Light-operated shape memory microcapsule as well as preparation method and application thereof

Abstract

The invention discloses a light-operated shape memory microcapsule as well as a preparation method and application thereof, and relates to the technical field of shape memory materials. The light-operated shape memory microcapsule comprises a capsule core and a capsule wall coating the capsule core, the capsule core comprises a two-dimensional photo-thermal nano material and a thermal response shape memory polymer material, and the capsule wall comprises a water-soluble polymer material. On the basis of the thermal response shape memory polymer material, the two-dimensional photo-thermal nanometer material is added, the two-dimensional photo-thermal nanometer material and the thermal response shape memory polymer material cooperate with each other, the two-dimensional photo-thermal nanometer material has a photo-thermal effect, and when illumination with a certain wavelength is adopted, the temperature rises, and the thermal response shape memory polymer material can be obtained. The shape memory effect of the heating response shape memory polymer material is promoted, so that the microcapsule is endowed with the light-operated shape memory ability, the microcapsule can be remotely regulated in vitro, and the controllability of the shape memory performance of the microcapsule is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of shape memory materials, and in particular to a light-controlled shape memory microcapsule and a preparation method and application thereof. Background Art

[0002] As a new type of smart material, shape memory polymers have attracted widespread attention in recent years. It can sense and respond to changes in the environment and return to a pre-set original shape to achieve a specific effect. It has been widely used in cardiovascular stents, smart sutures, tissue engineering, controlled drug release, and antibacterial materials, and is one of the current research hotspots in the field of biomaterials. Compared with the macroscopic scale, micro-nanoscale shape memory polymers have unique properties such as injectability, large specific surface area, customized biodistribution, and controllable interaction with cells. They show unique advantages in biological applications such as cell tissue engineering, drug loading and release, cancer chemotherapy, and biosensing. In practical applications, shape memory polymers are usually affected by the complex microenvironment in the body. Therefore, shape memory polymers that respond to external stimuli and have controllable deformation capabilities have attracted widespread attention from researchers. The commonly used response sources of shape memory polymers are mainly heat, light, electricity, force, magnetism, etc. Among them, thermal responsive shape memory polymers can respond to changes in temperature before and after implantation as implants, and have been widely used in the biomedical field. However, due to the uncontrollable response process and the difficulty in achieving remote regulation in vitro, they are subject to certain limitations in certain specific biological applications.

[0003] Therefore, the prior art still needs to be improved and developed. Summary of the invention

[0004] Based on the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a light-controlled shape memory microcapsule and a preparation method and application thereof, aiming to solve the problem that thermally responsive shape memory polymer materials are not easy to achieve in vitro remote regulation.

[0005] The technical solution of the present invention is as follows:

[0006] According to a first aspect of the present invention, a light-controlled shape memory microcapsule is provided, wherein the light-controlled shape memory microcapsule comprises a capsule core and a capsule wall covering the capsule core, the capsule core comprises a two-dimensional photothermal nanomaterial and a thermally responsive shape memory polymer material, and the capsule wall comprises a water-soluble polymer material.

[0007] Optionally, the two-dimensional photothermal nanomaterial is a biodegradable two-dimensional photothermal nanomaterial.

[0008] Optionally, the biodegradable two-dimensional photothermal nanomaterial includes at least one of two-dimensional MXene nanosheets, two-dimensional niobium selenide nanosheets and two-dimensional bismuth oxide selenide nanosheets.

[0009] Optionally, the thermally responsive shape memory polymer material includes at least one of poly (D, L-lactic acid), poly (D, lactide-trimethylene carbonate), polyurethane and polylactic acid.

[0010] Optionally, the water-soluble polymer material includes at least one of polyvinyl alcohol, polyethylene glycol and polyvinyl pyrrolidone.

[0011] Optionally, the particle size of the light-controlled shape memory microcapsule is 5 to 55 μm.

[0012] The second aspect of the present invention provides a method for preparing the light-controlled shape memory microcapsule as described above, which comprises the following steps:

[0013] The two-dimensional photothermal nanomaterial and the thermal responsive shape memory polymer material are added into an organic solvent and dispersed by ultrasonication to obtain a dispersion;

[0014] A water-soluble polymer material solution is provided, and the water-soluble polymer material solution is mixed with the dispersion, and stirred at a rotation speed of 800 to 1200 rpm to obtain the light-controlled shape memory microcapsule.

