CN112321650B - Preparation method and application of novel cobalt complex with two-dimensional structure - Google Patents
Preparation method and application of novel cobalt complex with two-dimensional structure Download PDFInfo
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- 150000004700 cobalt complex Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- HXKWSTRRCHTUEC-UHFFFAOYSA-N 2,4-Dichlorophenoxyaceticacid Chemical compound OC(=O)C(Cl)OC1=CC=C(Cl)C=C1 HXKWSTRRCHTUEC-UHFFFAOYSA-N 0.000 claims abstract description 17
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 4
- 238000000844 transformation Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 238000002447 crystallographic data Methods 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- 102000008100 Human Serum Albumin Human genes 0.000 description 19
- 108091006905 Human Serum Albumin Proteins 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 19
- 230000003993 interaction Effects 0.000 description 13
- 238000000862 absorption spectrum Methods 0.000 description 9
- 238000010791 quenching Methods 0.000 description 8
- 230000000171 quenching effect Effects 0.000 description 8
- 150000004696 coordination complex Chemical class 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 244000309466 calf Species 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 210000001541 thymus gland Anatomy 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 2
- 230000001093 anti-cancer Effects 0.000 description 2
- 230000002155 anti-virotic effect Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- -1 cobalt metal complex Chemical class 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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Abstract
The invention provides a novel two-dimensional structure cobalt complex, a preparation method and application thereof, and belongs to the technical field of drug synthesis. The novel cobalt complex with a two-dimensional structure [ Co (dpoa) (CH)3OH)]The molecular formula is C18H16Cl4CoO8Molecular weight is 561.04, dpoa is 2, 4-dichlorophenoxyacetic acid radical. The complex belongs to a monoclinic system, P21/c space group, the unit cell parameters are a-19.0517 (11) nm, b-7.3537 (4) nm and c-7.3537 (4) nm; α is 90 °, β is 100.860(6 °), and γ is 90 °. The preparation method of the novel two-dimensional structure cobalt complex comprises the following steps: respectively dissolving 2, 4-dichlorophenoxyacetic acid and cobalt sulfate heptahydrate in a solvent, dropwise adding the cobalt sulfate heptahydrate solution into the 2, 4-dichlorophenoxyacetic acid solution, enabling the solution to develop pink, adjusting the pH value with NaOH, stirring at room temperature, placing the solution in a reaction kettle, placing the reaction kettle in an oven for reaction, opening the kettle and standing to obtain pink blocky crystals.
Description
Technical Field
The invention relates to the technical field of drug synthesis, in particular to a novel two-dimensional structure cobalt complex, and a preparation method and application thereof.
Background
The metal complex has fat solubility and penetrability, and generally has good biological activities of bacteriostasis, antivirus, anticancer and the like. Meanwhile, the bonding mechanism of the metal complex and the biomacromolecule DNA shows that the metal complex has a DNA targeting effect, and the interaction between the metal complex and the ligand is researched by changing the coordination mode between the metal ions and the ligand, so that the metal complex has important significance for the exploration and research of the metal complex in the aspects of bacteriostasis, antivirus and anticancer application, and is also a hotspot in the research field of bio-inorganic chemistry.
Disclosure of Invention
The invention aims to: aiming at the problems, the invention provides a novel two-dimensional structure cobalt complex, a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention firstly provides a novel two-dimensional structure cobalt complex [ Co (dpoa) (CH)3OH)]The molecular formula is C18H16Cl4CoO8Molecular weight is 561.04, dpoa is 2, 4-dichlorophenoxyacetic acid radical. The complex belongs to a monoclinic system, P21/c space group, the unit cell parameters are a-19.0517 (11) nm, b-7.3537 (4) nm and c-7.3537 (4) nm; α is 90 °, β is 100.860(6 °), and γ is 90 °. The implementation diagram of the complex is as follows:
the invention also provides a preparation method of the novel two-dimensional structure cobalt complex, which comprises the following steps: respectively dissolving 2, 4-dichlorophenoxyacetic acid and cobalt sulfate heptahydrate in a solvent, dropwise adding the cobalt sulfate heptahydrate solution into the 2, 4-dichlorophenoxyacetic acid solution, enabling the solution to develop pink, adjusting the pH value with NaOH, stirring at room temperature, placing the solution in a reaction kettle, placing the reaction kettle in an oven for reaction, opening the kettle and standing to obtain pink blocky crystals.
In the invention, the molar ratio of the 2, 4-dichlorophenoxyacetic acid to the cobalt sulfate heptahydrate is preferably 3: 0.8-1.2.
In the present invention, the pH is preferably 6.0 to 6.5, and the standing time at room temperature is preferably 1 to 3 days.
