CN102603642A - Nickel-containing sandwich polyoxometallate anti-cancer drug and synthesis method thereof - Google Patents
Nickel-containing sandwich polyoxometallate anti-cancer drug and synthesis method thereof Download PDFInfo
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- CN102603642A CN102603642A CN201110450744XA CN201110450744A CN102603642A CN 102603642 A CN102603642 A CN 102603642A CN 201110450744X A CN201110450744X A CN 201110450744XA CN 201110450744 A CN201110450744 A CN 201110450744A CN 102603642 A CN102603642 A CN 102603642A
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Abstract
The invention relates to a nickel-containing sandwich polyoxometallate anti-cancer drug and a synthesis method thereof. In recent years, great progresses are made in the pharmaceutical and chemical researches of polyoxometallate. However, only a proliferation inhibiting effect and the like are obtained. The synthesis method comprises the steps of: 1) under the effect of magnetic agitation, dissolving 4-5mmol of Na2WO4 in 80-120ml of deionized water and heating to 80-120 DEG C, then adding hydrochloric acid with concentration being 6mol/L to regulate pH to 5.0-7.0 to obtain solution A; and 2) adding 0.5-1mmol of NiCl2, 0.8-1.2mmol of solid imidazole and 0.3-0.8mmol of Bi(NO3)3 dissolved in 10ml of HCl with concentration being 6mol/L into the solution A at the same time, evenly mixing, heating to 80-120 DEG C for reaction for 1-2h, cooling to room temperature, filtering and finally statically placing for 5-10 days. The nickel-containing sandwich polyoxometallate anti-cancer drug is used for inhibiting human gastric cancer cells and colon cancer cells.
Description
Technical field:
the present invention relates to a kind of people's liver cancer and people's cancer of the stomach tumour cell etc. to be had bismuth tungstate and the compound method thereof that active transiting metal nickel and imidazoles are modified, and are specifically related to a kind of nickeliferous sandwich polyoxometallate cancer therapy drug and compound method thereof.
Background technology:
in recent years, the pharmaceutical chemistry research of polyoxometallate has obtained impressive progress, its pharmacology, physiologically active are identified, in research Showed Very Brisk antiviral, anti-tumor aspect.1971, French scientist Raynaud found that at first Keggin type tungsten sila polyanionic can suppress mouse fibrosarcoma virus (MLSV), found [BW later in succession
12
O
40
]
5-
Deng at the external antiviral activity that shows.1985, discovery HPA-23 such as Dormont had restraining effect to the reversed transcriptive enzyme of HIV, and were applied to clinical in the France and the U.S. very soon.The substituted Keggin structure of discovery organosilicon silicotungstates such as Hill in 1992 HIV HIV-1 that can draw up.Nineteen ninety-five; The sandwich isostructural poly-tungstate of discovery Keggin such as Yamase, vacant Keggin, Wells-Dawson and Keggin has anti-microbial activity to staphylococcus aureus; Calendar year 2001, employing The study of computer simulation such as Hill contain the Wells-Dawson structure and the proteic interaction situation of HIV-1 of niobium.These researchs only comprise inhibited proliferation, morphological observation, the detection of cell cycle etc.Therefore, polyoxometallate meets the future studies and the development trend of field of medicaments anticancer chemotherapeutic agent as new drug development.
Summary of the invention:
the purpose of this invention is to provide a kind of nickeliferous sandwich polyoxometallate cancer therapy drug and compound method thereof, obtain a kind of cancers such as people's liver cancer, people's cancer of the stomach tumour cell being had active novel cpd.To have compound method simple for this technology simultaneously, and productive rate is high, is the anticancer newtype drug of a kind of potential broad-spectrum, has great application value.
Above-mentioned purpose realizes through following technical scheme:
The compound method of nickeliferous sandwich polyoxometallate cancer therapy drug, this method comprises the steps:
(1) under magnetic agitation, with the Na of 4～5mmol
2
WO
4
Be dissolved in the deionized water of 80～120ml, and be heated to 80～120 ℃, the HCl that dropwise adds 6mol/L then regulates pH to 5.0～7.0, obtains solution A;
(2) with the NiCl of 0.5～1mmol
2
, 0.8～1.2mmol the solid imidazoles, be dissolved in the Bi (NO of 0.3～0.8mmol among the 10mL 6 mol/L HCl
3
)
3
Join simultaneously in the solution A, mixing post-heating to 80～120 ℃ reaction 1～2h is cooled to room temperature then, filters the back and gets final product in static 5～10 days.
