CN114275818A - Copper-containing Weakley type tungsten-oxygen cluster compound, preparation method and anti-tumor application thereof - Google Patents
Copper-containing Weakley type tungsten-oxygen cluster compound, preparation method and anti-tumor application thereof Download PDFInfo
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Abstract
The application provides a copper-containing Weakley type tungsten-oxygen cluster compound with a structural formula of H8[Cu6(H2O)6(GeW9O34)2]·4H2O; belonging to the monoclinic system, P21/n space groups having cell parameters of
α is 90.00 °, β is 95.918(2 °), and γ is 90.00 °. The compound has simple preparation method and high antitumor activity.
Description
Technical Field
The application relates to a copper-containing Weakley type tungsten-oxygen cluster compound, a preparation method and an anti-tumor application thereof, belonging to the polyoxometallate technology.
Background
Polyoxometalates are also called Polyacids (POMs), and are metal-oxygen cluster compounds formed by connecting early transition metals (such as V, Mo, W and the like) and oxygen atoms through M-O-M bonds to form polyhedrons, and connecting the polyhedrons in a coplanar mode, a common-edge mode and the like. The polyacids can be divided into two main classes, isopoly acids and heteropoly acids, depending on their structure. Wherein, isopoly acid refers to polyacid only containing one transition metal and has a general formula of { MmOy}n-And contain some hetero atoms (e.g. Si)4+、As5+、Ge4+Etc.) are referred to as heteropoly acids. There are six classical configurations of polyacids: keggin type and Dawson type]Anderson type, Waugh type, Silverton type, Lindqvist type. Wherein Keggin type, Dawson type, Anderson type, Waugh type and Silverton type belong to heteropoly acid, and Lindqvist type belongs to isopoly acid.
In the current research on POMs, the research on Keggin type polyacid is common, and Keggin type polyacid can form various vacancy structures. Triple vacancy tungstic acid cluster [ XW ]9O34]10-It can be considered that the Keggin cluster block loses three WO6Octahedron is obtained. Based on [ XW9O34]10-Sandwich-type compounds of building blocks are a wide variety and are an important branch of polyacid chemistry. The Weakley type is a Keggin type derivative structure which is a sandwich type structure constructed by three-vacancy derivatives of two Keggin type polyanions and a transition metal cluster.
A great deal of literature reports that polyoxometallate has the effects of resisting tumors, viruses and bacteria, but the Weakley polyoxometallate has less reports on the aspects of resisting tumors. Therefore, the development of more polyoxometallates of the Weakley type is of great significance.
Disclosure of Invention
The application provides a copper-containing Weakley type tungsten oxide cluster compound, a preparation method and an anti-tumor application thereof, which can effectively solve the problems.
The application is realized as follows:
a copper-containing Weakley type tungsten-oxygen cluster compound has a structural formula of H8[Cu6(H2O)6(GeW9O34)2]·4H2O; belonging to the monoclinic system, P21/n space groups having cell parameters of
α＝90.00°， β＝95.918(2)°，γ＝90.00°。
As a further improvement, the asymmetric unit comprises a hexagon { Cu }6Keggin type sandwich anion [ Cu ] substituted by transition metal cluster6(H2O2)6(B-α-GeW9O33)2]8-And quarternary free water; its three-vacancy is [ B-alpha-GeW9O33]10-Is composed of three common vertices { W }3O13The trimetal cluster of (a) is connected to the central atom Ge through three 3-bridge oxygen atomsIVForming a cavity structure.
The preparation method of the copper-containing Weakley type tungsten oxide cluster compound comprises the following steps:
s1, configuring 1mmol/L La (ClO)4)3·6H2O solution, 1mmol/L dimethylamine hydrochloride solution, NH of pH 103·H2O-NH4Cl buffer, 0.2mmol/L Cu (NO)3)2Dissolving;
s2, weighing Na2WO4·2H2O、GeO2Adding prepared La (ClO)4)3·6H2O solution, dimethylamine hydrochloride solution, NH3·H2O-NH4Cl buffer, Cu (NO)3)2The solution is evenly mixed and kept stand for 3.5 to 4.5 days at normal temperature, and green blocky crystals are separated out.
As a further improvement, in step S2, the Na is2WO4·2H2O、GeO2、 La(ClO4)3·6H2O solution, dimethylamine hydrochloride solution, NH3·H2O-NH4Cl buffer, Cu (NO)3)2The ratio of the solution is 0.3-0.4 g: 0.1-0.2 g: 0.15-0.25 ml: 4.5-5.5 ml: 4.5-5.5 ml: 0.10-0.20 ml.
As a further improvement, the step S2 also needs to use acetic acid to adjust the pH value to 7.1-7.3.
