Preparation method of chiral nano mercuric sulfide

Abstract

The invention belongs to the technical field of nano material preparation, and provides a preparation method of chiral nano mercuric sulfide. The preparation method comprises the following steps: mixing water-soluble mercury salt, chiral penicillamine, inorganic base and water to obtain a precursor solution; mixing the chiral mercuric sulfide seed dispersion liquid, chiral penicillamine and inorganic base to obtain a seed solution; and sequentially adding the precursor solution and thioacetamide into the seed solution, carrying out a reaction, and after the reaction, adding isopropanol to obtain the chiral nano mercuric sulfide, the chiral mercuric sulfide seed dispersion liquid is prepared from water-soluble mercury salt, chiral penicillamine, inorganic base and thioacetamide through a self-assembly reaction. According to the preparation method disclosed by the invention, the precursor solution containing the water-soluble mercury salt and the chiral penicillamine, the chiral mercury sulfide seed dispersion liquid, the chiral penicillamine and the inorganic base are combined, so that the chiral nanometer mercury sulfide with chirality and good dispersity is obtained; meanwhile, the obtained chiral nanometer mercuric sulfide is in a ray shape.

Description

Technical Field

[0001] The invention relates to the technical field of nano material preparation, and in particular to chiral nano mercuric sulfide and a preparation method and application thereof. Background Art

[0002] Mercury sulfide, as an inorganic compound, is a twinned crystal. It is commonly found in the form of cinnabar (α-HgS) in nature. Mercury sulfide itself has the effects of calming the nerves, clearing away heat and detoxifying, and improving dizziness. Its combination with chiral morphology may make the material have better application performance. The relevant prior art discloses a preparation of chiral mercury sulfide, which uses a mercury salt aqueous solution and a sulfide aqueous solution as reaction raw materials, sulfur-containing amino acids as chiral inducers, and stirs the reaction in a water bath at 20 to 50°C to finally obtain a chiral metal compound nanomaterial mercury sulfide with optical isomerism and uniform size. However, the chiral metal compound nanomaterial sulfide is severely agglomerated. Summary of the invention

[0003] In view of this, the purpose of the present invention is to provide a chiral nano-mercury sulfide and a preparation method and application thereof. The chiral nano-mercury sulfide provided by the present invention has good dispersibility.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a method for preparing chiral nano-mercury sulfide, comprising the following steps:

[0006] mixing a water-soluble mercuric salt, chiral penicillamine, an inorganic base and water to obtain a precursor solution;

[0007] mixing a chiral mercuric sulfide seed dispersion, chiral penicillamine and an inorganic base to obtain a seed solution;

[0008] Adding a precursor solution and thioacetamide to the seed solution in sequence to react, and after the reaction, adding isopropanol to obtain the chiral nano-mercuric sulfide;

[0009] The preparation method of the chiral mercuric sulfide seed dispersion comprises the following steps:

[0010] Mixing a water-soluble mercuric salt, chiral penicillamine, an inorganic base and thioacetamide, and subjecting the obtained reaction raw material liquid to a self-assembly reaction to obtain the chiral mercuric sulfide seed dispersion;

[0011] The concentration of the chiral mercuric sulfide seed dispersion is 0.5-5 mg / mL.

[0012] Preferably, the water-soluble mercuric salt comprises mercuric nitrate, the inorganic base comprises sodium hydroxide, and the chiral penicillamine is L-penicillamine or D-penicillamine.

[0013] Preferably, in the precursor solution, the concentration of the water-soluble mercury salt is 20-25 mmol / L, the concentration of the chiral penicillamine is 18-22 mmol / L, and the concentration of the inorganic base is 0.05-0.1 mol / L.

[0014] Preferably, in the reaction raw material liquid, the concentration of water-soluble mercury salt is 35-40 mmol / L, the concentration of penicillamine is 10-15 mmol / L, the concentration of inorganic base is 0.01-0.05 mol / L, and the concentration of thioacetamide is 10-15 mmol / L.

[0015] Preferably, the temperature of the self-assembly reaction is 35-40° C., the time is 2-4 hours, and the self-assembly reaction is carried out in a water bath; after the self-assembly reaction, the method further comprises: solid-liquid separation of the obtained self-assembly reaction liquid to obtain an orange-red precipitate; after washing the orange-red precipitate with water, dispersing it in ultrapure water to obtain the chiral mercuric sulfide seed dispersion.

[0016] Preferably, in the seed solution, the concentration of chiral mercuric sulfide is 0.5-4.5 mg / mL, the concentration of chiral penicillamine is 20-25 mmol / L, and the concentration of inorganic base is 0.1-0.2 mmol / L.

[0017] Preferably, in the reaction step, thioacetamide is used in the form of a thioacetamide solution, the concentration of the thioacetamide solution is 0.5-1.5 mol / L, and the volume ratio of the seed solution, the precursor solution and the thioacetamide solution is 3.8:1-4:0.2-1.5.

[0018] Preferably, the reaction is carried out under light-proof conditions, and the reaction time is 3 to 5 hours;

[0019] The volume ratio of the isopropanol to the reaction liquid obtained by the reaction is 5-10:1-2.