A kind of with the nickeliferous sandwich polyoxometallate cancer therapy drug of aforesaid method synthetic, its molecular formula is: Na 4 Bi 2 Ni 2 W 20 C 6 H 84 N 4 O 105 , molecular weight: 6196.87,
Its structural formula is:
normal temperature is green bulk crystals down.
Beneficial effect:
1. synthetic Na of the present invention
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
Be a kind of polyoxometallate that active imidazoles is modified that has, it has very strong inhibited proliferation, people's gastric tumor cell and human colon carcinoma tumour cell is also had the better inhibited rate human liver cancer cell.Synthetic Na of the present invention
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
Adopt the MTT method to detect of the growth-inhibiting effect of this compound, its half-inhibition concentration IC to tumour cell
50
=0.081mmol/L, 24h.Fluorescence colour such as AO/EB, FITC/PI detects gained anticancer compound Na among the present invention
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
Tumor cell line had apoptosis-induced effect.Adopt agarose gel electrophoresis (DNA ladder) laboratory method of SCGE experiment (comet experiment) and apoptotic cell to detect gained anticancer compound Na among the present invention
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
Dna damage situation to the existence of tumor cell line experiment in vitro.Adopt transmission electron microscope and ESEM morphological observation, obtained gained anticancer compound Na among the present invention
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
The ultrastructure of cell death inducing adopts Flow Cytometry to detect apoptotic per-cent.The present invention is significant and researching value in the antitumor pharmacy functional study of polyoxometallate; To scientific basis be provided for the feasibility that polyoxometallate is treated new drug as the malignant tumour clinical chemistry, for antitumor chemical new drug development is established the scientific experiment basis.
2. gained anticancer compound Na of the present invention
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
, detect of the influence of its various dose to people's cancer of the stomach and colorectal carcinoma inhibition rate of tumor cell; The result is as shown in Figure 3, and is visible, along with anticancer compound Na
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
The increase of consumption, people's cancer of the stomach and colorectal carcinoma inhibition rate of tumor cell increase gradually, and gained anticancer compound Na among the present invention is described
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
People's cancer of the stomach and colorectal carcinoma tumour cell there is the good restraining rate.Adopt fluorescence colours such as AO/EB, FITC/PI to detect gained anticancer compound Na among the present invention simultaneously
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
Tumor cell line had apoptosis-induced effect.Adopt two kinds of experimental techniques of agarose gel electrophoresis (DNA ladder) of single cell gel electrophoresis (comet experiment) and apoptotic cell to detect gained anticancer compound Na among the present invention
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
To the external damaging action of tumor cell line with inducing DNA.Adopt transmission electron microscope and ESEM morphological observation, gained anticancer compound Na among the present invention is described
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
Ultrastructure that can inducing apoptosis of tumour cell adopts low cytometric analysis to detect apoptotic per-cent.Gained anticancer compound Na among the present invention
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
With the comparative studies of clinical chemotherapy medicine commonly used (5 FU 5 fluorouracil) at tumor inhibition effect; The result is as shown in Figure 4, and is visible, gained anticancer compound Na among the present invention
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
To human liver tumor cell's restraining effect greater than 5 FU 5 fluorouracil, explain that it has good anti-cancer activity.
3. the present invention is through the conventional soln method, and pH value, ingredient proportion and the temperature of control solution obtain a kind of cancers such as people's liver cancer, people's cancer of the stomach tumour cell being had active novel cpd.To have compound method simple for this technology simultaneously, and productive rate is high, proves through a large amount of experiments:
When other condition was constant, if after adjusting pH value was reacted same temporal filtering less than 5.5, placing a couple of days still was clear solution, no crystal produced
(1); Under the similarity condition,, then can not obtain green precipitate if pH is higher than 7.5.
(2) are when other condition is constant, if Heating temperature is lower than 40 ℃, react same temporal filtering after, placing a couple of days still be clear solution, no crystal generation.Under the similarity condition,, obtain thin and in small, broken bits crystal, can not satisfy test request if Heating temperature surpasses 80 ℃.
(3) when other condition was constant, during reaction times deficiency 1.5h, after the filtration, placing a couple of days still was clear solution, and no crystal produces; Under the similarity condition,, then can obtain green spherical noncrystal if when the reaction times surpasses 2.5h.
Description of drawings:
Fig. 1 uses preceding people's liver cancer tumour cell aspect graph for the present invention;
Fig. 2 is the people's liver cancer tumour cell aspect graph behind effect 24 h of the present invention;
Fig. 3 is the graphic representation of this product of various dose to the influence of people's cancer of the stomach and colorectal carcinoma inhibition rate of tumor cell;
Fig. 4 is the graphic representation that the present invention and 5 FU 5 fluorouracil influence human liver cancer cell.