An application of the copper-containing Weakley type tungsten oxygen cluster compound in the preparation of antitumor drugs.
The beneficial effect of this application is: the copper-containing Weakley type tungsten-oxygen cluster compound prepared by the application is simple in preparation method, has good anti-tumor activity and has wide application prospect.
Drawings
In order to more clearly explain the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and that for those skilled in the art, other related drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a crystal structure diagram of a copper-containing Weakley type tungsten oxo cluster compound provided in example 1 of the present application. Wherein, a) basic cluster block [ B-alpha-GeW9O33]10-(ii) a b) Dimer centered Cu6Cluster [ Cu ]6(H2O)6]12+(Symmetry codes:a[2-x,-y,1-z]) (ii) a c) Polyanionic structure [ Cu6(H2O)6(GeW9O34)2]8-。
FIG. 2 is a three-dimensional supramolecular structure of a copper-containing Weakley-type tungsten oxo-cluster compound provided in example 1 of the present application.
FIG. 3 is an X-ray powder diffraction pattern of a copper-containing Weakley type tungsten oxo cluster compound provided in example 1 of the present application.
FIG. 4 is an IR spectrum of a copper-containing Weakley type tungsten oxo compound provided in example 1 of the present application.
FIG. 5 is a thermal analysis of a copper-containing Weakley-type tungsten oxo cluster compound provided in example 1 of the present application.
FIG. 6 is a graph of the inhibitory effect of copper-containing Weakley-type tungsten oxo cluster compounds provided in example 1 of the present application on Huh7 and SW 480.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive work based on the embodiments in the present application are within the scope of protection of the present application. Thus, the following detailed description of the embodiments of the present application, as presented in the figures, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In the description of the present application, the terms "first", "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless specifically defined otherwise.
Example 1
0.3266g of Na are weighed out in turn by the volatilization method2WO4·2H2O，0.1743g GeO2In a beaker, La (ClO) was added4)3·6H2O (0.2ml,1mmol), dimethylamine hydrochloride (5ml, 1mmol), NH3·H2O-NH4Cl buffer (5ml, pH 10.0), Cu (NO)3)2(0.15ml,0.2mmol), 5 drops of acetic acid (final pH of the solution 7.2), mixed well, and left to stand at room temperature for 4 days, to precipitate green massive crystals.
Analysis of single crystal structure
Selecting crystals with proper size and good quality under an SZ680 continuous zoom type double microscope. Collected on a Bruker APEX II CCD diffractometer and under low temperature conditions. The crystal structure was simulated and calculated by direct method using the SHELX-97 program to obtain the crystallographic data of the compound as shown in Table 1.
TABLE 1
Table 2-3 crystal structure parameters of the compounds
aR1＝∑││F0│-│Fc││/∑│F0│.bwR2＝{∑[w(F0 2-Fc)2]/∑[w(F0 2)2]}1/2
Compound H8[Cu6(H2O)6(B-α-GeW9O33)2]·4H2O belongs to the monoclinic system, P21/n space groups. The compounds are zero-dimensional structures. Its asymmetric unit contains a hexagon { Cu }6Keggin type sandwich anion [ Cu ] substituted by transition metal cluster6(H2O2)6(B-α-GeW9O33)2]8-And four molecules of free water. Three-position-deficient [ B-alpha-GeW9O33]10-(FIG. 1a) is composed of three co-vertices { W }3O13The trimetallic cluster of (a) is connected to the central atom Ge by three 3-bridge oxygen atomsIVForming a cavity structure. The structural unit contains three oxygen atoms, wherein 9 terminal oxygen (O) atoms are connected with only one W atomt)，W-OtHas a bond length in the range of
15 oxygen atoms bridged by two W atoms (O)W2)，W-OW2Has a bond length in the range of
3 quadruple oxygen atoms (W-O) connecting three W atoms and one central Ge atomW3Ge：
Ge-OW3GeIs composed of
)。
Dimer centered Cu6Six Cu in a cluster pass twelve μ3-O is connected (Cu-O bond length:
) The twelve oxygens are respectively from three W connected in common at the waist positions of two vacancy blocks2O10Oxygen on the polyhedron. As shown in FIG. 1b, this Cu6The six Cu on the cluster can also be regarded as a regular hexagon, the Cu1 and the Cu2 in the cluster are both hexa-coordinated, and the Cu1 is connected with 2 mu3-O (O9, O34), 3 μ2-O (O12, O29, O33) and one coordinated water (O1W). Cu2 connection 3 μ3O (O9, O34, O34A), 3 μ2-O (O12, O18, O31). Cu3 is Cu3 with all penta-coordinates connecting 1 mu3-O (O9), 2 μ2O (O18, O33) and 2 coordinated waters (O2W, O3W). The cluster anions form a three-dimensional extended structure through hydrogen bonds of coordinated water (figure 2).
