CN109627210B - Gallium fluorescent probe, preparation method, application and application product thereof - Google Patents
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Abstract
The invention discloses a gallium fluorescent probe and a preparation method, application and application product thereof, wherein the structural formula of the fluorescent probe is as follows:
the preparation method comprises the following steps: 1) taking 2, 6-diacetylpyridine and 4-aminobenzoyl hydrazide to react by taking alcohol substances as solvents, collecting precipitates generated by the reaction and washing to obtainLigand 2, 6-diacetylpyridine 4-aminobenzoyl hydrazide; 2) taking ligand 2, 6-diacetylpyridine condensed 4-aminobenzoic hydrazide and GaCl3And reacting by taking an alcohol substance as a solvent, standing and crystallizing the reacted solution, and collecting crystals to obtain the gallium fluorescent probe. The gallium fluorescent probe is applied to preparing an anti-tumor drug or a tumor detection agent to obtain the anti-tumor drug or the tumor detection agent. The gallium fluorescent probe has good potential medicinal value and detection value, and is expected to be used for preparing various anti-tumor medicaments or tumor detection agents.
Description
Technical Field
The invention relates to a gallium fluorescent probe and a preparation method, application and an application product thereof, belonging to the technical field of medicines.
Background
Cancer (mainly malignant tumor) is one of the most serious diseases harmful to human health, and the most common and serious malignant tumors in China mainly comprise: breast cancer, cervical cancer, lymphoma, leukemia, lung cancer, liver cancer and the like (Farrell N, et al cancer res.,1992), while anti-tumor drugs are gradually developed along with the great threat of cancer to human health. Through research and development work of decades, researchers have come to the market successively and applied to clinical treatment and adjuvant therapy of antitumor drugs of different types, different efficacy characteristics and different action mechanisms, wherein in 1965 Rosenberg and the like find that cisplatin has significant anticancer activity (Rosenberg, BL, et al. Nature,1969), pioneering inorganic anticancer drugs, and forming a series of platinum anticancer drugs represented by cisplatin, carboplatin, oxaliplatin and the like. Therefore, the further design and synthesis of novel platinum antineoplastic drugs is a hot research direction and has important significance.
On the other hand, the benzoyl hydrazine compounds have many biological activities such as anti-tumor, anti-virus, anti-malaria and anti-bacterial, and some amino sulfur compounds have been used in cancer treatment, for example, isoniazid has been used in clinical treatment of tuberculosis. At present, no public report of the synthesis of a gallium (III) metal probe taking 2, 6-diacetylpyridine condensed 4-aminobenzene hydrazide as a ligand and the application of the gallium (III) metal probe in tumor diagnosis and treatment is found.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a gallium fluorescent probe, a preparation method, application and an application product thereof, wherein the gallium fluorescent probe takes 2, 6-diacetylpyridine condensed 4-aminobenzene hydrazide as a ligand, and the gallium fluorescent probe has fluorescence and anti-tumor activity and is used for tumor diagnosis and treatment under the condition of not changing the structure of a medicament.
The technical scheme is as follows: the invention provides a gallium fluorescent probe, which is a compound with a structure shown in a formula 1:
the invention also provides a preparation method of the gallium fluorescent probe, which comprises the following steps:
1) taking 2, 6-diacetylpyridine and 4-aminobenzoyl hydrazide, reacting by taking an alcohol substance as a solvent, collecting a precipitate generated by the reaction, and washing to obtain a ligand 2, 6-diacetylpyridine condensed 4-aminobenzoyl hydrazide;
2) taking ligand 2, 6-diacetylpyridine condensed 4-aminobenzoic hydrazide and GaCl3And reacting by taking an alcohol substance as a solvent, standing and crystallizing the reacted solution, and collecting crystals to obtain the gallium fluorescent probe.
Wherein:
the mass ratio of the 2, 6-diacetylpyridine to the 4-aminobenzoyl hydrazide in the step 1) is a stoichiometric ratio, and the ratio range is 1: 2-1: 10.
The amount of the solvent used in the step 1) is preferably such that the 2, 6-diacetylpyridine and 4-aminobenzoyl hydrazide which participate in the reaction can be dissolved, and usually, 2 to 20mL of the solvent is used to dissolve 1mmol of the 2, 6-diacetylpyridine or 2mmol of the 4-aminobenzoyl hydrazide.