Embodiment:
Just for better explanation the present invention, the present invention is not limited to following examples to
following examples.
Embodiment 1:
This embodiment anticancer compound Na
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
Compound method realize according to the following steps: one, under magnetic agitation, with the Na of 4～5mmol
2
WO
4
Be dissolved in the deionized water of 80～120ml, and be heated to 80～120 ℃, the HCl that dropwise adds 6mol/L then regulates pH to 5.0～7.0, obtains solution A; Two, with the NiCl of 0.5～1mmol
2
, 0.8～1.2mmol the solid imidazoles and be dissolved in the Bi (NO of 0.3～0.8mmol among the 6mol/L HCl
3
)
3
Join simultaneously in the solution A, mixing post-heating to 80～120 ℃ reaction 1～2h is cooled to room temperature then, filters the back static 5～10 days, promptly accomplishes anticancer compound Na
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
Synthetic; Wherein the consumption of HCl is 10mL in the step 2.
Gained anticancer compound Na in this embodiment 4 Bi 2 Ni 2 W 20 C 6 H 84 N 4 O 105 Be green bulk crystals.Its chemical formula is H 6 [Bi 2 W 20 Ni 2 (H 2 O) 6 O 70 Na 4 (H 2 O) 14 ] (H 4 C 3 N 2 ) 2 Its molecular weight: 6196.87,
Its structural formula is:
Embodiment 2:
Present embodiment and embodiment 1 are different is with the Na of 4～5mmol in the step 1
2
WO
4
Be dissolved in the deionized water of 80ml, and be heated to 80 ℃.Other step and parameter are identical with embodiment 1.
Embodiment 3:
Present embodiment and embodiment 1 are different is with the Na of 5mmol in the step 1
2
WO
4
Be dissolved in the deionized water of 120ml, and be heated to 120 ℃.Other step and parameter are identical with embodiment 1.
Embodiment 4:
Present embodiment and embodiment 1 are different is with the Na of 4.2～4.8mmol in the step 1
2
WO
4
Be dissolved in the deionized water of 90～110ml, and be heated to 90～110 ℃.Other step and parameter are identical with embodiment 1.
Embodiment 5:
Present embodiment and embodiment 1 are different be in the step 1 under magnetic agitation, with the Na of 4.5mmol
2
WO
4
Be dissolved in the deionized water of 100ml, and be heated to 100 ℃.Other step and parameter are identical with embodiment 1.
Embodiment 6:
Present embodiment and embodiment 1 are different be in the step 1 under magnetic agitation, with the Na of 4.7mmol
2
WO
4
Be dissolved in the deionized water of 105ml, and be heated to 105 ℃.Other step and parameter are identical with embodiment 1.
Embodiment 7:
What
present embodiment was different with the foregoing description 1-6 is that the HCl that dropwise adds 6mol/L in the step 1 regulates pH to 5.0.Other step and parameter are identical with one of embodiment 1-6.
Embodiment 8:
What
present embodiment was different with the foregoing description 1-6 is that the HCl that dropwise adds 6mol/L in the step 1 regulates pH to 7.0.Other step and parameter are identical with one of embodiment 1-6.
Embodiment 9:
What
present embodiment was different with the foregoing description 1-6 is that the HCl that dropwise adds 6mol/L in the step 1 regulates pH to 5.5～6.0.Other step and parameter are identical with one of embodiment 1-6.
Embodiment 10:
What
present embodiment was different with the foregoing description 1-6 is that the HCl that dropwise adds 6mol/L in the step 1 regulates pH to 6.0～6.5.Other step and parameter are identical with one of embodiment 1-6.
Embodiment 11:
What
present embodiment was different with the foregoing description 1-6 is that the HCl that dropwise adds 6mol/L in the step 1 regulates pH to 6.5～7.0.Other step and parameter are identical with one of embodiment 1-6.
Embodiment 12:
What
present embodiment was different with the foregoing description 1-6 is that the HCl that dropwise adds 6mol/L in the step 1 regulates pH to 5.5.Other step and parameter are identical with one of embodiment 1-6.
Embodiment 13:
Present embodiment is different with one of the foregoing description 1-12 is with the NiCl of 0.5mmol in the step 2
2
, 0.8mmol the solid imidazoles and be dissolved in the Bi (NO of the 0.3mmol among the 6mol/L HCl
3
)
3
Join in the solution A mixing post-heating to 80 ℃ reaction 1h simultaneously.Other step and parameter are identical with one of embodiment 1-12.