[0020] The present invention also provides chiral nano-mercury sulfide prepared by the preparation method described in the above technical solution, wherein the chiral nano-mercury sulfide is in the shape of a ray.

[0021] The present invention also provides the use of the chiral nano-mercury sulfide described in the above technical solution in the preparation of medicines.

[0022] The invention provides a method for preparing chiral nano-mercury sulfide.

[0023] The preparation method of the present invention uses a precursor solution containing a water-soluble mercuric salt, chiral penicillamine and an inorganic base and a chiral mercuric sulfide seed dispersion (prepared by a self-assembly reaction of a water-soluble mercuric salt, chiral penicillamine, an inorganic base and thioacetamide) to obtain chiral nano mercuric sulfide with good dispersibility and a ray-like morphology. When the chiral nano mercuric sulfide is used in drug preparation, the medicinal effect of mercuric sulfide can be better exerted. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a high-resolution transmission electron microscopy image of right-handed nano-mercury sulfide in the right-handed nano-mercury sulfide dispersion obtained in Example 1;

[0025] Figure 2 This is a high-resolution transmission electron microscopy image of left-handed nano-mercury sulfide in the left-handed nano-mercury sulfide dispersion obtained in Example 2;

[0026] Figure 3 The length distribution diagram of the right-handed nano-mercury sulfide obtained in Example 1 and the left-handed nano-mercury sulfide obtained in Example 2;

[0027] Figure 4 The width distribution diagram of the right-handed nano-mercury sulfide obtained in Example 1 and the left-handed nano-mercury sulfide obtained in Example 2;

[0028] Figure 5 Circular dichroism spectra of right-handed nano-mercury sulfide obtained in Example 1 and left-handed nano-mercury sulfide obtained in Example 2;

[0029] Figure 6 BV after exposure to 80ppm right-handed nano-mercury sulfide for 24 hours 2 Cell morphology;

[0030] Figure 7 BV after exposure to 80ppm L-HgS nanomaterials for 24h 2 Cell morphology. DETAILED DESCRIPTION

[0031] The present invention provides a method for preparing chiral nano-mercury sulfide, comprising the following steps:

[0032] mixing a water-soluble mercuric salt, chiral penicillamine, an inorganic base and water to obtain a precursor solution;

[0033] mixing a chiral mercuric sulfide seed dispersion, chiral penicillamine and an inorganic base to obtain a seed solution;

[0034] Adding a precursor solution and thioacetamide to the seed solution in sequence to react, and after the reaction, adding isopropanol to obtain the chiral nano-mercuric sulfide;

[0035] The preparation method of the chiral mercuric sulfide seed dispersion comprises the following steps:

[0036] Mixing a water-soluble mercuric salt, chiral penicillamine, an inorganic base and thioacetamide, and subjecting the obtained reaction raw material liquid to a self-assembly reaction to obtain the chiral mercuric sulfide seed dispersion;

[0037] The concentration of the chiral mercuric sulfide seed dispersion is 1-5 mg / mL.

[0038] Unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.

[0039] The invention mixes water-soluble mercuric salt, chiral penicillamine, inorganic base and water to obtain a precursor solution.

[0040] In the present invention, in the process of preparing the precursor solution, the water-soluble mercuric salt preferably includes mercuric nitrate. In the present invention, the inorganic base preferably includes sodium hydroxide (NaOH). In the present invention, the chiral penicillamine is preferably L-penicillamine or D-penicillamine.

[0041] In the present invention, in the process of preparing the precursor solution, the water-soluble mercuric salt is preferably used in the form of a water-soluble mercuric salt solution, and the concentration of the water-soluble mercuric salt solution is preferably 20 to 40 mmol / L, specifically preferably 20 mmol / L, 25 mmol / L, 30 mmol / L, 35 mmol / L or 40 mmol / L. In the present invention, the solvent of the water-soluble mercuric salt solution is preferably water, and more preferably ultrapure water. In the present invention, the preparation method of the water-soluble mercuric salt solution preferably includes the following steps: dispersing the water-soluble mercuric salt in water, and ultrasonicating to obtain the water-soluble mercuric salt solution.

[0042] In the present invention, in the process of preparing the precursor solution, the chiral penicillamine is preferably used in the form of a chiral penicillamine solution, and the concentration of the chiral penicillamine solution is preferably 80 to 100 mmol / L, and specifically preferably 80 mmol / L, 85 mmol / L, 90 mmol / L, 95 mmol / L or 100 mmol / L. In the present invention, the solvent of the chiral penicillamine solution is preferably water, and more preferably ultrapure water. In the present invention, the method for preparing the chiral penicillamine solution preferably comprises the following steps: dispersing the chiral penicillamine in water, and performing ultrasound to obtain the chiral penicillamine solution.

[0043] In the present invention, in the process of preparing the precursor solution, the inorganic base is preferably used in the form of an inorganic base solution, and the concentration of the inorganic base solution is preferably 1 to 3 mol / L, specifically preferably 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L or 3 mol / L. In the present invention, the method for preparing the inorganic base solution preferably comprises the following steps: dispersing the inorganic base in water, and performing ultrasound to obtain the inorganic base solution.

[0044] In the present invention, in the process of preparing the precursor solution, the volume ratio of the water-soluble mercury salt solution, the chiral penicillamine solution and the inorganic base solution is preferably 6:1.8:0.3.