In the step 1), in the reaction of taking 2, 6-diacetylpyridine and 4-aminobenzoyl hydrazide and taking an alcohol substance as a solvent, the specific steps are that the 2, 6-diacetylpyridine and the 4-aminobenzoyl hydrazide are respectively dissolved by the solvent and then mixed together for reaction, or the 2, 6-diacetylpyridine and the 4-aminobenzoyl hydrazide are mixed and then added with the solvent.
In the reaction with the alcohol as the solvent, the alcohol is one or a mixture of methanol and ethanol.
When the alcohol substance is methanol, the volume concentration of the methanol is 20-80%; when the alcohol substance is ethanol, the volume concentration of the ethanol is 20-80%; when the alcohol substance is a mixture of methanol and ethanol, the ratio of the methanol to the ethanol is any ratio.
In the step 1) and the step 2), alcohols are used as solvents for reaction, the reaction is carried out at normal temperature or by heating, the reaction temperature ranges from 20 ℃ to 80 ℃, and the reaction time is 1-24 h.
The preferable reaction in the step 1) with the alcohol as the solvent is carried out at the reaction temperature of 50-80 ℃ for 1-24 h
In the step 1), the reaction is carried out by taking the alcohol as the solvent, and the reaction temperature is more preferably 60-80 ℃.
In the step 1) of the reaction with the alcohol as the solvent, whether the reaction is complete or not can be tracked and detected by Thin Layer Chromatography (TLC).
The heating reaction is a conventional heating reaction or a heating reflux reaction, and the reflux reaction is preferably adopted.
In the step 1) of collecting and washing the precipitate generated by the reaction, one or more of methanol, absolute ethyl alcohol, ether or water is adopted to wash the precipitate generated by the reaction.
The ligand 2, 6-diacetyl pyridine condensed 4-aminobenzoic hydrazide and GaCl in the step 2)3The ratio of the amounts of the substances is a stoichiometric ratio, and the ratio ranges from 1:1 to 1: 10.
In the step 2) of standing and crystallizing the solution after the reaction, in order to improve the purity of the product, it is preferable that the reactant obtained by the reaction is filtered, then the filtrate is collected, and finally the filtrate is subjected to standing and crystallizing.
The step 2) of standing crystallization of the reacted solution refers to standing crystallization at the temperature of 0-8 ℃.
The step 2) of standing and crystallizing the reacted solution comprises the following steps: covering a layer of film on the opening of the container for containing the solution after reaction, and then forming a plurality of small holes on the film to slowly volatilize the solvent so as to obtain crystals with larger grains and higher crystal yield.
The solvent in the step 2) is used for dissolving the ligand 2, 6-diacetylpyridine condensation 4-aminobenzene hydrazide and GaCl which participate in the reaction3Preferably, 1mmol of the ligand 2, 6-diacetylpyridine 4-aminobenzoyl hydrazine or GaCl is used3Dissolving the mixture in 2-10 mL of solvent.
Step 2) taking ligand 2, 6-diacetylpyridine condensed 4-aminobenzoic hydrazide and GaCl3In the reaction by taking alcohol as a solvent, the specific steps are that the ligand 2, 6-diacetyl pyridine condensed 4-aminobenzene hydrazide and GaCl3Dissolving with solvent respectively, mixing, and reacting, or dissolving ligand 2, 6-diacetylpyridine 4-aminobenzene hydrazide and GaCl3After mixing, the solvent is added.
The invention also provides an application of the gallium fluorescent probe, and the gallium fluorescent probe is applied to preparation of antitumor drugs or tumor detection agents.
The invention also provides an application product of the gallium fluorescent probe, wherein the application product is an anti-tumor medicament or a tumor detection agent prepared by using the gallium fluorescent probe as an active ingredient.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the gallium fluorescent probe provided by the invention is a Ga (III) metal probe taking 2, 6-diacetylpyridine condensed 4-aminobenzene hydrazide as a ligand, has obvious in-vitro anti-tumor activity on HepG-2, MCF-7, NCI-H460, T24, Hela and A549 tumor cell strains, has good potential medicinal value, and is expected to be used for preparing various anti-tumor medicaments;
2. the gallium fluorescent probe provided by the invention can be positioned in mitochondria of tumor cells, has good potential tumor detection value, and is expected to be used for preparing various tumor detection agents;
3. the gallium fluorescent probe provided by the invention has fluorescence and anti-tumor activity, and is used for tumor diagnosis and treatment under the condition of not changing the structure of the medicine;
4. the preparation method of the gallium fluorescent probe provided by the invention can be completed by only two steps, the treatment process is relatively simple, and the purity of the target product is high.
