Chiral bismuth molybdate nanomaterial and its preparation method and application

Abstract

The present invention relates to a chiral bismuth molybdate nanomaterial and its preparation method and application, belonging to the field of nanomaterial synthesis technology. The present invention utilizes a variety of chiral amino acids as chiral inducers, synthesizes bismuth molybdate in a single step under hydrothermal reaction conditions, and interacts with chiral ligands to form chiral units. By regulating the type and proportion of solvents, temperature, time, and type of chiral ligands, chiral bismuth molybdates of various morphologies can be obtained. The chiral bismuth molybdates of different morphologies synthesized by the present invention have good chiral optical activity in the visible light region, have high biosafety, can be used in photocatalysis, sterilization and photodynamic therapy for cancer, and have broad application prospects in the field of gastric cancer treatment.

Description

Technical Field

[0001] The present invention relates to the technical field of nanomaterial synthesis, in particular to a chiral bismuth molybdate nanomaterial and a preparation method and application thereof. Background Art

[0002] Chirality is ubiquitous in biological systems. The basic substances that make up living organisms, such as amino acids and nucleotides, are molecules with a single chirality. The 20 amino acids that make up proteins are all L-configured, and the ribose in RNA that makes up the genes of living organisms is all D-configured, resulting in a special chiral environment in the body. This is of great significance to the development of chiral materials in the biomedical field.

[0003] Bismuth molybdate (bismuth molybdate) is a novel semiconductor material with high photoelectric energy storage capacity and photoelectric sensing properties. Therefore, it is currently being widely researched for applications in the optoelectronics field. Bismuth molybdate is composed of bismuth, molybdenum, and oxygen. Bismuth has an auxiliary effect in treating skin lesions and gastrointestinal diseases, while molybdenum has some effect in reducing the production of carcinogenic nitrosamines and treating cardiovascular disease. However, there are few reports on the biomedical applications of bismuth molybdate. Research on the biological applications of chiral bismuth molybdate remains underdeveloped, so its application in biomedical fields such as the treatment of gastric diseases, skin lesions, and cancer holds great promise.

[0004] The use of chiral ligands to induce the generation of bismuth molybdate materials with circular dichroism absorption signals in the visible and near-infrared regions has not been reported. Summary of the Invention

[0005] To address the above technical issues, the present invention provides a chiral bismuth molybdate nanomaterial, its preparation method, and application. Molybdenum salts and bismuth salts are used as molybdenum and bismuth sources, respectively, and various chiral amino acids are used as chiral inducers. Chiral units are formed through the interaction between chiral ligands and bismuth molybdate nanoparticles. By regulating the type and ratio of solvents, the chiral units are induced to form chiral bismuth molybdate nanoparticles through intermolecular interactions. By adjusting the type of chiral ligand, the ratio of molybdenum and bismuth sources, and the kinetic and thermodynamic parameters of the reaction, chiral bismuth molybdates with various morphologies are obtained, while also exhibiting circular dichroism absorption signals in the visible and near-infrared regions. These materials have been used in the treatment of gastric cancer, demonstrating excellent inhibitory and therapeutic effects.

[0006] The first object of the present invention is to provide a method for preparing a chiral bismuth molybdate nanomaterial, which is characterized by comprising the following steps: using a chiral ligand as a chiral inducer, and synthesizing a bismuth source and a molybdenum source under hydrothermal reaction conditions to obtain the chiral bismuth molybdate nanomaterial.

[0007] In any embodiment of the present invention, the chiral amino acid is selected from one or more of cysteine, tartaric acid, penicillamine and proline.

[0008] In any embodiment of the present invention, the cysteine, tartaric acid, penicillamine and proline are all L-form and / or D-form.

[0009] In any embodiment of the present invention, the bismuth source is selected from one or more of bismuth nitrate, bismuth oxide, bismuth chloride and bismuth sulfide.

[0010] In any embodiment of the present invention, the molybdenum source is selected from one or more of ammonium molybdate, sodium molybdate and molybdenum trioxide.

[0011] In any embodiment of the present invention, the temperature of the hydrothermal reaction is 90-150° C., and the reaction time is 2 h-12 h.

[0012] In any embodiment of the present invention, the molar ratio of the molybdenum source to the bismuth source is 1:0.5-3.

[0013] In any embodiment of the present invention, the molar ratio of the chiral ligand to the molybdenum source is 1:0.5-2.

[0014] In any embodiment of the present invention, the preparation method is as follows:

[0015] S1: dissolving a bismuth source in a solvent, then sequentially adding a molybdenum source and an aqueous solution of a chiral ligand, mixing them evenly, and heating at a high temperature to obtain a reaction solution containing chiral bismuth molybdate nanoparticles;

[0016] S2: performing solid-liquid separation on the reaction solution, washing, and drying to obtain the chiral bismuth molybdate nanomaterial.