Embodiment 14:
Present embodiment is different with one of the foregoing description 1-12 is with the NiCl of 1mmol in the step 2
2
, 1.2mmol the solid imidazoles and be dissolved in the Bi (NO of the 0.8mmol among the 6mol/L HCl
3
)
3
Join in the solution A mixing post-heating to 120 ℃ reaction 2h simultaneously.Other step and parameter are identical with one of embodiment 1-12.
Embodiment 15:
Present embodiment is different with one of the foregoing description 1-12 is with the NiCl of 0.8mmol in the step 2
2
, 1.1mmol the solid imidazoles and be dissolved in the Bi (NO of the 0.6mmol among the 6mol/L HCl
3
)
3
Join in the solution A mixing post-heating to 100 ℃ reaction 1.5h simultaneously.Other step and parameter are identical with one of embodiment 1-12.
Embodiment 16:
What
present embodiment was different with one of the foregoing description 1-15 is to filter the back static 5 days in the step 2.Other step and parameter are identical with one of embodiment 1-15.
Embodiment 17:
What
present embodiment was different with one of the foregoing description 1-15 is to filter the back static 10 days in the step 2.Other step and parameter are identical with one of embodiment 1-15.
Embodiment 18:
What
present embodiment was different with one of the foregoing description 1-15 is to filter the back static 6～9 days in the step 2.Other step and parameter are identical with one of embodiment 1-15.
Embodiment 19:
What
present embodiment was different with one of the foregoing description 1-15 is to filter the back static 7 days in the step 2.Other step and parameter are identical with one of embodiment 1-15.
Embodiment 20:
This embodiment anticancer compound Na
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
Compound method realize according to the following steps: one, under magnetic agitation, with the Na of 4.7mmol
2
WO
4
Be dissolved in the deionized water of 100ml, and be heated to 100 ℃, the HCl that dropwise adds 6mol/L then regulates pH to 6.0, obtains solution A; Two, with the NiCl of 0.7mmol
2
, 1mmol the solid imidazoles and be dissolved in the Bi (NO of the 0.5mmol among the 6mol/L HCl
3
)
3
Join simultaneously in the solution A, mixing post-heating to 100 ℃ reaction 1.5h is cooled to room temperature then, filters the back static 8 days, promptly accomplishes anticancer compound Na
4
Bi
2
Ni
2
W
20
C
6
H
84
N
4
O
105
Synthetic; Wherein the consumption of HCl is 10mL in the step 2.
Claims (10)
1. the compound method of a nickeliferous sandwich polyoxometallate cancer therapy drug, it is characterized in that: this method comprises the steps:
(1) under magnetic agitation, with the Na of 4～5mmol
2WO
4Be dissolved in the deionized water of 80～120ml, and be heated to 80～120 ℃, the HCl that dropwise adds 6mol/L then regulates pH to 5.0～7.0, obtains solution A;
(2) with the NiCl of 0.5～1mmol
2, 0.8～1.2mmol the solid imidazoles, be dissolved in the Bi (NO of 0.3～0.8mmol among the 10mL 6 mol/L HCl
3)
3Join simultaneously in the solution A, mixing post-heating to 80～120 ℃ reaction 1～2h is cooled to room temperature then, filters the back and gets final product in static 5～10 days.
2. the compound method of nickeliferous sandwich polyoxometallate cancer therapy drug according to claim 1 is characterized in that: in the step 1 with the Na of 4.2～4.8mmol
2WO
4Be dissolved in the deionized water of 90～110ml, and be heated to 90～110 ℃.
3. the compound method of nickeliferous sandwich polyoxometallate cancer therapy drug according to claim 1 is characterized in that: in the step 1 under magnetic agitation, with the Na of 4.5mmol
2WO
4Be dissolved in the deionized water of 100ml, and be heated to 100 ℃.
4. the compound method of nickeliferous sandwich polyoxometallate cancer therapy drug according to claim 1 is characterized in that: in the step 1 under magnetic agitation, with the Na of 4.7mmol
2WO
4Be dissolved in the deionized water of 105ml, and be heated to 105 ℃.
5. according to claim 1 or 2 or the compound method of 3 or 4 described nickeliferous sandwich polyoxometallate cancer therapy drugs, it is characterized in that: the HCl that dropwise adds 6mol/L in the step 1 regulates pH to 5.5～6.0.
6. according to claim 1 or 2 or the compound method of 3 or 4 described nickeliferous sandwich polyoxometallate cancer therapy drugs, it is characterized in that: the HCl that dropwise adds 6mol/L in the step 1 regulates pH to 6.0～6.5.