Drawings
FIG. 1 is a confocal laser microscope image of gallium fluorescent probe cell in the cell nucleus.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
In the following examples and experimental examples, the abbreviations used have the following meanings:
[Ga(L)Cl2]a Cl probe: represents a gallium fluorescent probe taking 2, 6-diacetylpyridine condensed 4-aminobenzoic hydrazide as a ligand;
l: represents ligand 2, 6-diacetylpyridine 4-aminobenzoic hydrazide;
DMSO, DMSO: dimethyl sulfoxide.
Example 1:
a gallium fluorescent probe has a chemical formula of [ Ga (L) Cl2]Cl, having a formula shown in formula 1:
the synthetic route of the gallium fluorescent probe is as follows:
the preparation method comprises the following steps:
1) dissolving 1mmol of 2, 6-diacetylpyridine in 10ml of ethanol (the concentration of solvent ethanol is 20 v/v%), stirring at 80 ℃ for 15min to prepare a solution, dropwise adding the solution into 10ml of ethanol (the concentration of solvent ethanol is 20 v/v%) solution added with 2mmol of 4-aminobenzoyl hydrazine, refluxing and stirring at 60 ℃ for 24h to obtain a light yellow precipitate, filtering the light yellow precipitate, washing with absolute ethanol and diethyl ether for 3 times respectively, and drying to obtain a ligand 2, 6-diacetylpyridine condensed 4-aminobenzoyl hydrazide;
2) will contain 1mmol of GaCl3Dropwise adding 10ml of methanol (the concentration of the solvent methanol is 60 v/v%) solution into 10ml of ethanol (the concentration of the solvent ethanol is 20 v/v%) solution containing 1mmol of 2, 6-diacetylpyridine condensation 4-aminobenzophenozide ligand, refluxing and stirring at 80 ℃ for 24 hours, filtering the reacted solution into a 50ml beaker, sealing the beaker by using a preservative film, pricking 20 holes with a needle, volatilizing for several days at 8 ℃, standing and crystallizing to obtain a dark brown crystal, namely the gallium fluorescent probe.
The obtained yellow crystal is subjected to element analysis, nuclear magnetism and mass spectrum analysis, and the specific spectral characteristics are as follows:
(1) elemental analysis:
the chemical formula is as follows: c23H23Cl3GaN7O2；
The elemental analysis results were:
calculated values: c, 45.62; h, 3.83; n, 16.19; o, 5.28; analytical values: c, 45.69; h, 3.75; n, 16.11; and O, 5.20.
(2) Nuclear magnetic analysis:
1H NMR(600MHz,DMSO-d6)δ11.21(s,2H),10.78(d,J＝25.9Hz,4H),7.99–7.95(m,1H),7.92(s,2H),7.85(d,J＝8.2Hz,4H),7.10–7.07(m,4H),2.53(s,6H)。
(3) mass spectrometry analysis:
calculated values: [ Ga (L) Cl2]Cl, 603.05; test values are: [ Ga (L) Cl2]+，568.05。
The anti-tumor activity experiments of the gallium fluorescent probe (prepared by the method of the embodiment 1) and the ligand L and the like of the invention are as follows:
1) cell lines and cell cultures
Tumor cell lines HepG-2, MCF-7, NCI-H460, T24, Hela and A549 tumor cell lines are all from the American Type Culture Collection ((Rockville M)D, USA), cells were incubated at 37 ℃ in a 5% volume incubator with 10% fetal bovine serum and 100. mu.g mL-1Streptomycin was cultured in RPM-1640 medium with 100 units per ml penicillin.
2) Cell growth inhibition assay (MTT method)
Note: MTT is named as 3- (4,5-dimethyl-2-thiazolyl) -2,5-diphenyl-2-H-tetrazolium bromide, and the Chinese chemical name is 3- (4, 5-dimethylthiazole-2) -2,5-diphenyl tetrazolium bromide, the trade name is: thiazole blue, a yellow dye.
