroscopy, and the ratio of the absorbance values at wavelengths of 260nm and 280nm was calculated to be in the range of 1.8 to 1.9, thus indicating that the solution contained no protein and was usable for the experiment. The molar absorptivity at 260nm is known to be 6600M -1 cm -1 The concentration value of the prepared solution can be calculated from the absorbance value of the solution at 260nm according to the Lambert beer law. Respectively dripping the CT-DNA solution to 1.0X 10 -5 mol/L of the solution of the heteropolyacid salt-organic ligand compound.
Intrinsic binding constant K b Is prepared by [ DNA ]]/(ε a -ε f ) And [ DNA ]]Is calculated by the formula (1):
Figure BDA0003633411110000071
as shown in FIG. 8, DNA was gradually added while keeping the concentration of the compound constant, and the ultraviolet absorption spectrum was recorded at each corresponding DNA concentration. The occurrence of an additive blue shift indicates the heteropolyacid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]There may be electrostatic interactions with the DNA.

Claims (5)

1. Heteropolyacid salt-organic ligand compound of the formula K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]The crystal data are as follows:
Figure FDA0003633411100000011
2. the process for the preparation of a heteropolyacid salt-organic ligand compound according to claim 1, characterized by comprising the steps of:
according to { P 8 W 48 O 184 } 40- The molar ratio of the silver nitrate to the 1,2, 4-triazole is (0.30-0.35): (4.5-5.0): (5.0-5.5), firstly adding { P ] into a lithium nitrate solution at normal temperature 8 W 48 O 184 } 40- Stirring until the mixture is uniformly mixed, adjusting the pH value to 1.45 by using dilute nitric acid, changing the solution from turbid to clear, adding silver nitrate and 1,2, 4-triazole, after the solution is completely dissolved, carrying out self-assembly, changing the solution from clear to turbid, filtering, collecting clear liquid, volatilizing to obtain the heteropoly acid salt-organic ligand compound K 2 [Ag 4 (Ag 2 O) 3 (trz) 6 {P 2 W 18 O 62 }]。
3. The preparation method according to claim 2, wherein { P } is 8 W 48 O 184 } 40- The molar ratio of the silver nitrate to the 1,2, 4-triazole is 0.34: 4.9: 5.1.
4. the method according to claim 2, wherein the dilute nitric acid has a concentration of 1M.
5. Use of the heteropolyacid salt-organic ligand compound according to claim 1 for producing an antitumor agent.
CN202210496358.2A 2022-05-09 2022-05-09 Heteropolyacid salt-organic ligand compound and synthetic method and application thereof Pending CN114907418A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210496358.2A CN114907418A (en) 2022-05-09 2022-05-09 Heteropolyacid salt-organic ligand compound and synthetic method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210496358.2A CN114907418A (en) 2022-05-09 2022-05-09 Heteropolyacid salt-organic ligand compound and synthetic method and application thereof

Publications (1)

Publication Number Publication Date
CN114907418A true CN114907418A (en) 2022-08-16

Family

ID=82766279

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210496358.2A Pending CN114907418A (en) 2022-05-09 2022-05-09 Heteropolyacid salt-organic ligand compound and synthetic method and application thereof

Country Status (1)

Country Link
CN (1) CN114907418A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1786005A (en) * 2005-10-25 2006-06-14 东北师范大学 Hetero poly phosphorus vanadate antitumour medicine and its synthesis method
CN101679167A (en) * 2007-04-19 2010-03-24 埃克森美孚化学专利公司 Process for oxidizing alkylaromatic compounds
CN107266507A (en) * 2017-06-09 2017-10-20 扬州大学 The sandwich type polymetallic tungstens hydrochlorate of imidazole covalent coordination, preparation method and applications
CN110423252A (en) * 2019-06-25 2019-11-08 扬州大学 Krebs type polyacid compound and preparation method thereof
CN114746367A (en) * 2019-11-21 2022-07-12 埃克森美孚化学专利公司 Polyoxometallate containing noble metal and metal cluster unit thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1786005A (en) * 2005-10-25 2006-06-14 东北师范大学 Hetero poly phosphorus vanadate antitumour medicine and its synthesis method
CN101679167A (en) * 2007-04-19 2010-03-24 埃克森美孚化学专利公司 Process for oxidizing alkylaromatic compounds
CN107266507A (en) * 2017-06-09 2017-10-20 扬州大学 The sandwich type polymetallic tungstens hydrochlorate of imidazole covalent coordination, preparation method and applications
CN110423252A (en) * 2019-06-25 2019-11-08 扬州大学 Krebs type polyacid compound and preparation method thereof
CN114746367A (en) * 2019-11-21 2022-07-12 埃克森美孚化学专利公司 Polyoxometallate containing noble metal and metal cluster unit thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
章瀚之: "基于氮杂环配体构筑的多酸基有机-无机杂化晶态材料的制备及体外抗肿瘤活性研究", 《扬州大学硕士学位论文》 *