7. according to claim 1 or 2 or the compound method of 3 or 4 described nickeliferous sandwich polyoxometallate cancer therapy drugs, it is characterized in that: in the step 2 with the NiCl of 0.8mmol
2, 1.1mmol the solid imidazoles and be dissolved in the Bi (NO of the 0.6mmol among the 6mol/L HCl
3)
3Join in the solution A mixing post-heating to 100 ℃ reaction 1.5h simultaneously.
8. the compound method of nickeliferous sandwich polyoxometallate cancer therapy drug according to claim 5 is characterized in that: in the step 2 with the NiCl of 0.8mmol
2, 1.1mmol the solid imidazoles and be dissolved in the Bi (NO of the 0.6mmol among the 6mol/L HCl
3)
3Join in the solution A mixing post-heating to 100 ℃ reaction 1.5h simultaneously.
9. the compound method of nickeliferous sandwich polyoxometallate cancer therapy drug according to claim 6 is characterized in that: in the step 2 with the NiCl of 0.8mmol
2, 1.1mmol the solid imidazoles and be dissolved in the Bi (NO of the 0.6mmol among the 6mol/L HCl
3)
3Join in the solution A mixing post-heating to 100 ℃ reaction 1.5h simultaneously.
10. one kind with the nickeliferous sandwich polyoxometallate cancer therapy drug of aforesaid method synthetic, and it is characterized in that: its molecular formula is: Na
4Bi
2Ni
2W
20C
6H
84N
4O
105, molecular weight: 6196.87, its structural formula is:
Normal temperature is green bulk crystals down.
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| CN103524567A (en) * | 2013-09-29 | 2014-01-22 | 哈尔滨工业大学 | Anti human osteosarcoma zinc-containing heteropoly compound and synthetic method thereof |
| CN104922149A (en) * | 2015-06-19 | 2015-09-23 | 昆明学院 | Novel use of multi-anion oxometallate compound (AlMo6HO24)3- |
| CN104971359A (en) * | 2015-06-19 | 2015-10-14 | 昆明学院 | New use of organic-inorganic hybrid polyanion oxometallate compounds |
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| CN107098392A (en) * | 2017-05-12 | 2017-08-29 | 昆明学院 | A kind of arsenowolframic acid sandwich type polyoxometalates compound based on Manganic ion and preparation method and application |
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| CN103011120A (en) * | 2012-12-24 | 2013-04-03 | 金华职业技术学院 | Five-vacancy transition metal di-hepta-tungsten phosphorus oxygen cluster series compound and preparation method thereof |
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| CN103011300B (en) * | 2012-12-24 | 2014-10-08 | 金华职业技术学院 | Preparation method of five-vacancy ferrum di-hepta-tungsten phosphorus oxygen cluster compound |
| CN103011120B (en) * | 2012-12-24 | 2014-12-10 | 金华职业技术学院 | Five-vacancy transition metal di-hepta-tungsten phosphorus oxygen cluster series compound and preparation method thereof |
| CN103524567A (en) * | 2013-09-29 | 2014-01-22 | 哈尔滨工业大学 | Anti human osteosarcoma zinc-containing heteropoly compound and synthetic method thereof |
| CN103524567B (en) * | 2013-09-29 | 2016-03-23 | 哈尔滨工业大学 | A kind of anti-human osteosarcoma is containing the application of zinc heteropoly compound |
| CN104971359A (en) * | 2015-06-19 | 2015-10-14 | 昆明学院 | New use of organic-inorganic hybrid polyanion oxometallate compounds |
| CN104922149A (en) * | 2015-06-19 | 2015-09-23 | 昆明学院 | Novel use of multi-anion oxometallate compound (AlMo6HO24)3- |
| CN104922149B (en) * | 2015-06-19 | 2017-09-26 | 昆明学院 | Many the moon oxometallic acid salt compound [AlMo6H6O24]3‑Purposes |
| CN104971359B (en) * | 2015-06-19 | 2017-11-28 | 昆明学院 | The purposes of the how cloudy oxometallic acid salt compound of organic inorganic hybridization |
| CN106986344A (en) * | 2017-04-18 | 2017-07-28 | 吉林大学 | Silicotungstate and its preparation method and application |
| CN106986344B (en) * | 2017-04-18 | 2019-04-26 | 吉林大学 | Silicotungstate and its preparation method and application |
| CN107098392A (en) * | 2017-05-12 | 2017-08-29 | 昆明学院 | A kind of arsenowolframic acid sandwich type polyoxometalates compound based on Manganic ion and preparation method and application |
| CN107098392B (en) * | 2017-05-12 | 2019-03-05 | 昆明学院 | A kind of arsenowolframic acid sandwich type polyoxometalates compound and the preparation method and application thereof based on Manganic ion |
| 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 |
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