[0045] In a specific embodiment of the present invention, the mixing of water-soluble mercuric salt, chiral penicillamine, inorganic base and water preferably comprises: placing chiral penicillamine solution in a glass bottle, and sequentially adding water-soluble mercuric salt solution and inorganic base solution; after the water-soluble mercuric salt solution is added, preferably a first horizontal oscillation is performed, and the first horizontal oscillation time is preferably 3 minutes. In the present invention, after the inorganic base solution is added, preferably a second horizontal oscillation is performed, and the second horizontal oscillation time is preferably 1 minute.

[0046] In the present invention, in the precursor solution, the concentration of water-soluble mercury salt is preferably 20-25mmol / L, specifically preferably 20mmol / L, 21mmol / L, 22mmol / L, 22.22mmol / L, 23mmol / L, 24mmol / L or 25mmol / L; the concentration of chiral penicillamine is preferably 18-22mmol / L, specifically preferably 18mmol / L, 19mmol / L, 20mmol / L, 21mmol / L or 22mmol / L; the concentration of inorganic base is preferably 0.05-0.1mol / L, specifically preferably 0.05mmol / L, 0.06mmol / L, 0.07mmol / L, 0.074mmol / L, 0.08mmol / L, 0.09mmol / L or 0.1mmol / L.

[0047] The invention mixes chiral mercuric sulfide seed dispersion, chiral penicillamine and inorganic base to obtain a seed solution.

[0048] In the present invention, the concentration of the chiral mercuric sulfide seed dispersion is preferably 0.5 to 5 mg / mL, and specifically preferably 0.5 mg / mL, 0.855 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 2.7 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL or 5 mg / mL. In the present invention, the preparation method of the chiral mercuric sulfide seed dispersion comprises the following steps: mixing a water-soluble mercuric salt, chiral penicillamine, an inorganic base and thioacetamide, and subjecting the obtained reaction raw material liquid to a self-assembly reaction to obtain the chiral mercuric sulfide seed dispersion. In the present invention, in the process of preparing the chiral mercuric sulfide seed dispersion, the types of the water-soluble mercuric salt, chiral penicillamine and inorganic base are preferably consistent with the technical scheme in preparing the precursor solution, and will not be repeated here. In the present invention, in the process of preparing the chiral mercuric sulfide seed dispersion, the water-soluble mercuric salt is preferably used in the form of a water-soluble mercuric salt solution, and the concentration of the water-soluble mercuric salt solution is preferably 40-60 mmol / L, and specifically preferably 40 mmol / L, 50 mmol / L or 60 mmol / L. In the present invention, in the process of preparing the chiral mercuric sulfide seed dispersion, the chiral penicillamine is preferably used in the form of a chiral penicillamine solution, and the concentration of the chiral penicillamine solution is preferably 80-100 mmol / L, and specifically preferably 80 mmol / L, 90 mmol / L or 100 mmol / L. In the present invention, in the process of preparing the chiral mercuric sulfide seed dispersion, the inorganic base is preferably used in the form of an inorganic base solution, and the concentration of the inorganic base solution is preferably 1-3 mol / L, and specifically preferably 1 mol / L, 2 mol / L or 3 mol / L. In the present invention, in the process of preparing the chiral mercuric sulfide seed dispersion, the thioacetamide is preferably used in the form of a thioacetamide solution, and the concentration of the thioacetamide solution is preferably 150 to 200 mmol / L, and specifically preferably 150 mmol / L, 160 mmol / L, 170 mmol / L, 180 mmol / L, 190 mmol / L or 200 mmol / L. In the present invention, in the process of preparing the chiral mercuric sulfide seed dispersion, the volume ratio of the water-soluble mercury salt solution, the chiral penicillamine solution, the inorganic base solution and the thioacetamide solution is preferably 10:2:0.3:1. In the present invention, the mixing of water-soluble mercury salt, chiral penicillamine, inorganic base and thioacetamide preferably comprises the following steps: placing a water-soluble mercury salt solution in a container, adding a chiral penicillamine solution at a time under normal temperature and magnetic stirring conditions, then adding an inorganic base solution dropwise, stirring magnetically, and then adding thioacetamide solution dropwise, stirring magnetically; the magnetic stirring time is preferably 1 to 3 minutes, more preferably 2 minutes.In the present invention, in the reaction raw material liquid, the concentration of the water-soluble mercury salt is preferably 35 to 40 mmol / L, and specifically preferably 35 mmol / L, 36 mmol / L, 37 mmol / L, 37.6 mmol / L, 38 mmol / L, 39 mmol / L or 40 mmol / L; the concentration of the chiral penicillamine is preferably 10 to 15 mmol / L, and specifically preferably 10 mmol / L, 11 mmol / L, 12 mmol / L, 13 mmol / L, 13.53 mmol / L, 14 mmol / L or 15mmol / L; the concentration of the inorganic base is preferably 0.01-0.05mol / L, and specifically preferably 0.01mol / L, 0.02mol / L, 0.03mol / L, 0.04mol / L, 0.045mol / L or 0.05mol / L; the concentration of thioacetamide is preferably 10-15mmol / L, and specifically preferably 10mmol / L, 11mmol / L, 12mmol / L, 13mmol / L, 13.53mmol / L, 14mmol / L or 15mmol / L. In the present invention, the temperature of the self-assembly reaction is preferably 35-40°C, and more preferably 38°C; the time is preferably 2-4h, and more preferably 3h; the self-assembly reaction is preferably carried out under water bath conditions, and the self-assembly reaction is preferably carried out under stirring conditions. After the self-assembly reaction, the present invention preferably further comprises: subjecting the obtained self-assembly reaction liquid to solid-liquid separation after ultrasonic treatment to obtain an orange-red precipitate; after washing the orange-red precipitate with water, dispersing it in ultrapure water to obtain the chiral mercuric sulfide seed dispersion. In the present invention, the solid-liquid separation method is preferably centrifugation, the speed of the centrifugation is preferably 15000-15500rpm, specifically preferably 15300rpm, the time is preferably 10-20min, specifically preferably 15min. In the present invention, the reagent for the water washing is preferably water, and the water is preferably ultrapure water. In the present invention, the water washing method is preferably ultrasonic oscillation. In the present invention, the number of water washings is preferably 4 times, and after each water washing, the present invention preferably further comprises centrifugal separation, the speed of the centrifugal separation is preferably 15000-15500rpm, specifically preferably 15300rpm, the time is preferably 10-20min, specifically preferably 15min.