X-ray powder diffraction (XRD)
The X-ray powder diffraction data were measured on a Mini-Flex II bench powder diffractometer, Rigaku corporation, laboratory teaching center, Fuzhou university chemical industry school.
Compound H8[Cu6(H2O)6(GeW9O34)2]·4H2The X-ray powder diffraction pattern of O (as shown in fig. 3) shows that the positions of the main absorption peaks of the two spectra coincide with each other by comparison, thus indicating that the compound is a pure phase.
Fourier transform Infrared Spectroscopy (FT-IR)
The infrared spectrogram IS measured on a Nicolet IS 10 Fourier transform infrared spectrometer of a chemical laboratory building of the Ningde institute of academic and vocational school. The conventional test experiment was carried out at room temperature (293K) using KBr pellet method, where the number of scans was 32 and the range of scans was from 500cm-1-4000cm-1。
The infrared spectrum of the compound shows that the compound is 3158cm-1、3030cm-1、1625 cm-1、1418cm-1、915cm-1、856cm-1、652cm-1There is an absorption peak (as shown in fig. 4). 3158cm-1And 3030cm-1The absorption peak appeared here is attributed to the O-H stretching vibration of water in the compound, 1625cm-1And 1418cm-1The absorption peak appeared here is ascribed to the bending vibration of H-O-H of water in the compound. And vas(W–Od)，νas(W–Ob–W)，νas(W–Oc-W) has an absorption peak position of 915cm respectively-1、856cm-1、652cm-1。
Thermogravimetric analysis (TGA)
The thermogravimetric analysis is obtained by using a NETZSCH STA 409 PC synchronous thermal analyzer of a chemical laboratory building of the university of Ningde.
Thermogravimetric analysis of the compound showed that the compound underwent a total of two weight losses (as shown in figure 5). The first stage occurs in the region of 30-200 ℃, with a 4.66% weight loss (theoretical 5.01% weight loss), corresponding to the loss of 4 free waters, 6 coordinated waters in the structure. The second stage is carried out in the temperature range of 210-800 ℃, the weight loss is 12.62 percent (the theoretical weight loss is 13.22 percent), and [ Cu ] in the corresponding structure6(H2O2)6(B-α-GeW9O33)2]8-Loss of anions and collapse of germanium tungsten oxygen cluster skeleton structure.
Antitumor Activity test
In the present application, the CCK-8 method was used to determine the inhibition of tumor cell proliferation by various compounds. And measuring the OD value at the wavelength of 450nm by using a microplate reader. The half Inhibitory Concentration (IC) of the compound on the cells was calculated using GradPad Prism 8 software based on the measured cytostatic rate50Value).
Percent cytostatic rate is 1- (OD)Experimental group-ODBlank group)/(ODNegative group-ODBlank group)*100％
Human liver cancer cell Huh7 and human colon cancer cell SW480 are selected to respectively test the inhibition effect of the compounds on the human liver cancer cell Huh7 and the human colon cancer cell SW 480. FIG. 6 shows the inhibitory effect of compounds on two types of cancer cells at different concentrations, at high concentrations,the compound has obvious inhibition effect on cell growth. Fitting the half-inhibitory concentration IC of different cells by a least square method50The results are shown in Table 2.
The results show that the compound has better inhibition effect on Huh7 cells and SW480 cells, and IC50The values were 72.96. + -. 1.54. mu.M and 93.94. + -. 1.45. mu.M, respectively. Comparative precursor K9Na2[A-α-GeW9O34]·25H2IC of O50The inhibition effect of the compound on Huh7 and SW480 is found to be stronger, which is probably caused by the introduction of copper ions, and the mechanism of the specific antitumor activity is still to be further researched.
TABLE 2 IC of compounds on intestinal cancer cells HCT116, SW48050Value ofa
aCell viability of cells treated with serial dilutions for 72h was tested using the CCK-8 method. IC (integrated circuit)50Values were calculated using GraphPad Prism 8 software.