In the present invention, the solvent is preferably methanol or a methanol-water mixed solvent.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention provides a novel structure of a two-dimensional structure cobalt complex and a preparation method thereof, and the novel structure has the advantages of simple process, low cost, good repeatability and the like.
2. The invention proves that the combination mode of the synthesized novel two-dimensional structure cobalt complex and CT-DNA is plug-in through ultraviolet absorption spectrum, fluorescence spectrum and viscosity; ultraviolet absorption spectrum and fluorescence spectrum prove that the synthesized novel two-dimensional structure cobalt complex has interaction with Human Serum Albumin (HSA), and the fluorescence quenching of the complex on HSA is static quenching.
Drawings
FIG. 1 is a block diagram of a complex of the present invention;
FIG. 2 is a diagram of an embodiment of a complex of the present invention;
FIG. 3 is the ultraviolet absorption spectrum of the interaction between the synthesized complex of the invention and calf thymus DNA (CT-DNA).
FIG. 4 is a fluorescent spectrum of the interaction of the synthesized complex of the present invention and calf thymus DNA (CT-DNA).
FIG. 5 is a diagram of the UV absorption spectrum of the interaction between the synthesized complex of the present invention and Human Serum Albumin (HSA).
FIG. 6 is a fluorescence spectrum of the interaction of the complex synthesized according to the present invention with Human Serum Albumin (HSA).
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In order to obtain more complexes with higher activity, the invention provides the following complexes through research and verification.
In one exemplary embodiment of the present invention, a novel cobalt complex having a two-dimensional structure is provided.
The novel two-dimensional structure cobalt complex [ Co (dpoa)) (CH3OH)]The molecular formula is C18H16Cl4CoO8Molecular weight is 561.04, dpoa is 2, 4-dichlorophenoxyacetic acid radical. The complex belongs to a monoclinic system, P21/c space group, unit cell parameters are a-19.0517 (11) nm, b-7.3537 (4) nm and c-7.3537 (4) nm; α is 90 °, β is 100.860(6 °), and γ is 90 °.
The invention also provides an embodiment of the preparation method of the novel two-dimensional structure cobalt complex, which comprises the following steps: respectively dissolving 2, 4-dichlorophenoxyacetic acid and cobalt sulfate heptahydrate in a solvent, dropwise adding the cobalt sulfate heptahydrate solution into the 2, 4-dichlorophenoxyacetic acid solution, enabling the solution to develop pink, adjusting the pH value with NaOH, stirring at room temperature, placing the solution in a reaction kettle, placing the reaction kettle in an oven for reaction, opening the kettle and standing to obtain pink blocky crystals.
In order to ensure that the ligand raw materials are fully reacted and obtain the target complex, the molar ratio of the 2, 4-dichlorophenoxyacetic acid to the cobalt sulfate heptahydrate is preferably 3: 0.8-1.2.
In the present invention, it is preferable that the NaOH solution has a concentration of 1.0 to 2.0mol/L and is stirred at room temperature for 30 to 50 min.
In the present invention, the reaction time in the reaction vessel is preferably 12 to 36 hours.
In the present invention, preferably, the pH is 6.0 to 6.5 and the standing time at room temperature is 1 to 3 days.
In the present invention, the solvent is preferably methanol and a methanol-water mixed solvent, and methanol is particularly preferred.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
First, preparation example
Example 1
And (3) synthesis of a complex: respectively dissolving 2, 4-dichlorophenoxyacetic acid (0.60mmol) and cobalt sulfate heptahydrate (0.16mmol) in methanol, dropwise adding the cobalt sulfate heptahydrate solution into the 2, 4-dichlorophenoxyacetic acid solution at the speed of 1.0mL/min, adjusting the pH value to 6.0 by using 1.0mol/L NaOH solution, stirring at room temperature for 30min, placing the solution in a reaction kettle, placing the reaction kettle in an oven for reaction for 12 hours, opening the kettle and standing for 1 day to obtain pink blocky crystals.
Example 2
And (3) synthesis of a complex: respectively dissolving 2, 4-dichlorophenoxyacetic acid (0.60mmol) and cobalt sulfate heptahydrate (0.20mmol) in methanol, dropwise adding the cobalt sulfate heptahydrate solution into the 2, 4-dichlorophenoxyacetic acid solution at the speed of 1.5mL/min, adjusting the pH value to 6.2 by using 1.5mol/L NaOH solution, stirring at room temperature for 40min, placing the solution in a reaction kettle, placing the reaction kettle in an oven for reacting for 24 hours, opening the kettle and standing for 2 days to obtain pink blocky crystals.