[0049] In the present invention, in the process of preparing the seed solution, the chiral penicillamine is preferably used in the form of a chiral penicillamine solution, and the concentration of the chiral penicillamine solution is preferably 80-100 mmol / L, and specifically preferably 80 mmol / L, 90 mmol / L or 100 mmol / L. In the present invention, in the process of preparing the seed solution, the inorganic base is preferably used in the form of an inorganic base solution, and the concentration of the inorganic base solution is preferably 1-3 mol / L, and specifically preferably 1 mol / L, 2 mol / L or 3 mol / L. In the present invention, in the process of preparing the seed solution, the volume ratio of the chiral mercuric sulfide seed dispersion, the chiral penicillamine solution and the inorganic base solution is preferably 2.5:1:0.3.

[0050] In the present invention, in the seed solution, the concentration of chiral mercuric sulfide is preferably 0.5-4.5 mg / mL, specifically preferably 0.5 mg / mL, 0.5625 mg / mL, 1 mg / mL, 1.32 mg / mL, 1.5 mg / mL, 1.776 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL or 4.5 mg / mL; the concentration of chiral penicillamine is preferably 20-25 mmol / L, specifically preferably 20 mmol / L, 21 mmol / L, 22 mmol / L, 23 mmol / L, 23.68 mmol / L, 24 mmol / L or 25 mmol / L; the concentration of inorganic base is preferably 0.1-0.2 mmol / L, specifically preferably 0.1 mmol / L, 0.12 mmol / L, 0.14 mmol / L, 0.16 mmol / L, 0.18 mmol / L or 0.2 mmol / L.

[0051] After obtaining the precursor solution and the seed solution, the present invention sequentially adds the precursor solution and thioacetamide to the seed solution for reaction. After the reaction, isopropanol is added to obtain the chiral nano-mercury sulfide.

[0052] In the present invention, in the reaction step, the thioacetamide is used in the form of a thioacetamide solution, and the concentration of the thioacetamide solution is preferably 0.5 to 1.5 mol / L, and specifically preferably 1 mol / L.

[0053] In the present invention, in the step of the reaction, the volume ratio of the seed solution, the precursor solution and the thioacetamide solution is preferably 3.8:1-4:0.2-1.5. In the present invention, when preparing right-handed nano-mercuric sulfide, in the step of the reaction, the volume ratio of the seed solution, the precursor solution and the thioacetamide solution is preferably 3.8:4:1.1. In the present invention, when preparing left-handed nano-mercuric sulfide, in the step of the reaction, the volume ratio of the seed solution, the precursor solution and the thioacetamide solution is preferably 3.8:1.33:0.367. In the present invention, in the step of the reaction, the volume ratio of the seed solution, the precursor solution and the thioacetamide solution will affect the morphology of the final nano-mercuric sulfide. The present invention controls the above ratios to ensure that ray-shaped nano-mercuric sulfide is obtained.

[0054] In the present invention, in the step of reacting, the precursor solution is preferably added dropwise, and the dropwise addition is preferably dropwise addition. In the present invention, in the step of reacting, the thioacetamide solution is preferably added dropwise, and the dropwise addition is preferably dropwise addition.

[0055] In the present invention, the reaction is preferably carried out under light-shielding conditions, the reaction temperature is preferably room temperature, the reaction time is preferably 3 to 5 hours, and more preferably 4 hours. In the present invention, the reaction is preferably carried out under stirring conditions.

[0056] In the present invention, the volume ratio of the isopropanol to the reaction liquid obtained by the reaction is preferably 5-10:1-2. In the present invention, when preparing right-handed nano-mercuric sulfide, the volume ratio of the isopropanol to the reaction liquid obtained by the reaction is preferably 8.9:2.5. In the present invention, when preparing left-handed nano-mercuric sulfide, the volume ratio of the isopropanol to the reaction liquid obtained by the reaction is preferably 5.497:1.25. In the present invention, the addition of the isopropanol can promote the formation of nano-mercuric sulfide into a ray shape.