After the gallium fluorescent probe is subjected to cosolvent by DMSO, sequentially diluting the gallium fluorescent probe into five gradients by using a complete culture medium, wherein the five gradients are working solution with the concentration 20 times that of the final concentration, and the contents of the cosolvent DMSO and the like are consistent among the gradients except for different drug concentrations; filtering with 0.22um microporous membrane for sterilization, and storing at 4 deg.C. The tumor cell strains HepG-2, MCF-7, NCI-H460, T24, Hela and A549 in logarithmic phase are respectively inoculated into a 96-well plate by 0.18ml per well, and the cell concentration is about 0.4-0.5 multiplied by 105After cells are cultured for 12 hours and adhered to the wall, test compounds with different concentrations are respectively added into each hole with 20 mul, the final concentration of each hole is respectively 0 mul, 1 mul, 5 mul, 10 mul, 20 mul, 50 mul and 100 mul, each gradient is provided with 4 compound holes, the final concentration of DMSO is less than 0.5 percent, corresponding negative control groups (only cells and the same amount of DMSO without drugs) are simultaneously arranged, each group is also provided with 4 compound holes, after the drugs act for 48 hours, the culture solution is poured out, 100 mul of DMSO is added, a plate oscillator is vibrated for 10min, crystals are fully dissolved, blank control groups are adjusted to zero, an enzyme labeling instrument is used for measuring the absorbance (A) value after the bottom light absorption value is removed by 550nm/655nm double-wavelength measurement, and the work done IC 549 of the compounds on tumor cell strains HepG-2, MCF-7, NCI-H460, T24, Hela and A549 are respectively calculated by a Bliss method50Values, all experiments were repeated 3 times.
The experimental results are shown in Table 1, and it can be seen that the cell activities of the gallium fluorescent probe to the tumor cells HepG-2, MCF-7, NCI-H460, T24, Hela and A549 are obviously higher than that of the corresponding ligand L.
TABLE 1 antitumor Activity of ligand L and gallium fluorescent probes
Intracellular localization experiments of the gallium fluorescent probe (prepared as described in example 1) and ligand L of the present invention.
1) Cell lines and cell cultures
Tumor cell line A549A tumor cell line is obtained from the American Type Culture Collection (Rockville MD, USA) by adding 10% fetal bovine serum and 100. mu.g mL into 5% volume incubator at 37 deg.C-1Streptomycin, 100 units per ml penicillin RPM-1640 medium;
2) gallium fluorescent probe cell localization experiments (note: Mito-Tracker Green is named as mitochondria Green fluorescent probe
The cell culture solution was removed and 1. mu.l Mito-Tracker Green and 37 ℃ preincubated Mito-Tracker Green staining medium were added and incubated with the cells at 37 ℃ for 15-45 min. The Mito-Tracker Green staining solution was removed, 1. mu.l of gallium fluorescent probe and fresh cell culture medium pre-incubated at 37 ℃ were added, and cells were incubated for 15-45 minutes at 37 ℃. And then, observing by using a laser confocal microscope, wherein the result is shown in figure 1, and the distribution of the gallium fluorescent probe in the cell is basically consistent with that of the Mito-Tracker Rad, which indicates that the gallium fluorescent probe is positioned in mitochondria.
An application of a gallium fluorescent probe is applied to preparing an anti-tumor drug or a tumor detection agent.
An application product of a gallium fluorescent probe is an antitumor drug or a tumor detection agent prepared by taking the gallium fluorescent probe as an active ingredient.
Example 2:
a gallium fluorescent probe has a chemical formula of [ Ga (L) Cl2]Cl, having a formula shown in formula 1:
the synthetic route of the gallium fluorescent probe is as follows:
the preparation method comprises the following steps:
1) dissolving 1mmol of 2, 6-diacetylpyridine in 10ml of ethanol (the concentration of solvent ethanol is 80 v/v%), stirring for 15min at 20 ℃ to prepare a solution, dropwise adding the solution into 10ml of ethanol (the concentration of solvent ethanol is 80 v/v%) solution added with 10mmol of 4-aminobenzoyl hydrazine, refluxing and stirring at 20 ℃ for 24h to obtain a light yellow precipitate, filtering the light yellow precipitate, washing with absolute ethanol and diethyl ether for 3 times respectively, and drying to obtain a ligand 2, 6-diacetylpyridine condensed 4-aminobenzoyl hydrazide;
2) will contain 10mmol of GaCl3Dropwise adding the solution into 10ml of methanol (the concentration of the solvent methanol is 80 v/v%) solution containing 1mmol of 2, 6-diacetylpyridine condensation 4-aminobenzophenozide ligand, refluxing and stirring for 1h at 20 ℃, filtering the reacted solution into a 50ml beaker, sealing the beaker by using a preservative film, pricking 20 holes with a needle, volatilizing for several days at 4 ℃, standing and crystallizing to obtain a dark brown crystal, namely the gallium fluorescent probe.