Example 3
And (3) synthesis of a complex: respectively dissolving 2, 4-dichlorophenoxyacetic acid (0.60mmol) and cobalt sulfate heptahydrate (0.24mmol) in methanol, dropwise adding the cobalt sulfate heptahydrate solution into the 2, 4-dichlorophenoxyacetic acid solution at the speed of 2.0mL/min, adjusting the pH value to 6.5 by using 2.0mol/L NaOH solution, stirring at room temperature for 50min, placing the solution in a reaction kettle, placing the reaction kettle in an oven for reacting for 36 hours, opening the kettle and standing for 3 days to obtain pink blocky crystals.
Identification of bis, Complex
Single crystal XRD test was performed on the pink bulk crystals prepared in examples 1-3, and the complex [ Co (dpoa) (CH)3OH)]The data of the crystallography, the key length and angle, the twist angle, etc. are shown in tables 1, 2 and 3, respectively.
TABLE 1 crystallographic data for the complexes
TABLE 2 major bond lengths and bond angles of the complexes
Symmetric transformations for generating equivalent atoms:
#1 -x+2,-y+1,-z+2 #2 x,-y+ 1/2,z+1/2 #3 -x+2,y+1/2,-z+ 3/2 #4 -x+2,y-1/2,-z+ 3/2
TABLE 3 major torsion angles of the complexes
Angle of torsion | Angle (°) | Angle of torsion | Angle (°) |
O(1)#1-Co(1)-O(1)-C(1) | -112(100) | C(3)-C(4)-C(5)-C(6) | 0(3) |
O(4)-Co(1)-O(1)-C(1) | 169.7(12) | C(4)-C(5)-C(6)-C(7) | 0(3) |
O(4)#1-Co(1)-O(1)-C(1) | -10.3(12) | C(4)-C(5)-C(6)-Cl(1) | -179.1(13) |
O(2)#2-Co(1)-O(1)-C(1) | 79.9(12) | C(5)-C(6)-C(7)-C(8) | 0(3) |
O(2)#3-Co(1)-O(1)-C(1) | -100.1(12) | Cl(1)-C(6)-C(7)-C(8) | 178.7(13) |
Co(1)-O(1)-C(1)-O(2) | 21(2) | C(6)-C(7)-C(8)-C(3) | 1(3) |
Co(1)-O(1)-C(1)-C(2) | -158.1(10) | C(6)-C(7)-C(8)-Cl(2) | 178.5(13) |
Co(1)#4-O(2)-C(1)-O(1) | 163.6(11) | C(4)-C(3)-C(8)-C(7) | -1(2) |
Co(1)#4-O(2)-C(1)-C(2) | -17(2) | O(3)-C(3)-C(8)-C(7) | 179.0(15) |
O(1)-C(1)-C(2)-O(3) | -15.3(18) | C(4)-C(3)-C(8)-Cl(2) | -178.7(13) |
O(2)-C(1)-C(2)-O(3) | 165.1(12) | O(3)-C(3)-C(8)-Cl(2) | 2(2) |
C(1)-C(2)-O(3)-C(3) | 177.8(12) | O(1)#1-Co(1)-O(4)-C(9) | -134.9(12) |
C(2)-O(3)-C(3)-C(4) | -10(2) | O(1)-Co(1)-O(4)-C(9) | 45.1(12) |
C(2)-O(3)-C(3)-C(8) | 169.6(13) | O(4)#1-Co(1)-O(4)-C(9) | 5(100) |
O(3)-C(3)-C(4)-C(5) | -179.4(16) | O(2)#2-Co(1)-O(4)-C(9) | 138.4(12) |
C(8)-C(3)-C(4)-C(5) | 1(3) | O(2)#3-Co(1)-O(4)-C(9) | -41.6(12) |
Symmetric transformations for generating equivalent atoms:
#1 -x+2,-y+1,-z+2 #2 x,-y+1/2,z+1/2 #3 -x+2,y+1/2,-z+3/2 #4 -x+2,y-1/2,-z+3/2
third, study of interaction of the Complex and DNA
The interaction capacity of the complex and DNA is researched, and calf thymus DNA (CT-DNA) is used as a research object.
1. The ultraviolet absorption spectrum of the action of the novel two-dimensional structure cobalt complex synthesized by the invention and CT-DNA is as follows:
after base line correction is carried out by taking Tris-HCl/NaCl as a buffer solution, the sample pool is changed into an isovolumetric complex solution, an electron absorption spectrum is scanned, an isovolumetric 2mmol/L CT-DNA solution is added, and the sample pool is stood for 5min and scanned after each addition. FIG. 3 is a graph showing the UV absorption spectrum of the interaction between the cobalt metal complex having a two-dimensional structure according to synthetic example 2 of the present invention and calf thymus DNA (CT-DNA). It can be seen that there are absorption peaks at the wavelengths of 293nm and 301 nm. As CT-DNA was increased, the absorbance of the complex decreased with a slight purple shift, indicating that the binding mode between the complex and DNA may be external. Calculating to obtain the binding constant K of the complex and the DNAb=1.36×103L·mol-1。
2. The fluorescent spectrum of the action of the novel two-dimensional structure cobalt complex synthesized by the invention and CT-DNA is as follows:
adding EB-CT-DNA mixed solution into a sample pool, wherein the excitation wavelength is 565nm, and the scanning speed is 240 nm.s-1Then, the emission spectrum in the wavelength range of 500 to 700nm is measured. And (3) dripping a complex solution into the EB-CT-DNA system, and measuring the emission spectrum after the complex solution reacts for 5 min. FIG. 4 is a fluorescence spectrum of interaction between the novel cobalt metal complex with a two-dimensional structure of synthetic example 2 of the present invention and calf thymus DNA (CT-DNA). It can be seen that the fluorescence intensity gradually decreases as the concentration of the complex increases. At different r ═ Complex]/[DNA]At this value, the fluorescence intensity decreased by 21.25%. Complexes with CThe T-DNA mode of action is similar to that of EB, the classical mode of insertion. Obtaining a quenching rate constant Kq=1.62×1011L·mol-1·S-1. The fluorescence quenching of the complex to EB-DNA is static quenching, and the binding site n is 1.
Fourthly, research on interaction of novel two-dimensional structure cobalt complex synthesized by the invention and Human Serum Albumin (HSA)
1. The ultraviolet absorption spectrum of the action of the complex synthesized by the invention and Human Serum Albumin (HSA) is as follows:
adding an HSA solution into the sample pool, adding a Tris-HCl/NaCl buffer solution into the reference pool, measuring the ultraviolet spectrum of the sample pool within 190-400 nm, respectively adding a complex solution into the two pools, standing at room temperature for 5min after each addition, and scanning within the same wavelength range. FIG. 5 is a diagram showing the UV absorption spectrum of the interaction between the complex synthesized in example 2 of the present invention and HSA. As can be seen, with the increase of the concentration of the complex, the absorption peak at 211nm generates a color reduction effect, and the position of the absorption peak is red-shifted, which indicates that the complex and HSA act in an insertion mode.
2. The fluorescent spectrum of the action of the complex synthesized by the invention and HSA is as follows:
the sample cell was added with a HSA solution, and the fluorescence spectrum was measured. And adding the complex solution into the sample pool, standing at room temperature for 5min after each addition, and scanning under the same conditions. FIG. 6 is a fluorescence spectrum of interaction between the complex synthesized in example 2 of the present invention and HSA. It can be seen that HSA has a strong absorption peak at 345nm, with decreasing absorption intensity as the complex concentration increases. Quenching rate constant value of 3.75X 1012L·mol-1·S-1The fluorescence quenching of HSA by the complex is static quenching, and the number of binding sites n is 1.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (5)
1. Novel two-dimensional structure cobalt is joined in marriageThe compound is characterized in that the molecular formula of the complex is C18H16Cl4CoO8The molecular weight is 561.04, and the data of the crystal structure parameters, the main bond length, the bond angle, the main torsion angle and the like of the complex are respectively listed in tables 1, 2 and 3;
TABLE 1 crystallographic data for the complexes
TABLE 2 major bond lengths and bond angles of the complexes
Symmetric transformations for generating equivalent atoms:
#1-x+2,-y+1,-z+2 #2 x,-y+1/2,z+1/2 #3-x+2,y+1/2,-z+3/2 #4-x+2,y-1/2,-z+3/2
TABLE 3 major torsion angles of the complexes
Symmetric transformations to produce equivalent atoms:
#1-x+2,-y+1,-z+2 #2 x,-y+1/2,z+1/2 #3-x+2,y+1/2,-z+3/2 #4-x+2,y-1/2,-z+3/2。
2. the preparation method of the novel cobalt complex with the two-dimensional structure as claimed in claim 1, characterized by comprising the following steps: respectively dissolving 2, 4-dichlorophenoxyacetic acid and cobalt sulfate heptahydrate in a solvent, dropwise adding the cobalt sulfate heptahydrate solution into the 2, 4-dichlorophenoxyacetic acid solution, enabling the solution to develop pink, adjusting the pH value with NaOH, stirring at room temperature, placing the solution in a reaction kettle, placing the reaction kettle in an oven for reaction, opening the kettle and standing to obtain pink blocky crystals.
3. The method for preparing a novel cobalt complex with a two-dimensional structure as claimed in claim 2, wherein the molar ratio of 2, 4-dichlorophenoxyacetic acid to cobalt sulfate heptahydrate is 3: 0.8-1.2.
4. The method for preparing a novel cobalt complex with a two-dimensional structure according to claim 2, wherein the pH is 6.0 to 6.5.
5. The method for preparing a novel cobalt complex with a two-dimensional structure according to claim 2, wherein the standing time is 1 to 3 days.
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