CN113332499A - Self-temperature-control photothermal effect microsphere and preparation method thereof - Google Patents
Self-temperature-control photothermal effect microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of medical materials, in particular to a self-temperature-control photothermal effect microsphere and a preparation method thereof. The microsphere comprises a core layer and a shell layer from inside to outside, the shell layer is formed by coating a core body structure of nanoparticles containing a photo-thermal effect by using a tungsten-doped vanadium dioxide/hydrogel intermediate, the self-temperature-control thermotherapy microsphere is obtained by utilizing the influence of W doping on the phase transition temperature of the vanadium dioxide nanoparticles, and the local temperature of a focus can be accurately controlled through photo-thermal conversion. According to the invention, W is added to the shell to dope vanadium dioxide nano-particles, the temperature of the microspheres is regulated and controlled through the phase transition temperature, and when the doping amount of tungsten is 1.5-1.85%, the temperature can be controlled to be 40-55 ℃. The dosage and the type of the hydrogel intermediate, the anion cross-linking agent and the nano-particles or the tungsten-doped vanadium dioxide nano-particles in the core layer and the shell layer are controlled, and the obtained microspheres have good elasticity and drug-loading performance.
Description
Technical Field
The invention relates to the field of medical materials, in particular to a self-temperature-control photothermal effect microsphere and a preparation method thereof.
Background
Nearly millions of patients with liver cancer are newly increased every year around the world, wherein China accounts for +55 percent. Liver cancer is the second largest cancer in China, second only to lung cancer, and more than 40 million operations are performed on liver cancer patients every year. Since liver cancer is a silent disease, with no symptoms in the early stage and a fast progression of the disease, most patients are found in the middle and late stages. For patients with middle and late stage liver cancer, the procedure of transcatheter arterial embolization chemotherapy (TACE) is basically performed according to clinical guidelines. TACE has first achieved embolization of diseased tumor arteries by injection of iodized oil, and subsequently, gelatin sponge particles, PVA particles, microspheres, drug-loaded microspheres, and the like, and even radioactive microspheres with radiotherapy effects, have been developed in succession.
In recent years, researchers have utilized photothermal effects of some special materials, such as nano gold particles, carbon nanotubes, nano dopamine particles, to combine them with drugs. The nano particles with the photothermal effect are enriched at the tumor focus part by utilizing drug targeting molecules. Because cancer cells are generally less heat resistant than normal tissue cells. The molecules with the photo-thermal effect can convert energy into heat energy by absorbing infrared light energy of an external field to improve the peripheral local temperature of tumor tissues. Thereby achieving the effect of killing cancer cells. However, no attempts have been made to combine such photothermal materials with medical devices. Because such instruments have to satisfy two basic conditions: 1, the instrument can accurately reach a tumor focus; 2, the local temperature of the focus can be accurately controlled by the photothermal conversion.
Obviously, a medical device that satisfies both of the above two conditions is very difficult. There are few medical devices that can accurately place a photothermal material on a tumor lesion at first. Either a percutaneous needle or various interventional devices introduced through an arterial interventional catheter. The percutaneous puncture probe can generate energy through radio frequency or microwave to achieve an ablation effect. Except that it is more damaging to normal tissue. Can achieve the treatment effect on early and middle-early liver cancer patients. Such devices do not require materials that rely on the photothermal effect. The temperature control of the thermocouple for interventional devices such as a spring ring, an embolization microsphere, a liquid embolization agent and the like is difficult to realize, and the combination of the photothermal material and a medical device is limited.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a self-temperature-controlling photothermal effect microsphere, which comprises, from inside to outside, a core layer and a shell layer, wherein the core layer is prepared from raw materials comprising a hydrogel intermediate, nanoparticles and an anionic crosslinking agent; the shell layer is prepared from the raw materials of a hydrogel intermediate, tungsten-doped vanadium dioxide and an anionic cross-linking agent.
As a preferred embodiment of the present invention, the hydrogel intermediate is prepared from a polyol and an acrylamide dialkoxyalkyl acetal.
In a preferred embodiment of the present invention, the polyol is one or more selected from polyvinyl alcohol, polyethylene glycol, polypropylene glycol, chitosan, and starch.
As a preferred technical solution of the present invention, the nanoparticles are selected from one or more of nanogold, carbon nanotubes, and nano dopamine.
As a preferable technical scheme of the invention, the doping amount of tungsten of the tungsten-doped vanadium dioxide is 1.5-1.85%.
As a preferred technical scheme of the invention, the anionic crosslinking agent is selected from one or more of 2-acrylamide-2-methylpropane carboxylate, 2-acrylamide-2-methylpropane sulfonate, allyl sulfonate and 1-propylene-oxy-2-hydroxypropane sulfonate sodium salt.
According to a preferable technical scheme of the invention, in the preparation raw materials of the core layer, the weight ratio of the hydrogel intermediate, the anionic cross-linking agent and the nano particles is (70-90): (4-8): (6-22).