[0017] In any embodiment of the present invention, the solvent is one or more of water, ethanol, ethylene glycol, methanol and isopropanol.

[0018] In any embodiment of the present invention, the solid-liquid separation adopts centrifugal separation method, and the conditions of the centrifugal separation method are: rotation speed 4000rpm-10000rpm, time 5min-10min, and number of times 1-3 times.

[0019] The second object of the present invention is to provide a chiral bismuth molybdate nanomaterial obtained by the preparation method; the chiral bismuth molybdate nanomaterial is a nanoscale twisted spiral structure; the characteristic peaks of the circular dichroism spectral signal of the chiral bismuth molybdate nanomaterial are 300-400nm and 800-1000nm.

[0020] In any embodiment of the present invention, the chiral bismuth molybdate nanomaterial is an L-chiral bismuth molybdate nanomaterial or a D-chiral bismuth molybdate nanomaterial.

[0021] The third purpose of the present invention is to use the chiral bismuth molybdate nanomaterial in the preparation of gastric cancer drugs.

[0022] The above technical solution of the present invention has the following advantages over the prior art:

[0023] (1) The chiral bismuth molybdate nanomaterial described in the present invention has excellent optical activity and strong CD activity in the visible light region. By utilizing CD in the visible light region, it can be used for the identification and detection of polarized light.

[0024] (2) The chiral bismuth molybdate nanomaterial described in the invention has excellent biocompatibility and can be used in fields such as bioengineering and the treatment of diseases such as gastric cancer.

[0025] In order to make the content of the present invention more clearly understood, the following is combined with specific embodiments of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to make the content of the present invention more clearly understood, the present invention is further described in detail below based on specific embodiments of the present invention in conjunction with the accompanying drawings, wherein

[0027] Figure 1 These are the CD and UV spectra of the chiral bismuth molybdate nanomaterial obtained in Example 1 of the present invention.

[0028] Figure 2 These are the CD and UV spectra of the chiral bismuth molybdate nanomaterial obtained in Example 2 of the present invention.

[0029] Figure 3 This is an SEM image of the chiral bismuth molybdate nanomaterial obtained in Example 1 of the present invention.

[0030] Figure 4 This is an SEM image of the chiral bismuth molybdate nanomaterial obtained in Example 2 of the present invention.

[0031] Figure 5 This is a TEM image of the chiral bismuth molybdate nanomaterial obtained in Example 1 of the present invention.

[0032] Figure 6 This is a TEM-Mapping image of the chiral bismuth molybdate nanomaterial obtained in Example 1 of the present invention.

[0033] Figure 7 This is the fluorescence imaging result of the chiral bismuth molybdate nanomaterial obtained in Example 1 of the present invention used to treat gastric cancer tumor sites in mice. DETAILED DESCRIPTION

[0034] The present invention will be further described below with reference to the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it. However, the embodiments are not intended to limit the present invention.

[0035] Example 1

[0036] This embodiment provides a method for preparing chiral bismuth molybdate nanoparticles, which is as follows:

[0037] Add 1 mL of (NH4)2MoO4 (0.3 M) to 2 mL of ethylene glycol, stir continuously at 600 rpm and dissolve, then add 1 mL of Bi(NO3)3 (0.2 M) and stir evenly, then add 1 mL of L- / D-Cys (0.2 M) and stir evenly, finally add 6 mL of high-purity water and stir evenly, then heat in an autoclave at 90 ° C for 8 h, and wash with water three times at 6000 rpm / 10 min to obtain L- / D-chiral bismuth molybdate nanoparticles.

[0038] Example 2

[0039] This embodiment provides a method for preparing chiral bismuth molybdate nanoparticles, which is as follows: 1 mL of (NH4)2MoO4 (0.3 M) is added to 2 mL of ethanol, stirred continuously at 600 rpm and dissolved, then 1 mL of Bi(NO3)3 (0.2 M) is added and stirred evenly, then 1 mL of L- / D-Cys (0.2 M) is added and stirred evenly, and finally 6 mL of high-purity water is added and stirred evenly, and then the mixture is autoclaved at 115°C for 8 h and washed with water three times at 6000 rpm / 10 min to obtain L- / D-chiral bismuth molybdate nanoparticles.

[0040] Test Example 1

[0041] The chiral bismuth molybdate nanoparticles prepared in Example 1-2 were tested using a circular dichroism instrument. First, 1 mL of the stock solution was taken, 6000 rpm, 10 min, the supernatant was removed, and dispersed in 1 mL of high-purity water. This was repeated twice, and then the test was performed. The range was 300-1700 nm, the temperature was 25 ° C; the scanning speed was 200 nm / min; the data spacing was 0.5 nm; the bandwidth was 5 nm (visible light bandwidth: 10 nm); the digital integration time was 2 s, and the results corresponded to Figure 1 and Figure 2 As can be seen from the data in the figure, the characteristic peak of the CD signal mainly appears in 700-1000nm, which is conducive to the utilization of circularly polarized light.

[0042] Test Example 2

[0043] The chiral bismuth molybdate nanoparticles prepared in Example 1-2 were examined by scanning electron microscopy (SEM). First, 0.1 mL of the stock solution was taken, 6000 rpm, 10 min, the supernatant was removed, and the solution was dispersed in 1 mL of high-purity water. This was repeated twice. The cut silicon wafer was cleaned and dried with nitrogen. Then 5 μL of the centrifuged sample was dropped onto the silicon wafer and allowed to dry naturally at room temperature. The scanning electron microscope image was taken using a Hitachi SU9000 with an accelerating voltage of 100 kV. The results are as follows: Figure 3-4 shown.

[0044] Test Example 3

[0045] The chiral bismuth molybdate nanoparticles prepared in Example 1-2 were subjected to transmission electron microscopy (TEM) detection. First, 0.1 mL of the stock solution was taken, 6000 rpm, 10 min, the supernatant was removed, and dispersed in 1 mL of high-purity water. This was repeated twice. Then 5 μL of the centrifuged sample was dropped onto a copper grid and naturally dried at room temperature. The transmission electron microscopy image was taken using F2100 with an accelerating voltage of 200 kV. The results are as follows: Figure 5 As shown, then Mapping is performed to collect element signals, and the result is as follows Figure 6 As shown, it can be seen that Mo, Bi, O, and S elements are evenly distributed on its surface.

[0046] Test Example 3

[0047] Chiral bismuth molybdate nanoparticles prepared in Example 1 were used to treat gastric cancer model mice. Seven days after the gastric cancer model was constructed, fluorescence imaging was performed for the first time to confirm whether the model was successful. After the model was confirmed to be successful, chiral bismuth molybdate nanoparticles were injected intraperitoneally into the gastric cancer model mice, and a blank control group was injected intraperitoneally with PBS. Fluorescence imaging was performed every 14 days for the experimental and control groups. Figure 7 The gastric cancer mouse models were successfully established on day 7 in both groups. However, on day 21, two mice in the control group had significantly enlarged tumors, and one of them died. All three mice in the control group died on day 35. However, the tumors in mice injected intraperitoneally with chiral bismuth molybdate nanoparticles showed no signs of worsening, and the mice remained in good condition. This suggests that chiral bismuth molybdate nanoparticles have a beneficial effect on inhibiting and treating gastric cancer.

[0048] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A method for preparing a chiral bismuth molybdate nanomaterial, characterized in that: The following steps are involved: The chiral bismuth molybdate nanomaterial is synthesized by using a chiral ligand as a chiral inducer, a bismuth source and a molybdenum source under hydrothermal reaction conditions; the chiral bismuth molybdate nanomaterial has a nanoscale twisted helical structure; and the characteristic peaks of the circular dichroism spectral signal of the chiral bismuth molybdate nanomaterial are 300-400 nm and 800-1000 nm. The chiral ligand is selected from one or more of cysteine, tartaric acid, penicillamine and proline; The temperature of the hydrothermal reaction is 90-150°C, and the reaction time is 2 h-12 h; The molar ratio of the molybdenum source to the bismuth source is 1:0.5-3; the molar ratio of the chiral ligand to the molybdenum source is 1:0.5-2.

2. The preparation method according to claim 1, characterized in that The cysteine, tartaric acid, penicillamine and proline are all L-type and / or D-type.

3. The preparation method according to claim 1, characterized in that The bismuth source is selected from one or more of bismuth nitrate, bismuth oxide, bismuth chloride and bismuth sulfide.

4. The preparation method according to claim 1, characterized in that The molybdenum source is selected from one or more of ammonium molybdate, sodium molybdate and molybdenum trioxide.

5. The chiral bismuth molybdate nanomaterial obtained by the preparation method according to any one of claims 1 to 4, wherein the chiral bismuth molybdate nanomaterial has a nanoscale twisted spiral structure; and the characteristic peaks of the circular dichroism spectral signal of the chiral bismuth molybdate nanomaterial are 300-400 nm and 800-1000 nm.

6. Use of the chiral bismuth molybdate nanomaterial as claimed in claim 5 in the preparation of gastric cancer drugs.

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