[0057] In the present invention, the chiral nano-mercury sulfide is preferably dispersed in water, that is, the chiral nano-mercury sulfide is preferably present in the form of a chiral nano-mercury sulfide dispersion.

[0058] After adding isopropanol, the present invention preferably further comprises: separating the obtained reaction mixture liquid solid-liquid to obtain a precipitate; washing and dispersing the precipitate in sequence to obtain the chiral nano mercuric sulfide. In the present invention, the solid-liquid separation method is preferably centrifugation, the centrifugal speed is preferably 9000-10000rpm, more preferably 9600rpm, the time is preferably 10-20min, more preferably 15min. In the present invention, the washing reagent is preferably water, and the water is preferably ultrapure water. In the present invention, the number of washings is preferably 3 times, and after each washing, it is preferably further comprised of solid-liquid separation, the solid-liquid separation method is preferably centrifugation, the centrifugal speed is preferably 9000-10000rpm, more preferably 9600rpm; the time is preferably 10-30min, specifically preferably 10min, 15min, 20min, 25min or 30min. In the present invention, the dispersed dispersant is preferably ultrapure water. In the present invention, the dispersion is preferably carried out under the condition of ultrasonic oscillation.

[0059] The present invention also provides chiral nano-mercury sulfide prepared by the preparation method described in the above technical solution, wherein the chiral nano-mercury sulfide is in the shape of a ray.

[0060] The present invention also provides the use of the chiral nano-mercury sulfide described in the above technical solution in the preparation of medicines.

[0061] The mercuric sulfide provided by the invention has chirality and good dispersibility, and when applied in medicine, it can better exert its medicinal effect.

[0062] The chiral nano-mercury sulfide and its preparation method and application provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0063] Example 1

[0064] The preparation method of right-handed nano mercuric sulfide is as follows:

[0065] (1) Prepare 5 mL of 90 mmol / L dextrorotatory penicillamine solution, 6 mL of 30 mmol / L mercuric nitrate solution, 10 mL of 1 mol / L thioacetamide solution, and 5 mL of 2 mol / L sodium hydroxide solution.

[0066] (2) Take 1.8 mL of 90 mmol / L dextrorotatory penicillamine solution, then add it to 6 mL of 30 mmol / L mercuric nitrate solution at one time, shake horizontally for 3 minutes, then add 0.3 mL of 2 mol / L sodium hydroxide solution at one time, shake horizontally for 1 minute, and obtain a precursor solution.

[0067] (3) Take 2.5 mL of dextrorotatory mercuric sulfide seed dispersion (2.7 mg / mL) in a round-bottom flask, add 1 mL of 90 mmol / L dextrorotatory penicillamine solution and 0.3 mL of 2 mol / L sodium hydroxide solution at once under magnetic stirring at room temperature to obtain a seed solution. 4 mL of the precursor solution and 1.1 mL of the 1 mol / L thioacetamide solution prepared above were added dropwise to the round-bottom flask in sequence using a peristaltic pump, and the reaction was continued for 4 h under magnetic stirring at room temperature in the dark. When the reaction was completed, 2.5 mL of isopropanol was immediately added to obtain an orange-yellow suspension.

[0068] (4) The orange-yellow suspension was centrifuged at 9600 rpm for 15 min, the supernatant was discarded and the precipitate was collected, and then ultrapure water was added for washing. After centrifugation at 9600 rpm for 15 min, the supernatant was discarded and the orange-red precipitate was retained. The above washing cycle was continued for 1 time. The last washing was centrifuged at 9600 rpm for 30 min, the supernatant was discarded and the orange-red precipitate was retained. 200 μL of ultrapure water was added to the orange-red precipitate obtained, and ultrasonic vibration was performed to obtain the final product, right-handed nanomercury sulfide (D-HgSNPs) dispersion.

[0069] The preparation method of right-handed mercuric sulfide seed dispersion includes: placing 10 mL of 50 mmol / L mercuric nitrate solution in a 50 mL round-bottom flask, adding 2 mL of 90 mmol / L D-penicillamine solution at a time under normal temperature and magnetic stirring conditions, then adding 0.3 mL of 2 mol / L sodium hydroxide solution dropwise, stirring magnetically for 2 minutes, then adding 1 mL of 180 mmol / L thioacetamide solution dropwise, stirring magnetically for 2 minutes, and then placing the round-bottom flask in a 38°C water bath and stirring magnetically. The reaction was continued for 3 hours to obtain an orange-red suspension; the orange-red suspension was ultrasonically divided into 2 mL centrifuge tubes, 1.5 mL in each tube, and centrifuged at 15300 rpm for 15 min to separate the solid and liquid, and the clear liquid was discarded to retain the orange-red precipitate, 0.5 g of ultrapure water was added to the orange-red precipitate in each centrifuge tube, ultrasonically shaken, centrifuged at 15300 rpm for 15 min again and separated the solid and liquid, and the washing was repeated 3 times. The orange-red precipitate obtained by washing was concentrated in one tube with ultrapure water and fixed to 4 mL to obtain a right-handed mercuric sulfide seed dispersion with a concentration of 2.7 mg / mL.