Similar Documents

Publication Publication Date Title
Kolks et al. Imidazolate-bridged complexes of copper (II)
Costa et al. Synthesis and stereochemistry of mono-, bi-, and tetranuclear manganese thiolates
Wang et al. A novel 1D zigzag chain organic–inorganic polymer with Dawson-type polyoxometalates as building blocks: synthesis and crystal structure of H1. 5 [Sm (H2O) 8] 0.5 [Sm (DMF) 6 (H2O)(α-P2W18O62)]· DMF· 3H2O
Krakowiak et al. Preparation and structural properties of large-cavity peraza macrocycles containing pyridine, phenanthroline, or piperazine subcyclic units
Mura et al. Synthesis, molecular structure and solution chemistry of the iridium (III) complex imidazolium [trans (bisimidazole) tetrachloro iridate (III)](IRIM)
Chandrasekhar et al. Ferrocene-based compartmental ligand for the assembly of neutral Zn II/Ln III heterometallic complexes
Shi et al. A 3D inorganic-organic hybrid constructed from Strandberg-type polyoxometalates and silver complexes: Synthesis, structure and properties
CN107098392A (en) A kind of arsenowolframic acid sandwich type polyoxometalates compound based on Manganic ion and preparation method and application
Kaliva et al. Systematic studies on pH-dependent transformations of dinuclear vanadium (V)–citrate complexes in aqueous solutions: A perspective relevance to aqueous vanadium (V)–citrate speciation
Fan et al. Synthesis, crystal structures and luminescent properties of two 4d–4f Ln–Ag heterometallic coordination polymers based on anion template
WO2015098152A1 (en) Method for preparing crystallography sample and method for determining molecular structure of metabolite
Plenio et al. Metal complexes of ferrocene cryptands
Lou et al. Coordination polymers as potential solid forms of drugs: three zinc (II) coordination polymers of theophylline with biocompatible organic acids
CN114907418A (en) Heteropolyacid salt-organic ligand compound and synthetic method and application thereof
Song et al. Controllable synthesis of two adenosine 5′-monophosphate nucleotide coordination polymers via pH regulation: crystal structure and chirality
Matoga et al. [PPh4] 3 [W (CN) 7 (O2)]⊙ 4H2O as the Representative of the [M (L) 7 (LL)] Class for Nine-Coordinate Complexes
Park et al. New Class of Scorpionate: Tris (tetrazolyl)–Iron Complex and Its Different Coordination Modes for Alkali Metal Ions
Bu et al. Syntheses, crystal structures and properties of new manganese (II) complexes with macrocyclic polyamine ligands bearing pyridyl donor pendants
Kaliva et al. Synthesis, isolation, spectroscopic and structural characterization of a new pH complex structural variant from the aqueous vanadium (V)-peroxo-citrate ternary system
Prasad et al. Heterometallic coordination compounds of dipicolinic acid with Ce (III, IV) and Cu (II): Synthesis, crystal structure and spectral studies
CN113980286A (en) Synthesis method and application of Ni-based coordination polymer
Hou et al. Coordination and supramolecular assemblies of meta-hexamethyl-substituted cucurbit [6] uril with alkali metal ions
Bai et al. Two polyoxometalate-based metal–organic complexes constructed from a pyridine-polyazole: Assembly, structures, electrochemistry and adsorption properties
Comba et al. Synthesis of a Cis-N2s2 Donor Macrocycle by Metal-Directed Condensation of Formaldehyde, Nitroethane and a Diaminodithiaalkane-Crystal-Structure of the (6-Methyl-6-Nitro-1, 11-Dithia-4, 8-Diazacyclotetradecane)-Copper (II) Perchlorate Product
Mironov et al. Octahedral aqua fluoride rhenium cluster complexes K [Re6S8F3 (H2O) 3]· 7H2O, H3O [Re6Se8F3 (H2O) 3]· 7H2O and [Re6Q8F2 (H2O) 4]· 12H2O (Q= S, Se): Synthesis and structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination