阅读说明：本技术 一种含铁的金属-有机配位聚合物及制备方法与应用 (Iron-containing metal-organic coordination polymer, preparation method and application ) 是由 孟江平 唐洁 于 2019-11-04 设计创作，主要内容包括：一种含铁的金属-有机配位聚合物,其特征在于：其为三维(3D)结构,分子式为C<Sub>50</Sub>H<Sub>35</Sub>FeN<Sub>6</Sub>O<Sub>4</Sub>,其中配体为1,1’:2’,1”-三联苯-4,4”-二羧酸(<I>H</I><Sub><I>2</I></Sub><I>tpdca</I>)和1,4-二苯并咪唑基苯(<I>bbib</I>),本发明提出的所述含铁的金属-有机配位聚合物C<Sub>50</Sub>H<Sub>35</Sub>FeN<Sub>6</Sub>O<Sub>4</Sub>合成简单,产率为84%,120-400℃稳定存在,稳定性强,对乳腺癌MDA-MB-453有显著的抗癌活性,对乳腺癌MDA-MB-453的IC<Sub>50</Sub>为1.4mM,作为抗乳腺癌药物具有可进一步开发应用的前景。(An iron-containing metal-organic coordination polymer characterized by: it is of three-dimensional (3D) structure with molecular formula of C 50 H 35 FeN 6 O 4 Wherein the ligand is 1,1 ', 2', 1 '-terphenyl-4, 4' -dicarboxylic acid(s) ((II)) H 2 tpdca ) And 1, 4-dibenzoimidazolylbenzene (b) bbib ) The iron-containing metal-organic coordination polymer C provided by the invention 50 H 35 FeN 6 O 4 Simple synthesis, 84% yield, stable existence at the temperature of 120-400 ℃, strong stability, obvious anticancer activity to breast cancer MDA-MB-453 and IC of breast cancer MDA-MB-453 50 Is 1.4mM, and has the prospect of further development and application as an anti-breast cancer medicament.)

1. An iron-containing metal-organic coordination polymer characterized by: it is of three-dimensional (3D) structure with molecular formula of C₅₀H₃₅FeN₆O₄Wherein the ligand is 1,1 ', 2', 1 '-terphenyl-4, 4' -dicarboxylic acid (H)₂tpdca) and 1, 4-dibenzoimidazolylbenzene (bbib), the iron-containing metal-coordination polymer having asymmetric units of:

the asymmetric unit comprises 4 Fe (III) ions and 1 tpdca^2-And 0.5 bbib from each of the 3 bbibs; the crystallographically independent Fe1 appeared to be in a penta-coordinate mode with Fe1 from four tpdca^2-Coordinated to 1 nitrogen atom from 1 bbib ligand, to form a twisted triangular bipyramid structure.

2. An iron-containing metal-organic coordination polymer according to claim 1, wherein: the iron-containing metal-organic coordination polymer belongs to a triclinic system, the space group is P ī, and the unit cell parameters are as follows:

3. an iron-containing metal-organic coordination polymer according to claim 1 or 2, wherein: unit cell volume of the iron-containing metal-organic coordination polymer

4. The method of claim 1, wherein the metal-organic coordination polymer comprising iron is prepared by: specifically, Fe is added separately₂(SO₄)₃、H₂the tpdca, the bbib and the DMF are sequentially added into a lining of a 15mL polytetrafluoroethylene high-pressure reaction kettle, and the high-pressure reaction kettle is screwed downAnd (3) putting the reaction kettle into the ultrasonic wave, carrying out ultrasonic treatment for 10 minutes, transferring the reaction kettle into a microwave reactor, heating to 150 ℃, reacting for about 30-40 minutes, naturally cooling to room temperature, standing for 2 days, filtering, washing with 95% ethanol to obtain light green blocky crystals, collecting the crystals, washing with absolute ethanol, and drying to obtain the target substance.

5. The method of claim 4, wherein the metal-organic coordination polymer comprising iron is prepared by: said Fe₂(SO₄)₃、H₂the mole ratio of tpdca to bbib is Fe₂(SO₄)₃：H₂tpdca：bbib＝1:3:2。

6. Use of the iron-containing metal-organic coordination polymer of any one of claims 1 to 3 for preparing a medicament for treating breast cancer MDA-MB-453, wherein IC is the IC₅₀At 1.4. mu.M.

Technical Field

The invention belongs to the technical field of metal-organic coordination polymers, and particularly relates to an iron-containing metal-organic coordination polymer with anti-breast cancer activity, and a preparation method and application thereof.

Background

Metal-organic coordination polymers (coordination polymers) have high specific surface area, adjustable pore size, and are widely used in the fields of gas adsorption, gas storage, catalysis, photoelectric devices, biomedical imaging, active molecule and drug molecule delivery, etc.

Tumors, particularly malignant tumors, are one of the common diseases that have serious threats to human health in recent years. According to incomplete statistics, the incidence rate of breast cancer in the world is on the rising trend from the end of the 70 th 20 th century, and breast cancer becomes a major problem seriously threatening human health in the current society. Therefore, the design and construction of the metal-organic coordination polymer which has novel structure and anti-tumor activity, particularly anti-breast cancer activity, have important practical significance.