[0070] Comparative Example 1

[0071] The difference from Example 1 is that: in (3), the reaction is continued for 4 hours without adding isopropanol to obtain an orange-yellow solution. (4) The orange-yellow solution is centrifuged at 9600 rpm for 15 minutes, the supernatant is discarded, and the precipitate is collected, and then ultrapure water is added for washing. After centrifugation at 9600 rpm for 15 minutes, the supernatant is discarded to retain the orange-red precipitate, and the above washing is repeated for 2 cycles. Finally, 200 μL of ultrapure water is added to the orange-red precipitate obtained, and ultrasonic vibration is performed to obtain the final product, a right-handed nano-mercuric sulfide dispersion, and the rest is the same as in Example 1.

[0072] The obtained right-handed nano-mercury sulfide dispersion is clearer and more transparent in appearance. The electron microscopy results show that there are no particles with a ray-like microstructure, indicating that the addition of isopropanol after the reaction has a great influence on the morphology of the product, and isopropanol must be added at the end of the reaction.

[0073] Comparative Example 2

[0074] The difference from Example 1 is as follows: (4) the orange-yellow suspension was centrifuged at 9600rpm for 15min, the supernatant was discarded and the precipitate was collected, and then ultrapure water was added for washing. After centrifugation at 9600rpm for 15min, the supernatant and the orange-red precipitate were collected, and the above washing cycle was continued for 2 cycles, the supernatant and the orange-red precipitate were collected, and the precipitate was ultrasonically dispersed with ultrapure water. The two collected supernatants were combined, divided into 2mL centrifuge tubes, centrifuged at 14000rpm for 15min, the supernatant was discarded, ultrapure water was added and combined into 2 tubes, centrifuged at 14000rpm for 15min, the supernatant was discarded, ultrapure water was added and combined to make the volume 2mL, centrifuged and the supernatant was discarded, and the washing was repeated once. Finally, the precipitate was added into ultrapure water for ultrasonic dispersion to obtain a right-handed nano-mercuric sulfide dispersion. The other steps are the same as those in Example 1.

[0075] The obtained right-handed nano-mercury sulfide dispersion and the original bottom precipitate were characterized under an electron microscope, and it was found that the supernatant contained many impurities and the particle morphology was not obvious, while the original bottom precipitate particles had a good morphology, indicating that the yield of the product cannot be increased by collecting the supernatant.

[0076] Example 2

[0077] The preparation method of left-handed nano mercuric sulfide is as follows:

[0078] (1) Prepare 5 mL of 90 mmol / L L-penicillamine solution, 6 mL of 30 mmol / L mercuric nitrate solution, 10 mL of 1 mol / L thioacetamide solution, and 5 mL of 2 mol / L sodium hydroxide solution.

[0079] (2) Take 1.8 mL of 90 mmol / L L-penicillamine solution, then add it to 6 mL of 30 mmol / L mercuric nitrate solution at one time, shake horizontally for 3 minutes, then add 0.3 mL of 2 mol / L sodium hydroxide solution at one time, shake horizontally for 1 minute, and obtain a precursor solution.

[0080] (3) Take 2.5 mL of the L-mercuric sulfide seed dispersion (0.855 mg / mL) in a round-bottom flask, add 1 mL of a 90 mmol / L L-penicillamine solution and 0.3 mL of a 2 mol / L sodium hydroxide solution at once under magnetic stirring at room temperature to obtain a seed solution. 1.33 mL of the precursor solution and 367 μL of the 1 mol / L thioacetamide solution prepared above were added dropwise to the round-bottom flask using a peristaltic pump, and the reaction was continued for 4 h under magnetic stirring at room temperature in the dark. After the reaction was completed, 1.25 mL of isopropanol was added to obtain an orange-yellow suspension.

[0081] (4) The orange-yellow suspension was centrifuged at 9600 rpm for 15 min, the supernatant was discarded and the precipitate was collected, and then ultrapure water was added for washing. After centrifugation at 9600 rpm for 15 min, the supernatant was discarded and the orange-red precipitate was retained. The above washing cycle was continued for 1 time. The last washing was centrifuged at 9600 rpm for 30 min, the supernatant was discarded and the orange-red precipitate was retained, ultrapure water was added, and ultrasonic vibration was performed to obtain the final product, left-handed nano-mercury sulfide (L-HgSNPs) dispersion.

[0082] The preparation method of the L-mercuric sulfide seed dispersion is as follows: 10 mL of a 50 mmol / L mercuric nitrate solution is placed in a 50 mL round-bottom flask, and 2 mL of a 90 mmol / L L-penicillamine solution is added at one time under normal temperature and magnetic stirring conditions, and then 0.3 mL of a 2 mol / L sodium hydroxide solution is added dropwise, and after magnetic stirring for 2 minutes, 1 mL of a 180 mmol / L thioacetamide solution is added dropwise, and magnetic stirring is performed for 2 minutes. The round-bottom flask is then placed in a 38°C water bath, and magnetic stirring is continued. The reaction was carried out for 3 hours to obtain an orange-red suspension; the orange-red suspension was ultrasonically divided into 2 mL centrifuge tubes, 1.5 mL in each tube, and centrifuged at 15300 rpm for 15 min to separate the solid and liquid, and the clear liquid was discarded to retain the orange-red precipitate, 0.5 g of ultrapure water was added to the orange-red precipitate in each centrifuge tube, ultrasonically shaken, centrifuged at 15300 rpm for 15 min again and separated the solid and liquid, and the washing was repeated 3 times. The orange-red precipitate obtained by washing was concentrated in one tube with ultrapure water and fixed to 4 mL to obtain a left-handed mercuric sulfide seed dispersion with a concentration of 0.855 mg / mL.