As a preferred technical scheme, in the preparation raw materials of the shell layer, the weight ratio of the hydrogel intermediate, the anionic cross-linking agent and the tungsten-doped vanadium dioxide is (70-90): (4-8): (6-22).
As a preferable technical scheme, the weight ratio of the core layer to the shell layer is 1: (1.5-5).
The second aspect of the invention provides a preparation method of the self-temperature-control photothermal effect microsphere, which comprises the following steps:
preparation of a nuclear layer: adding water into the nuclear layer preparation raw materials, mixing, and adding the mixture into an organic solvent for reaction to obtain a nuclear layer mixture;
preparing a shell layer: and adding water into the shell layer preparation raw material, mixing, adding the mixture into the core layer mixture, reacting, filtering, washing and drying to obtain the microsphere.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method comprises the steps of designing microspheres with core-shell structures, wherein tungsten doped vanadium dioxide/hydrogel intermediates are used for shell layers to coat core body structures of nano-particles with photo-thermal effects, the self-temperature-control thermotherapy microspheres are obtained by utilizing the influence of W doping on the phase transition temperature of the vanadium dioxide nano-particles, and the local temperature of focus can be accurately controlled through photo-thermal conversion.
(2) In the invention, W-doped vanadium dioxide nano-particles are added to the shell layer, and VO is generated when the shell layer is higher than the phase transition temperature2The monoclinic semiconductor phase is transformed into a metal tetragonal phase, so that the transmittance of infrared rays is reduced to zero, and the total reflection is shown for the infrared rays, so that the external infrared rays cannot transmit VO2And below the phase transition temperature, infrared rays can transmit VO2The temperature of the microsphere is regulated and controlled through the phase transition temperature, and when the doping amount of tungsten is 1.5-1.85%, the temperature can be controlled to be 40-55 ℃.
(3) The dosage and the type of the hydrogel intermediate, the anionic cross-linking agent and the nano-particles or the tungsten-doped vanadium dioxide nano-particles in the core layer and the shell layer are controlled, and the reverse suspension polymerization mode is used, so that the obtained microspheres have good elasticity and drug-loading property, can avoid agglomeration among particles, improve the cross-linking degree, and avoid reduction of hydrophilicity and suspension property.
(4) The self-temperature-control photothermal effect microsphere obtained by the invention has stable property, smooth outer surface, similar spherical shape, good fluidity, no bonding and the like.
Drawings
Fig. 1 is a schematic structural diagram of the microsphere, wherein an inner dot 1 represents a nanoparticle, and an outer dot 2 represents a tungsten-doped vanadium dioxide nanoparticle.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
As shown in fig. 1, the first aspect of the present invention provides a self-temperature-controlling photothermal effect microsphere, which comprises, from inside to outside, a core layer and a shell layer, wherein the core layer is prepared from raw materials comprising a hydrogel intermediate, nanoparticles and an anionic crosslinking agent; the shell layer is prepared from the raw materials of a hydrogel intermediate, tungsten-doped vanadium dioxide and an anionic cross-linking agent.
Nuclear layer
In one embodiment, in the raw materials for preparing the core layer, the weight ratio of the hydrogel intermediate, the anionic crosslinking agent and the nanoparticles is (70-90): (4-8): (6 to 22), there may be mentioned, for example, 70: 8: 22. 90: 4: 6. 75: 7: 18. 80: 6: 14. 85: 5: 10.
the hydrogel intermediate is used as a matrix material of a core layer and a shell layer, is obtained by crosslinking through a crosslinking agent, and has good water absorption and elasticity. Preferably, the hydrogel intermediate of the present invention is prepared from a polyol and an acrylamide dialkoxyalkyl acetal in a weight ratio of 1: (0.01-0.05).
Examples of the polyhydric alcohol include polyvinyl alcohol, polyethylene glycol, polypropylene glycol, chitosan, and starch, and polyvinyl alcohol is preferable. In one embodiment, the polyvinyl alcohol has a number average molecular weight of 20000 to 50000. The statistical average by number of molecules is referred to as the number average molecular weight.
As an example of the acrylamide dialkoxyalkyl acetal, there may be mentioned N-acrylamidodimethoxyethyl acetal.
The present invention is not particularly limited to the method for preparing the hydrogel intermediate, and in one embodiment, the method for preparing the hydrogel intermediate comprises: adding polyhydric alcohol into water, mixing at 90-100 ℃, cooling to below 25 ℃, adding acrylamide dialkoxy alkyl acetal, mixing, dropwise adding hydrochloric acid, reacting for 6-7 h, washing, and drying to obtain the hydrogel intermediate.
The hydrochloric acid is 36 to 38 wt% aqueous hydrogen chloride solution and is used as a catalyst to promote the reaction of the polyhydric alcohol and the acrylamide dialkoxyalkyl acetal, and in one embodiment, the hydrochloric acid accounts for 30 to 60 wt% of the polyhydric alcohol.
More preferably, the anionic crosslinking agent of the present invention is selected from one or more of 2-acrylamide-2-methylpropane carboxylate, 2-acrylamide-2-methylpropane sulfonate, allyl sulfonate, and 1-acryloxy-2-hydroxypropane sulfonate sodium salt. The anionic crosslinking agent of the present invention may be potassium salt, sodium salt, etc. of carboxylic acid or sulfonic acid, and is not particularly limited, but is preferably 2-acrylamide-2-methylpropane carboxylate, 2-acrylamide-2-methylpropane sulfonate, and more preferably 2-acrylamide-2-methylpropane sulfonate.
The nano particles are substances with photo-thermal effect, and the photo-thermal effect refers to the fact that after the materials are irradiated by light, photon energy interacts with crystal lattices, vibration is aggravated, temperature is increased, and the electric characteristics of the substances are caused by the change of the temperature. The photo-thermal conversion material can convert weak light energy in a near-infrared light region absorbed by a human body into heat energy, and selectively kill cancer cells and the like. Further preferably, the nanoparticle of the present invention is selected from one or more of nanogold, carbon nanotube and nano dopamine.
The nano-particles can be prepared or purchased by self, and are not particularly limited, for example, the nano-gold can be purchased from Beijing Anbiqi Biotech Co., Ltd, the carbon nano-tube can be purchased from Beijing German island gold Tech Co., Ltd, the nano-dopamine is the nano-particles of poly-dopamine, can be purchased from XianRexi Biotech Co., Ltd, or prepared by self, for example, 20-40 wt% of ammonia water is added into ethanol and water to obtain a mixed solution, the hydrochloric acid dopamine solution is dissolved in the water and added into the mixed solution, the mixed solution is stirred for 1-1.5 days, and the nano-dopamine is obtained by washing, centrifuging and drying.
Shell layer
In one embodiment, in the raw materials for preparing the shell layer, the weight ratio of the hydrogel intermediate, the anionic cross-linking agent and the tungsten-doped vanadium dioxide is (70-90): (4-8): (6 to 22), there may be mentioned, for example, 70: 8: 22. 90: 4: 6. 75: 7: 18. 80: 6: 14. 85: 5: 10. preferably, the weight ratio of the core layer to the shell layer is 1: (1.5 to 5), there may be mentioned, 1: 1.5, 1: 2. 1: 2.5, 1: 3. 1: 3.5, 1: 4. 1: 4.5, 1: 5.
more preferably, the doping amount of tungsten in the tungsten-doped vanadium dioxide is 1.5-1.85%. The doping amount is the percentage of tungsten in the tungsten-doped vanadium dioxide in the total elements of tungsten and vanadium, namely V in the element structural formula of the tungsten-doped vanadium dioxide1- xWxO2X in (1).
The tungsten-doped vanadium dioxide can be prepared by self or purchased, and when The tungsten-doped vanadium dioxide is prepared by self according to The methods provided by CN102295312B, Peng Z, Jiang W, Liu H.Synthesis and electronic properties of tungsten-doped vanadium dioxide nanoparticles by thermal catalysis [ J ]. The Journal of chemical Chemistry C,2007,111(3):1119-1122, Jianqiu, Fangxin, Yowabble, and The like, The preparation of tungsten-doped vanadium dioxide powder and The thermochromism performance [ J ]. multideck report (Nature science edition), and (2007 03):102-107 and The like, so that tungsten-doped vanadium dioxide with different doping amounts can be obtained.
Vanadium dioxide (vanadium (IV) oxide) is an oxide with the molecular formula of VO2The phase transition temperature of the metal-semiconductor is 68 ℃, and the metal-semiconductor phase transition material is widely applied to photoelectric switches and intelligent glass windows. VO at a temperature higher than 68 DEG C2The monoclinic semiconductor phase is transformed into a metal tetragonal phase, so that the transmittance of infrared rays is reduced to zero. The total reflection is shown for infrared rays, so that external infrared rays cannot transmit VO2. And when the temperature is lower than the phase transition temperature, the infrared ray can transmit VO2And (3) a layer. The applicants have found that as the doping level of tungsten increases, the phase transition temperature decreases. When the doping amount of W is 1.5-1.85%, the phase transition temperature can be controlled to 40-55 deg.C, for example, 43 deg.C when the doping amount of W is 1.7%.
The applicant finds that the phase transition temperature can be accurately regulated and controlled in a tungsten doping mode so as to control the temperature of the microspheres, but the dispersion uniformity of nanoparticles in a core-shell structure is influenced due to the agglomeration and adsorption phenomena of nanoparticles and tungsten doped vanadium dioxide, so that the microspheres are difficult to accurately control the temperature, the prepared microspheres are easy to adhere to each other, the problems of wide particle size distribution, poor surface smoothness of the microspheres and the like are caused, and the flowing and elasticity of the microspheres in blood vessels are influenced, and the applicant finds that the hydrogel intermediate, the crosslinking agent, the nanoparticles and the tungsten doped vanadium dioxide in core layer and shell layer materials are controlled by adopting the polyhydric alcohol with proper surface modification, so that on one hand, the acrylamide and the anionic crosslinking agent which are modified on the surface of the polyhydric alcohol can be promoted to be rapidly crosslinked, on the other hand, the nanoparticles are uniformly dispersed under charge exclusion and steric hindrance, promotes the accurate adjustment of the temperature of the microspheres and obtains the microspheres with smoothness and narrow particle size distribution.
Further preferably, the raw materials for preparing the core layer and the shell layer of the present invention include at least one of an initiator, an organic solvent, and a thickener. Examples of initiators include, but are not limited to, persulfates, such as potassium persulfate, sodium persulfate, ammonium persulfate, 2,2' azobisisobutylamidine dihydrochloride, tert-butyl hydroperoxide, hydrogen peroxide, cumene hydroperoxide, tetramethylethylenediamine, preferably a mixture of persulfates and tetramethylethylenediamine. As examples of the organic solvent, ester solvents such as ethyl acetate, butyl acetate, propyl acetate and the like can be cited. As examples of the thickener, cellulose acetate, methyl cellulose, carboxymethyl cellulose may be cited.
The specific use amounts of the initiator, the organic solvent and the thickener are not specifically limited, and in one embodiment, in the core layer preparation raw materials, the weight ratio of persulfate to the total weight of the hydrogel intermediate, the nanoparticles and the anionic crosslinking agent is (3-6): (50-100), wherein the weight ratio of the tetramethylethylenediamine to the total weight of the hydrogel intermediate, the nanoparticles and the anionic crosslinking agent is (1-5): (50-100), wherein the weight ratio of the thickening agent to the total weight of the hydrogel intermediate, the nanoparticles and the anionic crosslinking agent is (2-4): (50-100); in the shell layer preparation raw materials, the weight ratio of persulfate to the total weight of the hydrogel intermediate, the tungsten-doped vanadium dioxide and the anion crosslinking agent is (3-6): (50-100), wherein the weight ratio of the tetramethylethylenediamine to the total weight of the hydrogel intermediate, the tungsten-doped vanadium dioxide and the anionic crosslinking agent is (1-5): (50-100), wherein the weight ratio of the thickening agent to the total weight of the hydrogel intermediate, the tungsten-doped vanadium dioxide and the anionic crosslinking agent is (2-4): (50-100).
The second aspect of the present invention provides a preparation method of the self-temperature-control photothermal effect microsphere, including:
preparation of a nuclear layer: adding water into the nuclear layer preparation raw materials, mixing, and adding the mixture into an organic solvent for reaction to obtain a nuclear layer mixture;
preparing a shell layer: and adding water into the shell layer preparation raw material, mixing, adding the mixture into the core layer mixture, reacting, filtering, washing and drying to obtain the microsphere.
In one embodiment, in the core layer preparation, the anionic cross-linking agent, the persulfate, the hydrogel intermediate and the nanoparticles in the raw materials for core layer preparation are added into water and mixed to obtain a water phase; and introducing nitrogen into the organic solvent and the thickening agent in the core layer preparation raw material, mixing, heating to 50-75 ℃, sequentially adding the water phase and the tetramethyl ethylenediamine in the core layer preparation raw material, and reacting for 2-4 hours to obtain a core layer mixture.
In one embodiment, in the shell preparation, persulfate, an anionic crosslinking agent, a hydrogel intermediate and tungsten-doped vanadium dioxide in shell preparation raw materials are added into water and mixed, and then the mixture is added into a core-layer mixture and mixed to obtain a shell mixture; mixing an organic solvent and a thickening agent in the shell layer preparation raw material, introducing nitrogen gas, mixing, heating to 50-75 ℃, sequentially adding the shell layer mixture and tetramethylethylenediamine in the shell layer preparation raw material, reacting for 5-7 h, filtering, washing and drying to obtain the microsphere.
Examples
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Example 1
As shown in fig. 1, the present example provides a microsphere, which includes a core layer and a shell layer from inside to outside, wherein the core layer is prepared from raw materials including a hydrogel intermediate, an anionic crosslinking agent, and nanoparticles, and the weight ratio of the core layer to the shell layer is 85: 5: 10, the raw materials for preparing the core layer further comprise sodium persulfate, tetramethylethylenediamine and cellulose acetate, wherein the sodium persulfate, the tetramethylethylenediamine and the cellulose acetate respectively account for 3: 100. 2: 100. 4: 100, respectively; the shell layer is prepared from the following raw materials in parts by weight: 5: 10, the raw materials for preparing the core layer further comprise sodium persulfate, tetramethylethylenediamine and cellulose acetate, wherein the sodium persulfate, the tetramethylethylenediamine and the cellulose acetate respectively account for 3 parts by weight of the total weight of the hydrogel intermediate, the tungsten-doped vanadium dioxide and the anion cross-linking agent: 100. 2: 100. 4: 100.
the hydrogel intermediate is prepared from polyalcohol and acrylamide dialkoxy alkyl acetal, and the weight ratio of the polyalcohol to the acrylamide dialkoxy alkyl acetal is 1: 0.04. the preparation method of the hydrogel intermediate comprises the following steps: adding polyalcohol into water, mixing at 95 ℃, cooling to below 25 ℃, adding acrylamide dialkoxy alkyl acetal, mixing, dropwise adding hydrochloric acid, reacting for 6.5h, washing and drying to obtain the hydrogel intermediate, wherein the hydrochloric acid accounts for 40 wt% of the polyalcohol. The polyalcohol is polyvinyl alcohol (the number average molecular weight is 20000), and the acrylamide dialkoxy alkyl acetal is N-acrylamide dimethoxy ethyl acetal.
The anionic crosslinking agent is 2-acrylamide-2-methylpropanesulfonate.
The nano-particles are nano-gold purchased from Beijing Anbiqi Biotech limited.
The tungsten-doped vanadium dioxide is prepared according to the method provided by CN102295312B, and the doping amount of tungsten is 1.5%.
The embodiment also provides a preparation method of the self-temperature-control photothermal effect microsphere, which comprises the following steps:
preparation of a nuclear layer: adding an anionic cross-linking agent, sodium persulfate, a hydrogel intermediate and nanoparticles in the core layer preparation raw materials into water, and mixing to obtain a water phase; introducing nitrogen into butyl acetate and cellulose acetate in the nuclear layer preparation raw material for mixing, heating to 70 ℃, sequentially adding water phase and tetramethyl ethylenediamine in the nuclear layer preparation raw material, and reacting for 3 hours to obtain a nuclear layer mixture;
preparing a shell layer: adding sodium persulfate, an anion cross-linking agent, a hydrogel intermediate and tungsten-doped vanadium dioxide in raw materials for preparing the shell into water, mixing, adding the mixture into the nuclear layer mixture, and mixing to obtain a shell layer mixture; mixing butyl acetate and cellulose acetate in the shell preparation raw material, introducing nitrogen for mixing, heating to 70 ℃, sequentially adding the shell mixture and tetramethyl ethylenediamine in the shell preparation raw material, reacting for 6 hours, filtering, washing and drying to obtain the microsphere.
Example 2
As shown in fig. 1, the present example provides a microsphere, which includes a core layer and a shell layer from inside to outside, wherein the core layer is prepared from raw materials including a hydrogel intermediate, an anionic crosslinking agent, and nanoparticles, and the weight ratio of the core layer to the shell layer is 75: 7: 18, the raw materials for preparing the core layer further comprise potassium persulfate, tetramethylethylenediamine and cellulose acetate, wherein the weight ratio of the potassium persulfate, the tetramethylethylenediamine and the cellulose acetate in the total weight of the hydrogel intermediate, the nanoparticles and the anionic crosslinking agent is 5: 100. 4: 100. 4: 100, respectively; the shell layer is prepared from raw materials including a hydrogel intermediate, tungsten-doped vanadium dioxide and an anion cross-linking agent in a weight ratio of 75: 7: 18, the raw materials for preparing the core layer further comprise potassium persulfate, tetramethylethylenediamine and cellulose acetate, wherein the weight ratio of the potassium persulfate, the tetramethylethylenediamine and the cellulose acetate in the total weight of the hydrogel intermediate, the tungsten-doped vanadium dioxide and the anionic crosslinking agent is 5: 100. 4: 100. 4: 100.
the hydrogel intermediate is prepared from polyalcohol and acrylamide dialkoxy alkyl acetal, and the weight ratio of the polyalcohol to the acrylamide dialkoxy alkyl acetal is 1: 0.02. the preparation method of the hydrogel intermediate comprises the following steps: adding polyalcohol into water, mixing at 95 ℃, cooling to below 25 ℃, adding acrylamide dialkoxy alkyl acetal, mixing, dropwise adding hydrochloric acid, reacting for 6.5h, washing and drying to obtain the hydrogel intermediate, wherein the hydrochloric acid accounts for 40 wt% of the polyalcohol. The polyalcohol is polyvinyl alcohol (the number average molecular weight is 40000), and the acrylamide dialkoxy alkyl acetal is N-acrylamido dimethoxy ethyl acetal.
The anionic crosslinking agent is 2-acrylamide-2-methyl propane carboxylate.
The nanoparticles are nano dopamine and are purchased from sienna millennium biotechnology limited.
The tungsten-doped vanadium dioxide is prepared according to the method provided by CN102295312B, and the doping amount of tungsten is 1.85%.
The embodiment also provides a preparation method of the self-temperature-control photothermal effect microsphere, which comprises the following steps:
preparation of a nuclear layer: adding an anionic cross-linking agent, potassium persulfate, a hydrogel intermediate and nanoparticles in the core layer preparation raw materials into water, and mixing to obtain a water phase; introducing nitrogen into butyl acetate and cellulose acetate in the nuclear layer preparation raw material for mixing, heating to 65 ℃, sequentially adding water phase and tetramethyl ethylenediamine in the nuclear layer preparation raw material, and reacting for 4 hours to obtain a nuclear layer mixture;
preparing a shell layer: adding potassium persulfate, an anion cross-linking agent, a hydrogel intermediate and tungsten-doped vanadium dioxide in shell preparation raw materials into water, mixing, adding into the core-layer mixture, and mixing to obtain a shell mixture; mixing butyl acetate and cellulose acetate in the shell preparation raw material, introducing nitrogen for mixing, heating to 70 ℃, sequentially adding the shell mixture and tetramethyl ethylenediamine in the shell preparation raw material, reacting for 7 hours, filtering, washing and drying to obtain the microsphere.
Example 3
As shown in fig. 1, the present example provides a microsphere, which includes a core layer and a shell layer from inside to outside, wherein the core layer is prepared from raw materials including a hydrogel intermediate, an anionic crosslinking agent, and nanoparticles, and the weight ratio of the core layer to the shell layer is 80: 6: 14, the raw materials for preparing the core layer further comprise sodium persulfate, tetramethylethylenediamine and cellulose acetate, wherein the weight ratio of the sodium persulfate, the tetramethylethylenediamine and the cellulose acetate in the total weight of the hydrogel intermediate, the nanoparticles and the anionic crosslinking agent is 4: 100. 3: 100. 3: 100, respectively; the shell layer is prepared from the following raw materials in parts by weight: 6: 14, the raw materials for preparing the core layer further comprise sodium persulfate, tetramethylethylenediamine and cellulose acetate, wherein the sodium persulfate, the tetramethylethylenediamine and the cellulose acetate respectively account for 4: 100. 3: 100. 3: 100.
the hydrogel intermediate is prepared from polyalcohol and acrylamide dialkoxy alkyl acetal, and the weight ratio of the polyalcohol to the acrylamide dialkoxy alkyl acetal is 1: 0.03. the preparation method of the hydrogel intermediate comprises the following steps: adding polyalcohol into water, mixing at 95 ℃, cooling to below 25 ℃, adding acrylamide dialkoxy alkyl acetal, mixing, dropwise adding hydrochloric acid, reacting for 6.5h, washing and drying to obtain the hydrogel intermediate, wherein the hydrochloric acid accounts for 40 wt% of the polyalcohol. The polyalcohol is polyvinyl alcohol (the number average molecular weight is 30000), and the acrylamide dialkoxy alkyl acetal is N-acrylamido dimethoxy ethyl acetal.
The anionic crosslinking agent is 2-acrylamide-2-methylpropanesulfonate.
The nanoparticles are nano dopamine and are purchased from sienna millennium biotechnology limited.
The tungsten-doped vanadium dioxide is prepared according to the method provided by CN102295312B, and the doping amount of tungsten is 1.7%.
The embodiment also provides a preparation method of the self-temperature-control photothermal effect microsphere, which comprises the following steps:
preparation of a nuclear layer: adding an anionic cross-linking agent, sodium persulfate, a hydrogel intermediate and nanoparticles in the core layer preparation raw materials into water, and mixing to obtain a water phase; introducing nitrogen into butyl acetate and cellulose acetate in the nuclear layer preparation raw material for mixing, heating to 70 ℃, sequentially adding water phase and tetramethyl ethylenediamine in the nuclear layer preparation raw material for reacting for 3.5 hours to obtain a nuclear layer mixture;
preparing a shell layer: adding sodium persulfate, an anion cross-linking agent, a hydrogel intermediate and tungsten-doped vanadium dioxide in raw materials for preparing the shell into water, mixing, adding the mixture into the nuclear layer mixture, and mixing to obtain a shell layer mixture; mixing butyl acetate and cellulose acetate in the shell preparation raw material, introducing nitrogen for mixing, heating to 70 ℃, sequentially adding the shell mixture and tetramethyl ethylenediamine in the shell preparation raw material, reacting for 6.5 hours, filtering, washing and drying to obtain the microsphere.
Example 4
As shown in fig. 1, the present example provides a microsphere, which includes a core layer and a shell layer from inside to outside, wherein the core layer is prepared from raw materials including a hydrogel intermediate, an anionic crosslinking agent, and nanoparticles, and the weight ratio of the core layer to the shell layer is 82: 3: 15, the raw materials for preparing the core layer further comprise sodium persulfate, tetramethylethylenediamine and cellulose acetate, wherein the weight ratio of the sodium persulfate, the tetramethylethylenediamine and the cellulose acetate in the total weight of the hydrogel intermediate, the nanoparticles and the anionic crosslinking agent is 4: 100. 3: 100. 3: 100, respectively; the shell layer is prepared from the following raw materials in parts by weight: 6: 14, the raw materials for preparing the core layer further comprise sodium persulfate, tetramethylethylenediamine and cellulose acetate, wherein the sodium persulfate, the tetramethylethylenediamine and the cellulose acetate respectively account for 4: 100. 3: 100. 3: 100.
the hydrogel intermediate is prepared from polyalcohol and acrylamide dialkoxy alkyl acetal, and the weight ratio of the polyalcohol to the acrylamide dialkoxy alkyl acetal is 1: 0.03. the preparation method of the hydrogel intermediate comprises the following steps: adding polyalcohol into water, mixing at 95 ℃, cooling to below 25 ℃, adding acrylamide dialkoxy alkyl acetal, mixing, dropwise adding hydrochloric acid, reacting for 6.5h, washing and drying to obtain the hydrogel intermediate, wherein the hydrochloric acid accounts for 40 wt% of the polyalcohol. The polyalcohol is polyvinyl alcohol (the number average molecular weight is 30000), and the acrylamide dialkoxy alkyl acetal is N-acrylamido dimethoxy ethyl acetal.
The anionic crosslinking agent is 2-acrylamide-2-methylpropanesulfonate.
The nanoparticles are nano dopamine and are purchased from sienna millennium biotechnology limited.
The tungsten-doped vanadium dioxide is prepared according to the method provided by CN102295312B, and the doping amount of tungsten is 1.7%.
The embodiment also provides a preparation method of the self-temperature-control photothermal effect microsphere, which comprises the following steps:
preparation of a nuclear layer: adding an anionic cross-linking agent, sodium persulfate, a hydrogel intermediate and nanoparticles in the core layer preparation raw materials into water, and mixing to obtain a water phase; introducing nitrogen into butyl acetate and cellulose acetate in the nuclear layer preparation raw material for mixing, heating to 70 ℃, sequentially adding water phase and tetramethyl ethylenediamine in the nuclear layer preparation raw material for reacting for 3.5 hours to obtain a nuclear layer mixture;
preparing a shell layer: adding sodium persulfate, an anion cross-linking agent, a hydrogel intermediate and tungsten-doped vanadium dioxide in raw materials for preparing the shell into water, mixing, adding the mixture into the nuclear layer mixture, and mixing to obtain a shell layer mixture; mixing butyl acetate and cellulose acetate in the shell preparation raw material, introducing nitrogen for mixing, heating to 70 ℃, sequentially adding the shell mixture and tetramethyl ethylenediamine in the shell preparation raw material, reacting for 6.5 hours, filtering, washing and drying to obtain the microsphere.
Example 5
As shown in fig. 1, the present example provides a microsphere, which includes a core layer and a shell layer from inside to outside, wherein the core layer is prepared from raw materials including a hydrogel intermediate, an anionic crosslinking agent, and nanoparticles, and the weight ratio of the core layer to the shell layer is 80: 6: 14, the raw materials for preparing the core layer further comprise sodium persulfate, tetramethylethylenediamine and cellulose acetate, wherein the weight ratio of the sodium persulfate, the tetramethylethylenediamine and the cellulose acetate in the total weight of the hydrogel intermediate, the nanoparticles and the anionic crosslinking agent is 4: 100. 3: 100. 3: 100, respectively; the shell layer is prepared from the following raw materials in parts by weight: 3: 15, the raw materials for preparing the core layer further comprise sodium persulfate, tetramethylethylenediamine and cellulose acetate, wherein the sodium persulfate, the tetramethylethylenediamine and the cellulose acetate respectively account for 4 parts by weight of the total weight of the hydrogel intermediate, the tungsten-doped vanadium dioxide and the anion cross-linking agent: 100. 3: 100. 3: 100.
the hydrogel intermediate is prepared from polyalcohol and acrylamide dialkoxy alkyl acetal, and the weight ratio of the polyalcohol to the acrylamide dialkoxy alkyl acetal is 1: 0.03. the preparation method of the hydrogel intermediate comprises the following steps: adding polyalcohol into water, mixing at 95 ℃, cooling to below 25 ℃, adding acrylamide dialkoxy alkyl acetal, mixing, dropwise adding hydrochloric acid, reacting for 6.5h, washing and drying to obtain the hydrogel intermediate, wherein the hydrochloric acid accounts for 40 wt% of the polyalcohol. The polyalcohol is polyvinyl alcohol (the number average molecular weight is 30000), and the acrylamide dialkoxy alkyl acetal is N-acrylamido dimethoxy ethyl acetal.
The anionic crosslinking agent is 2-acrylamide-2-methylpropanesulfonate.
The nanoparticles are nano dopamine and are purchased from sienna millennium biotechnology limited.
The tungsten-doped vanadium dioxide is prepared according to the method provided by CN102295312B, and the doping amount of tungsten is 1.7%.
The embodiment also provides a preparation method of the self-temperature-control photothermal effect microsphere, which comprises the following steps:
preparation of a nuclear layer: adding an anionic cross-linking agent, sodium persulfate, a hydrogel intermediate and nanoparticles in the core layer preparation raw materials into water, and mixing to obtain a water phase; introducing nitrogen into butyl acetate and cellulose acetate in the nuclear layer preparation raw material for mixing, heating to 70 ℃, sequentially adding water phase and tetramethyl ethylenediamine in the nuclear layer preparation raw material for reacting for 3.5 hours to obtain a nuclear layer mixture;
preparing a shell layer: adding sodium persulfate, an anion cross-linking agent, a hydrogel intermediate and tungsten-doped vanadium dioxide in raw materials for preparing the shell into water, mixing, adding the mixture into the nuclear layer mixture, and mixing to obtain a shell layer mixture; mixing butyl acetate and cellulose acetate in the shell preparation raw material, introducing nitrogen for mixing, heating to 70 ℃, sequentially adding the shell mixture and tetramethyl ethylenediamine in the shell preparation raw material, reacting for 6.5 hours, filtering, washing and drying to obtain the microsphere.
Evaluation of Performance
1. Particle size distribution: the microspheres provided in examples were tested for the number average particle diameter and the weight average particle diameter, respectively, and the particle size distribution PDI ═ weight average particle diameter/number average particle diameter was tested, and it was found that PDIs of examples 1 to 3 were 1.4 to 1.6, and PDIs of examples 4 and 5 were greater than 1.6.
2. Temperature stability: the microspheres provided in the examples are irradiated by infrared light, and the temperature rise amplitude is observed, so that the temperature of the microspheres provided in the examples 1 to 3 is basically unchanged after the microspheres are irradiated for a period of time, and the temperature of the microspheres provided in the examples 4 and 5 is slightly increased after the microspheres are irradiated for a period of time.
3. Surface properties: the surface structure of the microspheres provided by the embodiment is observed through a microscope, and compared with the microspheres provided by the embodiments 4 and 5, the microspheres provided by the embodiments 1 to 3 have relatively smooth surfaces, are close to a circle, and almost have no adhesion.
4. Density of microspheres: the microspheres provided in example 3 were measured by Eppendorf microcentrifuge tubes, which were wetted with saline, centrifuged at 1200g for 1 minute and the total weight m of tube and saline recorded0. Adding the microspheres into the tube, and repeating the centrifuging and weighing steps to obtain the total weight m of the tube, the saline water and the microspheres1And the scale of the saline displacement in the tube is read as the volume V of the microspheres, by V/(m)1-m0) Repeating the steps for three times to obtain the wet microspheres with the density of 1.2-1.3 g/mL.
According to the test results, the microsphere provided by the invention can realize accurate temperature control, can be used for focus, and can accurately control the local temperature of the focus to kill tumors.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The self-temperature-control photothermal effect microsphere is characterized by comprising a core layer and a shell layer from inside to outside, wherein the preparation raw materials of the core layer comprise a hydrogel intermediate, nanoparticles and an anionic cross-linking agent; the shell layer is prepared from the raw materials of a hydrogel intermediate, tungsten-doped vanadium dioxide and an anionic cross-linking agent.
2. The self-regulating photothermal effect microspheres of claim 1, wherein said hydrogel intermediate is prepared from a polyol and an acrylamide dialkoxyalkyl acetal.
3. The self-regulating photothermal effect microspheres according to claim 1, wherein said polyol is selected from one or more of polyvinyl alcohol, polyethylene glycol, polypropylene glycol, chitosan, and starch.
4. The self-regulating photothermal effect microsphere according to claim 1, wherein said nanoparticles are selected from one or more of nano gold, carbon nanotubes, nano dopamine.
5. The self-temperature-control photothermal effect microsphere of claim 1, wherein the amount of tungsten doped in the tungsten-doped vanadium dioxide is 1.5-1.85%.
6. The self-regulating photothermal effect microspheres according to claim 1, wherein the anionic crosslinking agent is selected from one or more of 2-acrylamide-2-methylpropane carboxylate, 2-acrylamide-2-methylpropane sulfonate, allyl sulfonate, and 1-propenyloxy-2-hydroxypropane sulfonate sodium salt.
7. The self-temperature-control photothermal effect microsphere according to any one of claims 1 to 6, wherein the weight ratio of the hydrogel intermediate, the anionic crosslinking agent and the nanoparticles in the raw materials for preparing the core layer is (70-90): (4-8): (6-22).
8. The self-temperature-control photothermal effect microsphere according to any one of claims 1 to 6, wherein in the raw materials for preparing the shell layer, the weight ratio of the hydrogel intermediate, the anionic crosslinking agent and the tungsten-doped vanadium dioxide is (70-90): (4-8): (6-22).
9. The self-temperature-control photothermal effect microsphere according to any one of claims 1 to 6, wherein the weight ratio of the core layer to the shell layer is 1: (1.5-5).
10. The preparation method of the self-temperature-control photothermal effect microspheres according to any one of claims 1 to 9, comprising:
preparation of a nuclear layer: adding water into the nuclear layer preparation raw materials, mixing, and adding the mixture into an organic solvent for reaction to obtain a nuclear layer mixture;
preparing a shell layer: and adding water into the shell layer preparation raw material, mixing, adding the mixture into the core layer mixture, reacting, filtering, washing and drying to obtain the microsphere.
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