In conclusion, the compound H which is not reported is synthesized by a volatilization method8[Cu6(H2O)6(GeW9O34)2]·4 H2O is determined to be a novel inorganic-organic hybrid zero-dimensional structure based on six-nuclear transition metal cluster substituted polyoxometalates through X-single crystal diffraction. The PXRD spectrum shows that the crystal powder of the obtained compound is pure phase. The infrared spectrum shows that the intensity of the infrared spectrum is between 500 and 1000cm-1The characteristic peak appearing in the range is 915c m-1、856cm-1、652cm-1Respectively correspond to vas(W–Od)，νas(W–Ob–W)，νas(W–Oc-W). Thermal stability analysis indicated that the compound underwent a total of two weight losses. The first stage occurs in the 50-150 ℃ region with a 4.96% weight loss (5.21% theoretical weight loss), corresponding to the loss of 4 free waters, 6 coordinated waters in the structure. The second stage occurs in the temperature range of 210-800 ℃, and the weight loss is 12.62 percent (principle)Theoretical weight loss of 13.22%), corresponding to [ Cu ] in the structure6(H2O2)6(B-α-GeW9O33)2]8-Loss of anions and collapse of germanium tungsten oxygen cluster skeleton structure. The in vitro anti-tumor activity experiment of the compound shows that the compound has an inhibition effect on Huh7 cells and SW480 cells. The structural-activity relationship analysis shows that the germanotungstate modified by copper ions has stronger anti-tumor activity than the precursor, which provides a certain theoretical basis for the research and development of anti-tumor drugs.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall fall within the protection scope of the present application.
Claims (6)
1. The copper-containing Weakley type tungsten-oxygen cluster compound is characterized in that the structural formula is H8[Cu6(H2O)6(GeW9O34)2]·4H2O; belonging to the monoclinic system, P21/n space groups having cell parameters of
α＝90.00°，β＝95.918(2)°，γ＝90.00°。
2. The copper-containing Weakley-type tungsten oxo compound of claim 1, wherein the asymmetric unit comprises a hexagon { Cu }6Keggin type sandwich anion [ Cu ] substituted by transition metal cluster6(H2O2)6(B-α-GeW9O33)2]8-And quarternary free water; its three-vacancy is [ B-alpha-GeW9O33]10-Is composed of three common vertices { W }3O13The trimetal cluster of (a) is connected to the central atom Ge through three 3-bridge oxygen atomsIVForming a cavity structure.
3. A method for preparing a copper-containing Weakley-type tungsten oxo cluster compound according to claim 1 or 2, comprising the steps of:
s1, configuring 1mmol/L La (ClO)4)3·6H2O solution, 1mmol/L dimethylamine hydrochloride solution, NH of pH 103·H2O-NH4Cl buffer, 0.2mmol/L Cu (NO)3)2A solution;
s2, weighing Na2WO4·2H2O、GeO2Adding prepared La (ClO)4)3·6H2O solution, dimethylamine hydrochloride solution, NH3·H2O-NH4Cl buffer, Cu (NO)3)2The solution is evenly mixed and kept stand for 3.5 to 4.5 days at normal temperature, and green blocky crystals are separated out.
4. The method of claim 3, wherein in step S2, the Na2WO4·2H2O、GeO2、La(ClO4)3·6H2O solution, dimethylamine hydrochloride solution, NH3·H2O-NH4Cl buffer, Cu (NO)3)2The ratio of the solution is 0.3-0.4 g: 0.1-0.2 g: 0.15-0.25 ml: 4.5-5.5 ml: 4.5-5.5 ml: 0.10-0.20 ml.
5. The method of claim 3, wherein the step S2 further comprises adjusting the pH to 7.1-7.3 with acetic acid.
6. Use of the copper-containing Weakley type tungsten oxo group compound according to claim 1 or 2 for the preparation of an anti-tumor medicament.
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| CN109338471A (en) * | 2018-11-28 | 2019-02-15 | 同济大学 | A kind of mid-infrared light frequency-doubling crystal fluoro tungsten Potassiumiodate material and preparation and application |
| CN111672539A (en) * | 2020-06-15 | 2020-09-18 | 周口师范学院 | Six-core nickel substituted tungsten oxygen cluster hydrogenation catalytic desulfurization catalyst and preparation method and use method thereof |
| CN112934262A (en) * | 2021-02-01 | 2021-06-11 | 北京理工大学 | Nickel-substituted tungsten-oxygen cluster organic framework material and preparation method and application thereof |
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| WO1999021569A1 (en) * | 1997-10-24 | 1999-05-06 | Starpharma Limited | Polyoxometallate antifiloviral composition |
| CN103962184A (en) * | 2014-04-16 | 2014-08-06 | 西北大学 | Preparation method of Cu, Fe-doped vacancy Keggin type silicon tungsten polyoxometallate catalyst |
| CN109338471A (en) * | 2018-11-28 | 2019-02-15 | 同济大学 | A kind of mid-infrared light frequency-doubling crystal fluoro tungsten Potassiumiodate material and preparation and application |
| CN111672539A (en) * | 2020-06-15 | 2020-09-18 | 周口师范学院 | Six-core nickel substituted tungsten oxygen cluster hydrogenation catalytic desulfurization catalyst and preparation method and use method thereof |
| CN112934262A (en) * | 2021-02-01 | 2021-06-11 | 北京理工大学 | Nickel-substituted tungsten-oxygen cluster organic framework material and preparation method and application thereof |
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