[0083] Comparative Example 3

[0084] (1) Prepare 5 mL of 90 mmol / L L-penicillamine solution, 6 mL of 30 mmol / L mercuric nitrate solution, 10 mL of 1 mol / L thioacetamide solution, and 5 mL of 2 mol / L sodium hydroxide solution.

[0085] (2) Take 1.8 mL of 90 mmol / L L-penicillamine solution, then add it to 6 mL of 30 mmol / L mercuric nitrate solution at one time, shake and mix, and add 0.3 mL of 2 mol / L sodium hydroxide solution at one time. After complete mixing, a precursor solution is obtained.

[0086] (3) Take 2.5 mL of the L-mercuric sulfide seed dispersion (0.855 mg / mL) in a round-bottom flask, add 1 mL of a 90 mmol / L L-penicillamine solution and 0.3 mL of a 2 mol / L sodium hydroxide solution at once under magnetic stirring at room temperature to obtain a seed solution. Add 4 mL of the precursor solution and 1.1 mL of the 1 mol / L thioacetamide solution prepared above to the flask dropwise using a peristaltic pump, and continue the reaction for 4 h under magnetic stirring at room temperature in a dark environment. After the reaction is completed, add 2.5 mL of isopropanol to obtain an orange-yellow suspension.

[0087] (4) The orange-yellow suspension was centrifuged at 9600 rpm for 15 min, the supernatant was discarded and the precipitate was collected, and then ultrapure water was added for washing. After centrifugation at 9600 rpm for 15 min, the supernatant was discarded and the orange-red precipitate was retained. The above washing cycle was continued for one more time. The last washing was performed by centrifugation at 9600 rpm for 30 min, the supernatant was discarded and the orange-red precipitate was retained. Finally, 200 μL of ultrapure water was added to the orange-red precipitate obtained, and ultrasonic vibration was performed to obtain the final product, a left-handed nano-mercury sulfide dispersion.

[0088] The obtained left-handed nano-mercury sulfide dispersion does not show the required special ray-like microstructure under an electron microscope, but contains a large amount of impurities.

[0089] The right-handed nano-mercury sulfide in the right-handed nano-mercury sulfide dispersion obtained in Example 1 and the left-handed nano-mercury sulfide in the left-handed nano-mercury sulfide dispersion obtained in Example 2 were analyzed using a high-resolution transmission electron microscope. The results are as follows: Figure 1 and Figure 2 As shown, Figure 1 This is a high-resolution transmission electron microscopy image of right-handed nano-mercuric sulfide in the right-handed nano-mercuric sulfide dispersion obtained in Example 1. Figure 1 It can be seen that the obtained right-handed nano-mercury sulfide has uniform morphology and is evenly dispersed in ultrapure water; and ray-shaped right-handed nano-mercury sulfide can be observed. Figure 2 This is a high-resolution transmission electron microscopy image of left-handed nano-mercuric sulfide in the left-handed nano-mercuric sulfide dispersion obtained in Example 2. Figure 2It can be seen that the left-handed nano-mercury sulfide has a uniform morphology and is evenly dispersed in ultrapure water, and ray-shaped left-handed nano-mercury sulfide is observed.

[0090] The right-handed nano-mercuric sulfide dispersion obtained in Example 1 and the left-handed nano-mercuric sulfide dispersion obtained in Example 2 were subjected to UV-visible spectroscopy detection with a scanning wavelength of 200 nm to 600 nm. The results showed that the particles in the dispersions were mercury sulfide nanoclusters.

[0091] The size distribution of the right-handed nano-mercury sulfide in the right-handed nano-mercury sulfide dispersion obtained in Example 1 and the left-handed nano-mercury sulfide in the left-handed nano-mercury sulfide dispersion obtained in Example 2 was measured using a high-resolution transmission electron microscope. The results are as follows: Figure 3 and Figure 4 As shown, Figure 3 The length distribution diagram of the right-handed nano-mercury sulfide obtained in Example 1 and the left-handed nano-mercury sulfide obtained in Example 2 is shown in FIG. Figure 3 The horizontal axis Length represents the length, and the vertical axis Percentage represents the percentage; Figure 4 The width distribution diagram of the right-handed nano-mercury sulfide obtained in Example 1 and the left-handed nano-mercury sulfide obtained in Example 2 is shown in FIG. Figure 4 The horizontal axis Width represents the width, and the vertical axis Percentage represents the percentage. Figure 3 and Figure 4 It can be seen that the right-handed nano-mercury sulfide is ray-shaped with a length of 24 to 50 nm and a width of 16 to 28 nm, and the right-handed nano-mercury sulfide is ray-shaped with a length of 26 to 48 nm and a width of 12 to 20 nm.

