CN114949214B - Barium sulfate material with photothermal conversion surface layer and preparation method thereof - Google Patents
Barium sulfate material with photothermal conversion surface layer and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种具有光热转换表层的硫酸钡材料及其制备方法，该材料由硫酸钡和其外包覆的近红外光热涂层组成。制备方法包括方法(1)或(2)：(1)将硫酸钡乙醇分散液加入到聚多巴胺溶液中搅拌，离心清洗干燥，即得；(2)向硫酸钡乙醇分散液中，加入氯化铁和吡咯溶液，再加入盐酸搅拌，离心清洗干燥，即得。该材料可用于制备光热转换材料。本发明制备简单，材料廉价易得，光热产品可批量制备，适用性广，此外，材料在红外激光下能产生明显的光声信号，具有X‑ray显影和光声造影双重显影功能，生物相容性好，具有无毒无害的优势，结合其稳定可循环的光热能力，是具备诊疗一体的有效纳米平台，可应用于光热杀菌、光热治疗、光热显影等生物医药领域。
The invention discloses a barium sulfate material with a photothermal conversion surface layer and a preparation method thereof. The material is composed of barium sulfate and a near-infrared photothermal coating covering the barium sulfate. The preparation method includes method (1) or (2): (1) Add the barium sulfate ethanol dispersion to the polydopamine solution, stir, centrifuge, clean and dry to obtain; (2) Add chlorine to the barium sulfate ethanol dispersion. Iron and pyrrole solution, then add hydrochloric acid, stir, centrifuge, wash and dry to obtain. This material can be used to prepare photothermal conversion materials. The invention is simple to prepare, the materials are cheap and easy to obtain, the photothermal products can be prepared in batches, and have wide applicability. In addition, the material can produce obvious photoacoustic signals under infrared laser, and has the dual development functions of X-ray development and photoacoustic contrast imaging. It has good capacitance and is non-toxic and harmless. Combined with its stable and recyclable photothermal capabilities, it is an effective nano-platform that integrates diagnosis and treatment and can be used in biomedical fields such as photothermal sterilization, photothermal therapy, and photothermal development.
Description
Technical Field
The invention relates to the field of photothermal conversion materials and biomedical applications, in particular to a barium sulfate material with a photothermal conversion surface layer, and a preparation method and application thereof.
Background
The photothermal effect is a phenomenon in which a photothermal agent converts light energy into heat energy under light irradiation, and a material having the photothermal effect is called a photothermal agent or a photothermal conversion material. Photo-thermal conversion materials benefit from the advantage of being able to fully utilize light energy for thermal conversion, and have been attracting attention in many research fields such as biology, sea water desalination, high-energy application, and development of optical drives. Meanwhile, the related technology of the photo-thermal effect has the characteristics of non-contact and accurate control, can well accord with the exploration targets of modern medical treatment on novel diagnosis and treatment methods, and is attracting more and more interest. The photothermal conversion material can be directly used as a photothermal therapeutic agent for treating diseases, such as ablation of cancer cells after irradiation by near infrared laser, as a carrier for drug loading and light control release, photothermal sterilization, and the like. Therefore, the photo-thermal conversion material with multifunctional application can be developed, and has strong research value and application significance.
In biological applications, near infrared light energy exhibits minimal light absorption and minimal damage to skin and tissues compared to visible light that is easily absorbed by melanin and hemoglobin, or mid-far infrared light that is strongly absorbed by water, balances penetration depth and invasiveness of biological tissues, and has irreplaceable advantages, so that the adsorption of near infrared light between 700-1100nm is a key for application of photothermal conversion materials in biomedical fields. On the other hand, the application in the biomedical field has strict requirements on the photothermal conversion material, such as strong near infrared absorptivity, high photothermal conversion efficiency, good biocompatibility, high water solubility or dispersibility, low toxicity to healthy tissues and the like. In recent years, multifunctional photothermal agents combining various functions such as disease diagnosis and treatment have been a trend of application of photothermal effects in the field of biology. Over the past decade, various photothermal conversion materials including organic compounds, inorganic materials, carbon materials, polymers, and the like have been attracting attention. Among them, metal compounds are most widely used, and include various metal nanomaterials such as gold, silver nanoparticles and palladium nanoflakes, and some metal oxide nanomaterials such as iron oxide nanoparticles, tungsten oxide nanocrystals, black phosphorus quantum dots, and the like. The biological organic photothermal agent, such as polymer photothermal materials of Polydopamine (PDA), polythiophene (PT), polyaniline (PAn), polypyrrole (PPy) and the like, and derivatives thereof, have the characteristics of molecular level structural design, strong near infrared absorption, high photothermal conversion efficiency, good biocompatibility and the like, and are novel photothermal materials. Based on its flexible molecular design, good biocompatibility and potential biodegradability, it has a great advantage compared to inorganic nanomaterials.
The invention develops barium sulfate with a photo-thermal conversion surface layer. The barium sulfate is utilized to have the advantages of no toxicity and harm to human body, capability of excretion and the like, and the development of the multifunctional composite nano particles is realized by coating the barium sulfate with an organic photothermal coating. The barium sulfate with the photothermal conversion surface layer obtained by the method maintains the original excellent X-Ray contrast function of the barium sulfate, improves the aggregation condition of the barium sulfate, simultaneously further improves the biocompatibility of the barium sulfate by the photothermal polymer coating, can generate obvious photoacoustic signals under infrared laser after being combined with the photothermal coating, can be used for X-Ray development and photoacoustic contrast dual development, has good, stable and recyclable photothermal conversion performance, can be applied to a plurality of biomedical fields such as photothermal treatment, photothermal antibiosis, development and the like, has low cost, is easy to realize, and is beneficial to popularization and application.
Disclosure of Invention
The invention aims to provide a barium sulfate material with a photo-thermal conversion surface layer and a preparation method thereof, wherein the barium sulfate material with the photo-thermal effect can regulate and control the thickness and photo-thermal property of the barium sulfate photo-thermal conversion coating by controlling the type, concentration and compounding time of a polymer coating with the photo-thermal effect.
The barium sulfate material with the photothermal conversion surface layer consists of barium sulfate and a polymer coating with a photothermal effect, wherein the barium sulfate is coated by the polymer coating with the thickness of 10-20nm, and the barium sulfate and the polymer coating have a stable composite structure and good biocompatibility.
The polymer coating with the photo-thermal effect is one or more of polydopamine or polypyrrole.
The barium sulfate is particles with the diameter of 500nm-5 mu m.
The preparation method comprises the following steps of (1) or (2):
adding barium sulfate ethanol dispersion liquid into polydopamine solution (PDA), dripping Tris-HCl buffer solution into the polydopamine solution to titrate until the pH value is 8.5, stirring for a certain time, centrifugally cleaning and drying to obtain the barium sulfate material with the photothermal conversion surface layer;
adding ferric chloride and pyrrole solution with equal volume into barium sulfate ethanol dispersion liquid, adding a small amount of concentrated hydrochloric acid, stirring for a certain time, centrifuging, cleaning and drying to obtain the barium sulfate material with the photothermal conversion surface layer.
The concentration of the barium sulfate ethanol dispersion liquid in the preparation method (1) or (2) is 10-300mg/mL.
In the preparation method (1) or (2), the centrifugal speed is 5000-12000r/min, the time is 20min-1h, the deionized water cleaning is repeated at least three times, and the drying in the oven is carried out at 37 ℃ for overnight.
In the preparation method (1), the concentration of PDA is 2-30mg/mL, the concentration of Tris-HCl buffer solution is 1-10mol/mL, and the stirring time is 0.5-24 h.
In the preparation method (2), the concentration of ferric chloride and pyrrole solution is respectively 20mg/mL-300mg/mL and 9mg/mL-100mg/mL, concentrated hydrochloric acid with the volume ratio of 5:3-1:2 to pyrrole solution is added, and the stirring time is 0.5h-24h.
The barium sulfate with the photothermal conversion surface layer and the preparation method thereof have the following characteristics:
1) The barium sulfate ultrasonically rinsed by ethanol is used as an endogenous inorganic material, so that the serious condition of barium sulfate agglomeration can be improved, the specific surface area is increased, and the barium sulfate is favorable for compounding with a polymer coating.
2) The obtained polymer coating has excellent polymerization and adhesion characteristics, can be effectively compounded and combined with barium sulfate, and finally has stable photo-thermal characteristics for a long time.
3) The barium sulfate with the photothermal conversion surface layer not only utilizes the advantages of no toxicity and harm to human bodies, capability of excretion and the like, but also realizes the development of the multifunctional composite nano particles by coating the barium sulfate with the organic photothermal coating. The finally obtained barium sulfate with the photothermal conversion surface layer maintains the original excellent X-Ray contrast function of the barium sulfate, further improves the biocompatibility of the barium sulfate, and has good photothermal conversion performance. Low cost, easy realization and easy popularization and application.
The invention further provides application of the barium sulfate with the photothermal conversion surface layer in preparation of photothermal conversion materials and biomedical fields.
In the above application, the preparation of the photo-thermal conversion material includes photo-thermal nanoparticles and/or photo-thermal nano-films; the method can be particularly applied to the preparation of near infrared sensors and optically controlled degradable plastics.
In the above application, the biomedical uses include photothermal treatment of tumor, photothermal sterilization and/or drug-loaded light-controlled drug release.
Drawings
FIG. 1 is a schematic view of a barium sulfate structure with a photothermal surface layer and a scanning electron microscope. (BPA means a material obtained by the method (1), and BPy means a material obtained by the method (2).
Fig. 2 is a raman diagram of barium sulfate having a photothermal conversion surface layer prepared in example 6 and example 14 of the present invention.
FIG. 3 is a graph showing the real-time infrared heating/cooling of barium sulfate with photothermal conversion surface layers prepared in example 6 and example 14 according to the present invention under irradiation of near infrared laser at 808 nm.
Detailed Description
The invention will be further described with reference to the drawings and the specific examples.
Example 1
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 120mL of ethanol to prepare 20mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 100mg of dopamine hydrochloride in 50mL of deionized water to prepare 2mg/mL of dopamine solution for later use;
(3) And uniformly stirring and mixing the prepared barium sulfate ethanol dispersion liquid and the dopamine solution by magnetic force, and simultaneously dripping 1mol/L Tris-HCl buffer solution until the pH value of the mixed solution is 8.5.
(4) Stirring the uniformly mixed solution for 1h.
(5) Centrifuging the stirred mixed solution at 8000r/min for 20min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in a baking oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, wherein the obtained barium sulfate can be observed to have a uniform dispersion morphology under a scanning electron microscope, and the temperature rise at 5.1-6.5 ℃ can be realized after the obtained barium sulfate is irradiated with 808nm near infrared laser for 20min at the concentration of 200 mug/mL.
Example 2
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing the mixture in 120mL of deionized water to prepare 20mg/mL of barium sulfate dispersion liquid for later use;
(2) Dissolving 100mg of dopamine hydrochloride in 50mL of deionized water to prepare 2mg/mL of dopamine solution for later use;
(3) Uniformly stirring and mixing the prepared barium sulfate dispersion liquid and the dopamine solution by magnetic force, and simultaneously dripping 1mol/L Tris-HCl buffer solution until the pH value of the mixed solution is 8.5.
(4) Stirring the uniformly mixed solution for 1h.
(5) Centrifuging the stirred mixed solution at 8000r/min for 20min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in an oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, and irradiating the obtained barium sulfate with 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, so that the temperature rise at 3.4-4.8 ℃ can be realized.
Example 3
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 120mL of ethanol to prepare 20mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 100mg of dopamine hydrochloride in 50mL of deionized water to prepare 2mg/mL of dopamine solution for later use;
(3) And uniformly stirring and mixing the prepared barium sulfate ethanol dispersion liquid and the dopamine solution by magnetic force, and simultaneously dripping 1mol/L Tris-HCl buffer solution until the pH value of the mixed solution is 8.5.
(4) Stirring the uniformly mixed solution for 2 hours.
(5) Centrifuging the stirred mixed solution at 8000r/min for 30min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) placing the cleaned precipitate in a baking oven at 37 ℃ for drying overnight to obtain the barium sulfate with the photothermal conversion surface layer. The obtained barium sulfate can realize temperature rise of 6.5-8.5 ℃ after being irradiated by 808nm near infrared laser for 20min at the concentration of 200 mug/mL.
Example 4
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 120mL of ethanol to prepare 20mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 100mg of dopamine hydrochloride in 50mL of deionized water to prepare 2mg/mL of dopamine solution for later use;
(3) And uniformly stirring and mixing the prepared barium sulfate ethanol dispersion liquid and the dopamine solution by magnetic force, and simultaneously dripping 1mol/L Tris-HCl buffer solution until the pH value of the mixed solution is 8.5.
(4) Stirring the uniformly mixed solution for 4 hours.
(5) Centrifuging the stirred mixed solution at 8000r/min for 30min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in an oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, and irradiating the obtained barium sulfate with 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, so that the temperature rise at 6.1-9.4 ℃ can be realized.
Example 5
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 120mL of ethanol to prepare 20mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 100mg of dopamine hydrochloride in 50mL of deionized water to prepare 2mg/mL of dopamine solution for later use;
(3) And uniformly stirring and mixing the prepared barium sulfate ethanol dispersion liquid and the dopamine solution by magnetic force, and simultaneously dripping 1mol/L Tris-HCl buffer solution until the pH value of the mixed solution is 8.5.
(4) Stirring the uniformly mixed solution for 8 hours.
(5) Centrifuging the mixed solution at 6000r/min for 60min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) placing the cleaned precipitate in a baking oven at 37 ℃ for drying overnight to obtain the barium sulfate with the photothermal conversion surface layer. The obtained barium sulfate can realize temperature rise of 6.5-10.7 ℃ after being irradiated by 808nm near infrared laser for 20min at the concentration of 200 mug/mL.
Example 6
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 120mL of ethanol to prepare 20mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 100mg of dopamine hydrochloride in 50mL of deionized water to prepare 2mg/mL of dopamine solution for later use;
(3) And uniformly stirring and mixing the prepared barium sulfate ethanol dispersion liquid and the dopamine solution by magnetic force, and simultaneously dripping 1mol/L Tris-HCl buffer solution until the pH value of the mixed solution is 8.5.
(4) Stirring the uniformly mixed solution for 12 hours.
(5) Centrifuging the mixed solution at 6000r/min for 60min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) The cleaned precipitate is placed in a drying oven at 37 ℃ for drying overnight to obtain barium sulfate with a photothermal conversion surface layer, a schematic diagram of the barium sulfate with the photothermal conversion surface layer prepared by the method is shown in a graph in fig. 1, a Raman diagram in fig. 2 proves that dopamine exists in the barium sulfate with the photothermal conversion surface layer, a real-time infrared heating curve in fig. 3 shows that the barium sulfate with the photothermal conversion surface layer has obvious temperature rise after illumination, and the barium sulfate with the photothermal conversion surface layer can be heated to about 9-12 ℃ after illumination for 20min by 808nm near infrared laser at the concentration of 200 mug/mL, so that the barium sulfate with the photothermal conversion surface layer has photothermal effect. After stopping illumination for 20min, the barium sulfate with the light-heat conversion surface layer is cooled to room temperature, and a repeated cyclic heating and cooling curve has consistency, which shows that the light-heat effect of the barium sulfate with the light-heat conversion surface layer has stronger stability.