[0015] Optionally, the mass ratio of the two-dimensional photothermal nanomaterial, the thermally responsive shape memory polymer material and the water-soluble polymer material in the water-soluble polymer material solution is (0.5-2):(10-40):(37.5-150);

[0016] In the dispersion, the concentration of the two-dimensional photothermal nanomaterial is 0.5 to 2 mg / mL;

[0017] In the water-soluble polymer material solution, the concentration of the water-soluble polymer material is 1.25-5 mg / mL.

[0018] Optionally, the organic solvent includes at least one of dichloromethane and chloroform.

[0019] The third aspect of the present invention provides a use of the light-controlled shape memory microcapsule of the present invention as described above and / or the light-controlled shape memory microcapsule prepared by the preparation method of the present invention as described above in the preparation of tumor vascular embolization materials.

[0020] Beneficial effects: The present invention is based on thermally responsive shape memory polymer materials. By adding two-dimensional photothermal nanomaterials, the two-dimensional photothermal nanomaterials and thermally responsive shape memory polymer materials work together. The two-dimensional photothermal nanomaterials have a photothermal effect. When a certain wavelength of light is used, the temperature rises, thereby promoting the shape memory effect of the thermally responsive shape memory polymer material, thereby giving the microcapsules light-controlled shape memory capabilities, allowing the microcapsules to achieve in vitro remote regulation, and increasing the controllability of the shape memory performance of the microcapsules. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the UV-visible-near infrared absorption spectrum of the single-layer Ti3C2 nanosheet prepared in Example 1 of the present invention in aqueous solution.

[0022] Figure 2 This is a transmission electron microscope image of the single-layer Ti3C2 nanosheet prepared in Example 1 of the present invention.

[0023] Figure 3 This is a scanning electron microscope image of the MXene / PDLLA microcapsules prepared in Example 1 of the present invention.

[0024] Figure 4 This is the particle size distribution diagram of the MXene / PDLLA microcapsules prepared in Example 1 of the present invention.

[0025] Figure 5 This is the energy spectrum of the MXene / PDLLA microcapsules prepared in Example 1 of the present invention.

[0026] Figure 6 This is a graph showing the photothermal performance test results of the MXene / PDLLA microcapsules prepared in Example 1 of the present invention and the PDLLA microcapsules in Comparative Example 1.

[0027] Figure 7 The results of the light-controlled shape memory performance of the MXene / PDLLA microcapsules prepared in Example 1 of the present invention recorded using a scanning electron microscope, wherein (a) is the original morphology of the MXene / PDLLA microcapsules, (b) is the morphology of the spindle-shaped MXene / PDLLA microcapsules formed after the MXene / PDLLA microcapsules were stretched, and (c) is the original morphology of the spindle-shaped MXene / PDLLA microcapsules restored after near-infrared light irradiation.

[0028] Figure 8 This is a graph showing the cytotoxicity test results of the MXene / PDLLA microcapsules prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0029] The present invention provides a light-controlled shape memory microcapsule and a preparation method and application thereof. To make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0030] Unless otherwise defined, all technical terms and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0031] Tumor vascular embolization therapy is a new therapy currently widely used in clinical treatment of tumors. By injecting embolic materials into the arteries or tumor blood vessels that supply blood to the tumor, the blood supply of the arteries at that location is blocked, and the tumor's nutrition supply is cut off, thereby achieving the effect of controlling the shrinkage or even eliminating the tumor. For most cancer patients in clinical practice, anti-tumor treatment is mostly aimed at vascularized tumors. Therefore, tumor vascular embolization therapy presents a broad-spectrum and efficient clinical application prospect. However, to date, finding a safe and effective vascular embolization therapy is still a "bottleneck" problem in this research field. Thermally responsive shape memory polymers can respond to changes in temperature before and after implantation as implants and have been widely used in the biomedical field. However, due to the uncontrollable response process and the difficulty in achieving in vitro remote control, it has been subject to certain limitations in certain specific biological applications. However, compared with thermal response, the light response method has the great advantage of being controllable in both time and space scales. It can selectively and orderly control the shape recovery process of the material through artificial means, has remote controllability, and can achieve fixed-point, timing, speed regulation, and volume regulation of shape. Based on this, an embodiment of the present invention provides a light-controlled shape memory microcapsule, wherein the light-controlled shape memory microcapsule includes a capsule core and a capsule wall coating the capsule core, the capsule core includes a two-dimensional photothermal nanomaterial and a thermally responsive shape memory polymer material, and the capsule wall includes a water-soluble polymer material.

[0032] In the embodiment of the present invention, based on the thermal responsive shape memory polymer material, by adding the two-dimensional photothermal nanomaterial, the thermal responsive shape memory polymer material is indirectly transformed into the light-controlled shape memory material. The excellent photothermal effect of the two-dimensional photothermal nanomaterial can improve the shape memory performance of the microcapsule, that is, the two-dimensional photothermal nanomaterial and the thermal responsive shape memory polymer material are used in combination. The two-dimensional photothermal nanomaterial has a photothermal effect. When a certain wavelength of light is used, the temperature rises, thereby promoting the shape memory effect of the thermal responsive shape memory polymer material, thereby giving the microcapsule a light-controlled shape memory ability, so that the microcapsule can achieve in vitro remote regulation and control, and increase the controllability of the shape memory performance of the microcapsule. The light-controlled shape memory microcapsule provided by the present invention has important research significance and practical significance for tumor vascular embolization treatment.

[0033] In an embodiment of the present invention, the light-controlled shape memory microcapsule includes a capsule core and a capsule wall covering the capsule core. It can also be understood that the light-controlled shape memory microcapsule has a core-shell structure, wherein the core material includes two-dimensional photothermal nanomaterials and thermally responsive shape memory polymer materials, and the shell includes a water-soluble polymer material.

[0034] Among the many light sources of different wavelengths, near-infrared light is widely used as an excitation light. It is widely used in biomedical fields such as cancer photothermal therapy, drug controlled release, and bioimaging due to its excellent tissue penetration ability (penetration depth can reach about 10 cm) and minimal photodamage. However, a single near-infrared light-responsive shape memory material also has defects such as slow response, low response efficiency, difficult degradation of the materials used, and easy to induce toxic reactions in the body. Therefore, the development of a microcapsule with excellent near-infrared light-controlled shape memory properties that is biodegradable has important research significance and practical significance for tumor vascular embolization therapy. Therefore, in some embodiments, the two-dimensional photothermal nanomaterial is a biodegradable two-dimensional photothermal nanomaterial. In this way, the light-controlled shape memory microcapsule can have excellent biodegradability, reduce the body's residue, greatly reduce its biological toxicity, and make the light-controlled shape memory microcapsule have higher safety.

[0035] In some embodiments, the biodegradable two-dimensional photothermal nanomaterial comprises at least one of a two-dimensional MXene nanosheet, a two-dimensional niobium selenide nanosheet (i.e., niobium diselenide nanosheet), and a two-dimensional bismuth oxide selenide nanosheet. MXene is generally a MAX phase (which is a chemical formula of M n+1 AX n A non-van der Waals type layered compound, wherein M is a transition metal, A is a main group element, and X is a carbon or nitrogen element. It is obtained by etching away the A layer atoms in the material.

[0036] In some embodiments, the two-dimensional MXene nanosheets include at least one of Ti3C2 nanosheets, Ta4C3 nanosheets, Ti3CN nanosheets, Nb2C nanosheets, and Mo2C nanosheets, but are not limited thereto.

[0037] Taking the preparation of Ti3C2 nanosheets as an example, the preparation method of Ti3C2 nanosheets includes the following steps:

[0038] After mixing LiF and hydrochloric acid, Ti3AlC2 is added to obtain a suspension;

[0039] The suspension is placed at a preset temperature, stirred, and etched for a preset time, and then washed, filtered, and freeze-dried to obtain multilayer Ti3C2 nanosheets.

[0040] Furthermore, the multilayer Ti3C2 nanosheets can be treated by ultrasound to obtain single-layer Ti3C2 nanosheets.

[0041] In some embodiments, the thermally responsive shape memory polymer material includes at least one of poly(D,L-lactic acid), poly(D, lactide-trimethylene carbonate), polyurethane, and polylactic acid, but is not limited thereto.

[0042] In some embodiments, the water-soluble polymer material includes at least one of polyvinyl alcohol, polyethylene glycol, and polyvinyl pyrrolidone, but is not limited thereto.

[0043] In some embodiments, the particle size of the light-controlled shape memory microcapsule is 5 to 55 μm (for example, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or 55 μm, etc.). This micrometer-scale particle size makes the light-controlled shape memory microcapsule more suitable for in vivo application.

[0044] The present invention also provides a method for preparing the light-controlled shape memory microcapsule as described above in the present invention, which comprises the following steps:

[0045] S1, adding the two-dimensional photothermal nanomaterial and the thermal responsive shape memory polymer material into an organic solvent, and dispersing them by ultrasonication to obtain a dispersion;

[0046] S2. providing a water-soluble polymer material solution, mixing the water-soluble polymer material solution with the dispersion, and stirring at a rotation speed of 800 to 1200 rpm to obtain the light-controlled shape memory microcapsule.

[0047] In an embodiment of the present invention, a two-dimensional photothermal nanomaterial and a thermally responsive shape memory polymer material are added to an organic solvent and ultrasonically dispersed. The obtained dispersion is used as the oil phase, and a water-soluble polymer material solution is used as the water phase. The oil-in-water emulsion volatilization method is used to disperse the oil phase and the water-soluble polymer material solution by high-speed magnetic stirring to form oil-in-water droplets on the one hand, and on the other hand, the solvent of the oil phase (i.e., the above-mentioned organic solvent) is evaporated as much as possible through the action of high-speed stirring. Finally, the water-soluble polymer material is coated with the two-dimensional photothermal nanomaterial and the thermally responsive shape memory polymer material to form light-controlled shape memory microcapsules.

[0048] The preparation method provided by the embodiment of the present invention is simple and controllable, and the particle size of the prepared microcapsules is relatively uniform and adjustable. The addition of two-dimensional photothermal nanomaterials indirectly transforms the thermally responsive shape memory polymer material into a light-controlled shape memory material, thereby realizing the light-controlled shape memory characteristics of the microcapsules and efficient in vitro remote control characteristics. At the same time, due to the advantages of the microscale, the microcapsules are easier to use in vivo.

[0049] In this embodiment, the specific selection of the two-dimensional photothermal nanomaterial, the thermally responsive shape memory polymer material, and the water-soluble polymer material is as described above and will not be repeated here.

[0050] In some embodiments, the mass ratio of the two-dimensional photothermal nanomaterial, the thermally responsive shape memory polymer material and the water-soluble polymer material in the water-soluble polymer material solution is (0.5-2):(10-40):

[0051] (37.5-150), for example, it can be 0.5:10:37.5, 0.5:25:78, 0.5:40:150, 1:10:37.5, 1:25:78, 1:40:150, 2:10:37.5, 2:25:78 or 2:40:150, etc.

[0052] In some embodiments, in the dispersion, the concentration of the two-dimensional photothermal nanomaterial is 0.5 to 2 mg / mL, for example, 0.5 mg / mL, 1 mg / mL, 1.2 mg / mL, 1.5 mg / mL, 1.8 mg / mL or 2 mg / mL.

[0053] In some embodiments, in the water-soluble polymer material solution, the concentration of the water-soluble polymer material is 1.25 to 5 mg / mL, for example, it can be 1.25 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL or 5 mg / mL, etc.

[0054] In some embodiments, the organic solvent includes at least one of dichloromethane and chloroform, but is not limited thereto.

[0055] In step S2, the water-soluble polymer material solution and the dispersion are mixed, stirred at a speed of 800 to 1200 rpm, and then centrifuged to obtain light-controlled shape memory microcapsules.

[0056] The embodiment of the present invention also provides an application of the light-controlled shape memory microcapsule as described above in the embodiment of the present invention in the preparation of tumor vascular embolic materials. The embodiment of the present invention also provides an application of the light-controlled shape memory microcapsule prepared by the preparation method as described above in the embodiment of the present invention in the preparation of tumor vascular embolic materials. The embodiment of the present invention also provides an application of the light-controlled shape memory microcapsule as described above in the embodiment of the present invention and the light-controlled shape memory microcapsule prepared by the preparation method as described above in the embodiment of the present invention in the preparation of tumor vascular embolic materials. The light-controlled shape memory microcapsule provided by the present invention has excellent light-controlled shape memory properties and can be used as an embolic material for embolic treatment of tumor blood vessels.

[0057] The present invention will be further described below by means of specific examples.

[0058] Example 1

[0059] This embodiment provides a method for preparing light-controlled shape memory microcapsules, comprising the following steps:

[0060] (1) Preparation of MXene nanosheets (prepared by in situ etching away the Al atomic layer in Ti3AlC2 using a mixture of HCl and LiF)

[0061] 3.2 g of LiF was dissolved in 40 mL of hydrochloric acid (wherein the concentration of HCl was 9 mol / L), and then 2 g of Ti3AlC2 powder was slowly added (the addition process took about 15 minutes) to obtain a suspension.

[0062] The suspension was placed at 40°C, stirred at 600 rpm, and etched for 35 hours, then washed with deionized water and centrifuged three times (each centrifugation was performed at 3500 rpm for 5 minutes) until the pH value of the supernatant was 6. Then, vacuum filtration (0.22 μm cellulose membrane) and freeze drying were performed to obtain multilayer MXene nanosheets (i.e., multilayer Ti3C2 nanosheets).

[0063] 400 mg of multilayer Ti3C2 nanosheets were dispersed in 100 mL of deionized water, and ultrasonically treated at a power of 300 W for 4 hours in an ice water bath under argon protection, followed by centrifugation at a speed of 3500 rpm for 60 minutes to obtain a monolayer MXene colloidal solution, that is, a monolayer Ti3C2 nanosheet.

[0064] (2) Preparation of light-controlled shape memory microcapsules

[0065] 100 mg of poly (D, L-lactic acid) (PDLLA, glass transition temperature Tg = 41 ° C) was dissolved in 5 mL of dichloromethane by magnetic stirring. Then, 1 mL of the above solution was taken, 1 mg of single-layer Ti3C2 nanosheets was added thereto, and ultrasonic dispersion was uniformly performed using a probe with a power of 130 W to obtain a dispersion.

[0066] The above dispersion was added to 30 mL of a 0.25 wt% polyvinyl alcohol aqueous solution (i.e., the concentration of polyvinyl alcohol in the polyvinyl alcohol aqueous solution was about 2.506 mg / mL), and high-speed magnetic stirring was performed at a speed of 1200 rpm (the purpose of high-speed magnetic stirring is, on the one hand, to form oil-in-water droplets, and secondly, to evaporate dichloromethane as much as possible through stirring). After stirring overnight, centrifugation was performed at a speed of 2000 rpm to collect light-controlled shape memory microcapsules (referred to as MXene / PDLLA microcapsules), and washed with water twice.

[0067] Comparative Example 1

[0068] This embodiment provides a method for preparing microcapsules (not containing Ti3C2 nanosheets), comprising the following steps:

[0069] 100 mg of PDLLA was dissolved in 5 mL of dichloromethane by magnetic stirring to obtain a dispersion.

[0070] Take 1 mL of the above dispersion and add it into 30 mL of 0.25 wt% polyvinyl alcohol aqueous solution, and stir it with high-speed magnetic stirring at 1200 rpm. After stirring overnight, centrifuge it at 2000 rpm, collect microcapsules (referred to as PDLLA microcapsules), and wash them with water twice.

[0071] test:

[0072] (1) The UV-visible-near infrared absorption spectrum of the single-layer Ti3C2 nanosheet prepared in Example 1 in aqueous solution is shown in Figure 1 As shown, it can be seen that it presents an obvious absorption peak near the 808nm region, thus proving that it has excellent light absorption properties for near-infrared light.

[0073] (2) The transmission electron microscopy image of the single-layer Ti3C2 nanosheet prepared in Example 1 is as follows Figure 2 As shown, it can be seen that the small-sized single-layer Ti3C2 nanosheets have good monodispersity and uniform size, and their lateral size is about 100nm.

[0074] (3) The MXene / PDLLA microcapsules prepared in Example 1 were tested by scanning electron microscopy (SEM). The results are as follows: Figure 3 As shown, it can be seen that the prepared microcapsules are relatively uniform spherical and have good dispersion.

[0075] (4) The particle size analysis test of the MXene / PDLLA microcapsules prepared in Example 1 was performed. The results are as follows Figure 4 As shown, it can be seen that the average size of the prepared microcapsules is 26 μm.

[0076] (5) The MXene / PDLLA microcapsules prepared in Example 1 were subjected to energy spectrum (EDS) testing. The results are as follows: Figure 5 As shown, it can be seen that it contains a higher intensity of Ti element content, which proves the successful encapsulation of Ti3C2 nanosheets.

[0077] (6) Photothermal performance test

[0078] The MXene / PDLLA microcapsules prepared in Example 1 were added into ultrapure water to prepare a MXene / PDLLA microcapsule solution with a concentration of 50 μg / mL.

[0079] Take 1 mL of MXene / PDLLA microcapsule solution with a concentration of 50 μg / mL and use a power density of 1.0 W / cm 2 The samples were irradiated with 808 nm laser for 5 min. The PDLLA microcapsules and water in Comparative Example 1 were used as the control group under the same irradiation conditions. The temperature was recorded in real time using an infrared camera (Fotric 220). Figure 6 As shown, it can be seen that compared with PDLLA microcapsules and pure water, MXene / PDLLA microcapsules have a significant photothermal warming effect, rising from room temperature to 63.2°C in 10 minutes.

[0080] (7) Light-controlled shape memory performance test

[0081] The shape memory process uses SEM to photograph the memory morphology of the microcapsules. The specific process is as follows:

[0082] The MXene / PDLLA microcapsules prepared in Example 1 (SEM images of which are shown in FIG. Figure 7The MXene / PDLLA microcapsules (shown in (a) in the figure, which are spherical) are uniformly dispersed in a mixed solution of polyvinyl alcohol and glycerol (wherein the mass content of polyvinyl alcohol is 10% and the mass content of glycerol is 2%), and then air-dried at room temperature after coating. The formed film is stretched at a constant speed by 2 times using an automatic film stretching machine, and then the stretched film is dissolved in an aqueous solution, and finally centrifuged to obtain spindle-shaped MXene / PDLLA microcapsules (whose SEM is shown in FIG. Figure 7 (b) as a temporary shape of shape memory.

[0083] The spindle-shaped MXene / PDLLA microcapsules were added into ultrapure water to prepare a spindle-shaped MXene / PDLLA microcapsule solution with a concentration of 50 μg / mL. 1 mL of the spindle-shaped MXene / PDLLA microcapsule solution with a concentration of 50 μg / mL was taken and placed in a vacuum chamber with a power density of 1.0 W / cm 2 After irradiation with 808 nm laser for 5 min, the shuttle-shaped MXene / PDLLA microcapsules returned to their original shape, i.e., spherical (the SEM image of which is shown in Figure 2). Figure 7 (as shown in (c)).

[0084] It can be seen that the MXene / PDLLA microcapsules prepared in Example 1 can be stretched from the original form to a temporary form, and can gradually return to the original form under near-infrared light irradiation. It has excellent light-controlled shape memory properties and can be used in embolization treatment of tumor blood vessels.

[0085] (8) Cytotoxicity test

[0086] Mouse mononuclear macrophage leukemia cells (RAW 264.7) were seeded into 96-well plates at a density of 1×10 per well. 4 cells and cultured in a 5% CO2 incubator at 37°C for 24 hours. Subsequently, the original culture medium was replaced with 200 μL of fresh culture medium containing different concentrations (0 μg / mL, 1.25 μg / mL, 2.5 μg / mL, 5 μg / mL, 10 μg / mL, 20 μg / mL, 50 μg / mL and 100 μg / mL) of MXene / PDLLA microcapsules. After incubation for 24 hours, the culture medium was replaced with 10% CCK-8 culture medium and incubated for another 60 minutes. The absorbance at 450 nm was tested using a microplate reader (FilterMax F5, Molecular Devices, USA) for measuring cell viability. The results are shown in Figure 8 As shown. Even at a high concentration of 100 μg / mL, the MXene / PDLLA microcapsules still maintain more than 90% of cell activity, proving that the MXene / PDLL microcapsules provided by the present invention have excellent biosafety and can be used for embolization therapy of tumor blood vessels.

[0087] In summary, the present invention provides a light-controlled shape memory microcapsule and a preparation method and application thereof. The present invention is based on a thermally responsive shape memory polymer material, and by adding a two-dimensional photothermal nanomaterial, the two-dimensional photothermal nanomaterial and the thermally responsive shape memory polymer material cooperate. The two-dimensional photothermal nanomaterial has a photothermal effect. When a certain wavelength of light is used, the temperature rises, thereby promoting the shape memory effect of the thermally responsive shape memory polymer material, thereby giving the microcapsule a light-controlled shape memory ability, so that the microcapsule can be remotely regulated in vitro, thereby increasing the controllability of the shape memory performance of the microcapsule.

[0088] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A light-controlled shape memory microcapsule, characterized in that: The light-controlled shape memory microcapsule comprises a capsule core and a capsule wall covering the capsule core, the capsule core comprises a two-dimensional photothermal nanomaterial and a thermally responsive shape memory polymer material, and the capsule wall comprises a water-soluble polymer material.

2. The light-controlled shape memory microcapsule according to claim 1, characterized in that: The two-dimensional photothermal nanomaterial is a biodegradable two-dimensional photothermal nanomaterial.

3. The light-controlled shape memory microcapsule according to claim 2, characterized in that: The biodegradable two-dimensional photothermal nanomaterial includes at least one of a two-dimensional MXene nanosheet, a two-dimensional niobium selenide nanosheet, and a two-dimensional bismuth oxide selenide nanosheet.

4. The light-controlled shape memory microcapsule according to claim 1, characterized in that: The thermally responsive shape memory polymer material includes at least one of poly (D, L-lactic acid), poly (D, lactide-trimethylene carbonate), polyurethane and polylactic acid.

5. The light-controlled shape memory microcapsule according to claim 1, characterized in that: The water-soluble polymer material includes at least one of polyvinyl alcohol, polyethylene glycol and polyvinyl pyrrolidone.

6. The light-controlled shape memory microcapsule according to claim 1, characterized in that: The particle size of the light-controlled shape memory microcapsule is 5 to 55 μm.

7. A method for preparing the light-controlled shape memory microcapsule according to claim 1, characterized in that: The steps include: The two-dimensional photothermal nanomaterial and the thermal responsive shape memory polymer material are added into an organic solvent and dispersed by ultrasonication to obtain a dispersion; A water-soluble polymer material solution is provided, and the water-soluble polymer material solution is mixed with the dispersion, and stirred at a rotation speed of 800 to 1200 rpm to obtain the light-controlled shape memory microcapsule.

8. The preparation method according to claim 7, characterized in that: The mass ratio of the two-dimensional photothermal nanomaterial, the thermally responsive shape memory polymer material and the water-soluble polymer material in the water-soluble polymer material solution is (0.5-2):(10-40):(37.5-150); In the dispersion, the concentration of the two-dimensional photothermal nanomaterial is 0.5 to 2 mg / mL; In the water-soluble polymer material solution, the concentration of the water-soluble polymer material is 1.25-5 mg / mL.

9. The preparation method according to claim 7, characterized in that: The organic solvent includes at least one of dichloromethane and chloroform.

10. Use of the light-controlled shape memory microcapsule according to any one of claims 1 to 6 and / or the light-controlled shape memory microcapsule prepared by the preparation method according to any one of claims 7 to 9 in preparing tumor vascular embolization materials.

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