[0092] The chiral characteristics of the right-handed nano-mercury sulfide in the right-handed nano-mercury sulfide dispersion obtained in Example 1 and the left-handed nano-mercury sulfide in the left-handed nano-mercury sulfide dispersion obtained in Example 2 were investigated by circular dichroism. The results are as follows: Figure 5 As shown, Figure 5 Circular dichroism spectra of right-handed nano-mercuric sulfide obtained in Example 1 and left-handed nano-mercuric sulfide obtained in Example 2, Figure 5 The horizontal axis Wavelength represents the wavelength, and the vertical axis CD represents the circular dichroism intensity, the unit is mdeg; Figure 5 It can be seen that the obtained right-handed nano-mercury sulfide has right-handed chirality, and the obtained left-handed nano-mercury sulfide has left-handed chirality.

[0093] Mouse microglia (BV2) were exposed to culture medium containing 80 ppm of right-handed nano-mercuric sulfide material and left-handed nano-mercuric sulfide material. The results are as follows Figure 6 and Figure 7 As shown, Figure 6 BV after exposure to 80ppm right-handed nano-mercury sulfide for 24 hours 2 Cell morphology, Figure 7BV after exposure to 80ppm L-HgS nanomaterials for 24h 2 Cell morphology, from Figure 6 and Figure 7 It can be seen that the cell morphology is normal and direct exposure has no obvious effect on the cells, which proves that right-handed nano-mercury sulfide and left-handed nano-mercury sulfide have no obvious cytotoxicity, are bioavailable, and have application prospects.

[0094] It can be seen from the above examples and comparative examples that the prepared left-handed nano-mercuric sulfide and right-handed nano-mercuric sulfide have strong chiral optical activity, the nanoparticle morphology is very unique and stable, and the size distribution is uniform. The reaction conditions are mild and easy to control, the operation is simple, the reaction process is green and environmentally friendly, and the reaction yield is greatly improved.

[0095] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing chiral nano-mercury sulfide, characterized in that: The following steps are involved: mixing a water-soluble mercuric salt, chiral penicillamine, an inorganic base and water to obtain a precursor solution; mixing a chiral mercuric sulfide seed dispersion, chiral penicillamine and an inorganic base to obtain a seed solution; Adding a precursor solution and thioacetamide to the seed solution in sequence to react, and after the reaction, adding isopropanol to obtain the chiral nano-mercuric sulfide; The preparation method of the chiral mercuric sulfide seed dispersion comprises the following steps: Mixing a water-soluble mercuric salt, chiral penicillamine, an inorganic base and thioacetamide, and subjecting the obtained reaction raw material liquid to a self-assembly reaction to obtain the chiral mercuric sulfide seed dispersion; The concentration of the chiral mercuric sulfide seed dispersion is 0.5-5 mg / mL.

2. The preparation method according to claim 1, characterized in that: The water-soluble mercuric salt includes mercuric nitrate, the inorganic base includes sodium hydroxide, and the chiral penicillamine is L-penicillamine or D-penicillamine.

3. The preparation method according to claim 1, characterized in that: In the precursor solution, the concentration of the water-soluble mercury salt is 20-25 mmol / L, the concentration of the chiral penicillamine is 18-22 mmol / L, and the concentration of the inorganic base is 0.05-0.1 mol / L.

4. The preparation method according to claim 1, characterized in that: In the reaction raw material liquid, the concentration of water-soluble mercury salt is 35-40 mmol / L, the concentration of penicillamine is 10-15 mmol / L, the concentration of inorganic base is 0.01-0.05 mol / L, and the concentration of thioacetamide is 10-15 mmol / L.

5. The preparation method according to claim 1 or 4, characterized in that: The temperature of the self-assembly reaction is 35-40° C., the time is 2-4 hours, and the self-assembly reaction is carried out in a water bath; after the self-assembly reaction, the method further comprises: solid-liquid separation of the obtained self-assembly reaction liquid to obtain an orange-red precipitate; after washing the orange-red precipitate with water, the solution is dispersed in ultrapure water to obtain the chiral mercuric sulfide seed dispersion.

6. The preparation method according to claim 1, characterized in that: In the seed solution, the concentration of chiral mercuric sulfide is 0.5-4.5 mg / mL, the concentration of chiral penicillamine is 20-25 mmol / L, and the concentration of inorganic base is 0.1-0.2 mmol / L.

7. The preparation method according to claim 1, characterized in that: In the reaction step, thioacetamide is used in the form of thioacetamide solution, the concentration of the thioacetamide solution is 0.5-1.5 mol / L, and the volume ratio of the seed solution, the precursor solution and the thioacetamide solution is 3.8:1-4:0.2-1.

5.

8. The preparation method according to claim 1, characterized in that: The reaction is carried out under light-proof conditions, and the reaction time is 3 to 5 hours; The volume ratio of the isopropanol to the reaction liquid obtained by the reaction is 5-10:1-2.

9. The chiral nano-mercury sulfide prepared by the preparation method according to any one of claims 1 to 8, characterized in that: The chiral nano-mercury sulfide is in the shape of a ray.

10. Use of the chiral nano-mercury sulfide according to claim 9 in the preparation of medicines.

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