Based on the reasons, the inventor prepares an iron-containing metal-organic coordination polymer, which has remarkable in vitro anti-breast cancer activity and IC (integrated Circuit) of breast cancer MDA-MB-453₅₀1.4 mu M, can be further developed as an anti-breast cancer drug.

Disclosure of Invention

The first object of the present invention is to provide an iron-containing metal-organic coordination polymer having high stability.

The second object of the present invention is to provide a method for preparing the above iron-containing metal-organic coordination polymer.

The third object of the present invention is to provide the use of the above iron-containing metal-organic coordination polymer.

The purpose of the invention is realized by the following technical scheme:

an iron-containing metal-organic coordination polymer characterized by: it is of three-dimensional (3D) structure with molecular formula of C₅₀H₃₅FeN₆O₄Wherein the ligand is 1,1 ', 2', 1 '-terphenyl-4, 4' -dicarboxylic acid (H)₂tpdca) and 1, 4-dibenzoimidazolylbenzene (bbib), the iron-containing metal-coordination polymer having asymmetric units of:

the asymmetric unit comprises 4 Fe (III) ions and 1 tpdca^2-And 0.5 bbib from each of the 3 bbibs, crystallographically independent Fe1 behaves in a penta-coordination mode, with each of the four tpdca^2-Coordinated to 1 nitrogen atom from 1 bbib ligand, to form a twisted triangular bipyramid structure.

Further, the Fe-O bond length in the above asymmetric unit is

Fe-N bond length of

The key angle formed around Fe1 ranges from 86.82(11) ° to 163.12(13) °.

Further, the iron-containing metal-organic coordination polymer belongs to a triclinic system, the space group is P ī, and the unit cell parameters are as follows:

α＝76.865(10)°，β＝77.473(12)°，γ＝86.899(10)°。

further, the unit cell volume of the above iron-containing metal-organic coordination polymer

The number of molecules in the unit cell is Z ═ 2.

The preparation method of the iron-containing metal-organic coordination polymer is characterized by comprising the following steps:

respectively adding Fe₂(SO₄)₃、H₂Sequentially adding tpdca, bbib and DMF (dimethyl formamide) into a lining of a 15mL polytetrafluoroethylene high-pressure reaction kettle, screwing the high-pressure reaction kettle, moving the reaction kettle to ultrasonic waves for 10 minutes, transferring the reaction kettle to a microwave reactor, heating to 150 ℃, reacting for 30-40 minutes, naturally cooling to room temperature, standing for 2 days, filtering, washing with 95% ethanol to obtain light green blocky crystals, collecting the crystals, washing with absolute ethanol, and drying to obtain the target product.

Further, said Fe₂(SO₄)₃、H₂tpdca, bbib used in a molar ratio of Fe₂(SO₄)₃：H₂tpdca：bbib＝1:3:2。

Further, said H₂the molar volume ratio of tpdca to DMF was 1:106 mol/L.

If the control is not proper in the preparation process, the structure formed by the ligand and the metal ions is changed, the structure of the iron-containing metal-organic coordination polymer of the invention cannot be obtained, and even the combination of the metal and the ligand is inhibited. The invention selects specific raw materials, solvents and specific component proportions, and combines microwave heating to successfully prepare the iron-containing metal-organic coordination polymer.

The iron-containing metal-organic coordination polymer has remarkable anti-breast cancer activity, is applied to inhibiting breast cancer MDA-MB-453, and has IC (integrated circuit) effect on breast cancer MDA-MB-453₅₀At 1.4. mu.M.

The invention has the following beneficial effects:

the invention provides an iron-containing metal-organic coordination polymer C₅₀H₃₅FeN₆O₄Simple synthesis, 84 percent of yield, strong stability, stable existence at the temperature of 120 ℃ and 400 ℃, obvious anticancer activity to breast cancer MDA-MB-453 and IC to breast cancer MDA-MB-453₅₀Is 1.4 mu M, and has the prospect of further development and application as an anti-breast cancer medicament.

Drawings

FIG. 1: the invention provides an asymmetric unit of an iron-containing metal-organic coordination polymer.

FIG. 2: the invention provides a stacking diagram of a metal-organic coordination polymer containing iron.

FIG. 3: the invention provides a pore structure diagram of an iron-containing metal-organic coordination polymer.

FIG. 4: the invention provides a three-dimensional (3D) structure diagram (scale model) of a metal-organic coordination polymer containing iron.

FIG. 5: the X-powder diffraction pattern of the iron-containing metal-organic coordination polymer provided by the invention.

FIG. 6: the thermogravimetric graph of the iron-containing metal-organic coordination polymer provided by the invention is shown.

Detailed Description

The present invention is further described in detail by the following examples in conjunction with the accompanying drawings, it is to be noted that the following detailed description is provided for the purpose of further illustration only, and is not to be construed as limiting the scope of the present invention, and that certain insubstantial modifications and adaptations of the invention may be made by those skilled in the art based on the foregoing disclosure.