An application of a gallium fluorescent probe is applied to preparing an anti-tumor drug or a tumor detection agent.
An application product of a gallium fluorescent probe is an antitumor drug or a tumor detection agent prepared by taking the gallium fluorescent probe as an active ingredient.
Example 3:
a gallium fluorescent probe has a chemical formula of [ Ga (L) Cl2]Cl, having a formula shown in formula 1:
the synthetic route of the gallium fluorescent probe is as follows:
the preparation method comprises the following steps:
1) dissolving 1mmol of 2, 6-diacetylpyridine in 5ml of methanol (the concentration of solvent methanol is 50 v/v%), stirring at 60 ℃ for 15min to prepare a solution, dropwise adding the solution into 10ml of methanol (the concentration of solvent methanol is 50 v/v%) solution added with 5mmol of 4-aminobenzoyl hydrazine, refluxing and stirring at 60 ℃ for 12h to obtain a light yellow precipitate, filtering the light yellow precipitate, washing with absolute ethyl alcohol and diethyl ether for 3 times respectively, and drying to obtain a ligand 2, 6-diacetylpyridine condensed 4-aminobenzoyl hydrazide;
2) will contain 5mmol of GaCl3Dropwise adding 20ml of ethanol (the concentration of the solvent methanol is 50 v/v%) solution into 10ml of ethanol (the concentration of the solvent ethanol is 50 v/v%) solution containing 1mmol of 2, 6-diacetylpyridine condensation 4-aminobenzophenozide ligand, refluxing and stirring for 12h at 60 ℃, filtering the reacted solution into a 50ml beaker, sealing the beaker by using a preservative film, pricking 20 holes with a needle, volatilizing for several days at 0 ℃, standing and crystallizing to obtain a dark brown crystal, namely the gallium fluorescent probe.
An application of a gallium fluorescent probe is applied to preparing an anti-tumor drug or a tumor detection agent.
An application product of a gallium fluorescent probe is an antitumor drug or a tumor detection agent prepared by taking the gallium fluorescent probe as an active ingredient.
Example 4:
a gallium fluorescent probe has a chemical formula of [ Ga (L) Cl2]Cl, having a formula shown in formula 1:
the synthetic route of the gallium fluorescent probe is as follows:
the preparation method comprises the following steps:
1) dissolving 1mmol of 2, 6-diacetylpyridine in 10ml of ethanol (the concentration of solvent ethanol is 40 v/v%), stirring at 50 ℃ for 15min to prepare a solution, dropwise adding the solution into 5ml of ethanol (the concentration of solvent ethanol is 40 v/v%) solution added with 2mmol of 4-aminobenzoyl hydrazine, refluxing and stirring at 50 ℃ for reaction for 3h to obtain a light yellow precipitate, filtering the light yellow precipitate, washing with absolute ethanol and diethyl ether for 3 times respectively, and drying to obtain a ligand 2, 6-diacetylpyridine condensed 4-aminobenzoyl hydrazine;
2) will contain 7mmol of GaCl3And (2) dropwise adding the 5ml of methanol solution into 10ml of ethanol (the concentration of the solvent ethanol is 50 v/v%) solution containing 1mmol of 2, 6-diacetylpyridine condensation 4-aminobenzhydrazide ligand, refluxing and stirring for 2 hours at 50 ℃, filtering the reacted solution into a 50ml beaker, sealing the beaker by using a preservative film, and performing needle prick on 20 holes to volatilize for several days at 4 ℃ for standing and crystallizing to obtain a dark brown crystal, namely the gallium fluorescent probe.
An application of a gallium fluorescent probe is applied to preparing an anti-tumor drug or a tumor detection agent.
An application product of a gallium fluorescent probe is an antitumor drug or a tumor detection agent prepared by taking the gallium fluorescent probe as an active ingredient.
The above-mentioned embodiments are only preferred embodiments of the present invention, and it will be apparent to those skilled in the art that various modifications and equivalents can be made without departing from the principle of the present invention, and those modifications and equivalents that fall within the scope of the claims of the present invention.
Claims (9)
1. A gallium fluorescent probe, characterized in that: the gallium fluorescent probe is a compound with a structure shown in a formula 1:
2. a method for preparing a gallium fluorescent probe according to claim 1, characterized in that: the method comprises the following steps:
1) taking 2, 6-diacetylpyridine and 4-aminobenzoyl hydrazide, reacting by taking an alcohol substance as a solvent, collecting a precipitate generated by the reaction, and washing to obtain a ligand 2, 6-diacetylpyridine condensed 4-aminobenzoyl hydrazide;
2) taking ligand 2, 6-diacetylpyridine condensed 4-aminobenzoic hydrazide and GaCl3Reacting by taking alcohol substances as a solvent, standing and crystallizing the reacted solution, and collecting crystals to obtain the gallium fluorescent probe;
wherein: the mass ratio of the 2, 6-diacetylpyridine to the 4-aminobenzoyl hydrazide in the step 1) is a stoichiometric ratio, and the ratio range is 1: 2-1: 10; the ligand 2, 6-diacetyl pyridine condensed 4-aminobenzoic hydrazide and GaCl in the step 2)3The ratio of the amounts of the substances is a stoichiometric ratio, and the ratio ranges from 1:1 to 1: 10.
3. The method for preparing a gallium fluorescent probe according to claim 2, wherein: in the reaction with the alcohol as the solvent, the alcohol is one or a mixture of methanol and ethanol.
4. The method for preparing a gallium fluorescent probe according to claim 3, wherein: when the alcohol substance is methanol, the volume concentration of the methanol is 20-80%; when the alcohol substance is ethanol, the volume concentration of the ethanol is 20-80%; when the alcohol substance is a mixture of methanol and ethanol, the ratio of the methanol to the ethanol is any ratio.
5. The method for preparing a gallium fluorescent probe according to claim 2, wherein: in the step 1) and the step 2), alcohols are used as solvents for reaction, the reaction temperature ranges from 20 ℃ to 80 ℃, and the reaction time is 1-24 h.
6. The method for preparing a gallium fluorescent probe according to claim 2, wherein: in the step 1) of collecting and washing the precipitate generated by the reaction, one or more of methanol, absolute ethyl alcohol, ether or water is adopted to wash the precipitate generated by the reaction.
7. The method for preparing a gallium fluorescent probe according to claim 2, wherein: the step 2) of standing crystallization of the reacted solution refers to standing crystallization at the temperature of 0-8 ℃, and the specific steps are as follows: covering a layer of film on the opening of the container for holding reactant, and then forming a plurality of small holes on the film to slowly volatilize the solvent.
8. Use of a gallium fluorescent probe according to claim 1, characterized in that: the gallium fluorescent probe is applied to preparing anti-tumor drugs or tumor detection agents.
9. A product of use of a gallium fluorescent probe according to claim 1, characterized in that: the application product is an antitumor drug or a tumor detection agent prepared by using the gallium fluorescent probe as an active ingredient.
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| Investigation into aroylhydrazones as chelating agents. Part 7. Synthesis and spectroscopic characterization of complexes of manganese(II), cobalt(II), nickel(II), copper(II), and zinc(II) with 2,6-diacetylpyridine bis(2-aminobenzoylhydrazone);Corrado Pelizzi等;《Journal of the Chemical Society》;19851231(第11期);第2387-2392页 * |
| Investigation on the pharmacological profile of 2,6-diacetylpyridine bis(benzoylhydrazone) derivatives and their antimony(III) and bismuth(III) complexes;Karina S.O. Ferraz等;《European Journal of Medicinal Chemistry》;20120329;第53卷;第98-106页 * |
| Seven coordinated cobalt(II) complexes with 2,6-diacetylpyridine bis(4-acylhydrazone) ligands: Synthesis, characterization, DNA-binding and nuclease activity;Cansu Gokce等;《Inorganica Chimica Acta》;20150418;第432卷;第213-220页 * |
| Synthesis and spectral investigation of manganese(II), cadmium(II) and oxovanadium(IV) complexes with 2,6-diacetylpyridine bis(2-aminobenzoylhydrazone): Crystal structure of manganese(II) and cadmium(II) complexes;Kalagouda B. Gudasi等;《Inorganica Chimica Acta》;20061231;第359卷;第3229-3236页 * |
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