Example 7
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 80mL of ethanol to prepare 30mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 100mg of dopamine hydrochloride in 50mL of deionized water to prepare 2mg/mL of dopamine solution for later use;
(3) And uniformly stirring and mixing the prepared barium sulfate ethanol dispersion liquid and the dopamine solution by magnetic force, and simultaneously dripping 1mol/L Tris-HCl buffer solution until the pH value of the mixed solution is 8.5.
(4) Stirring the uniformly mixed solution for 1h.
(5) Centrifuging the mixed solution at 6000r/min for 60min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in an oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, and irradiating the obtained barium sulfate with 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, so that the temperature rise at 6.2-8.7 ℃ can be realized.
Example 8
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 80mL of ethanol to prepare 30mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 100mg of dopamine hydrochloride in 50mL of deionized water to prepare 2mg/mL of dopamine solution for later use;
(3) And uniformly stirring and mixing the prepared barium sulfate ethanol dispersion liquid and the dopamine solution by magnetic force, and simultaneously dripping 1mol/L Tris-HCl buffer solution until the pH value of the mixed solution is 8.5.
(4) Stirring the uniformly mixed solution for 8 hours.
(5) Centrifuging the mixed solution at 6000r/min for 60min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in an oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, and irradiating the obtained barium sulfate with 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, so that the temperature rise at 4.2-5.7 ℃ can be realized.
Example 9
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 80mL of ethanol to prepare 30mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 100mg of dopamine hydrochloride in 50mL of deionized water to prepare 2mg/mL of dopamine solution for later use;
(3) And uniformly stirring and mixing the prepared barium sulfate ethanol dispersion liquid and the dopamine solution by magnetic force, and simultaneously dripping 1mol/L Tris-HCl buffer solution until the pH value of the mixed solution is 8.5.
(4) Stirring the uniformly mixed solution for 12 hours.
(5) Centrifuging the stirred mixed solution at 8000r/min for 40min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in an oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, and irradiating the obtained barium sulfate with 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, so that the temperature rise at 8.9-11.3 ℃ can be realized.
Example 10
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 120mL of ethanol to prepare 20mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 2.4g of ferric chloride hexahydrate in 100mL of deionized water to prepare 24mg/mL of ferric chloride solution for later use;
(3) 280. Mu.L of pyrrole monomer solution was dissolved in 100mL of water to prepare a 2.7mg/mL pyrrole solution for further use.
(4) Mixing the prepared ferric chloride solution and pyrrole solution according to a ratio of 1:1 was added to 30mL each of the barium sulfate ethanol dispersion with stirring, and 40 μl of concentrated hydrochloric acid solution was added thereto with stirring for 1 hour.
(5) Centrifuging the mixed solution at 5000r/min for 70min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in a baking oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, wherein the obtained barium sulfate can be observed to have a uniform dispersion morphology under a scanning electron microscope, and the temperature rise at 10.6-13.1 ℃ can be realized after the obtained barium sulfate is irradiated with 808nm near infrared laser for 20min at the concentration of 200 mug/mL.
Example 11
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing the mixture in 120mL of deionized water to prepare 20mg/mL of barium sulfate dispersion liquid for later use;
(2) Dissolving 2.4g of ferric chloride hexahydrate in 100mL of deionized water to prepare 24mg/mL of ferric chloride solution for later use;
(3) 280. Mu.L of pyrrole monomer solution was dissolved in 100mL of water to prepare a 2.7mg/mL pyrrole solution for further use.
(4) Mixing the prepared ferric chloride solution and pyrrole solution according to a ratio of 1:1 was added to 30mL each of the barium sulfate dispersion with stirring, and 40 μl of concentrated hydrochloric acid solution was added thereto with stirring for 1 hour.
(5) Centrifuging the mixed solution at 5000r/min for 70min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in an oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, and irradiating the obtained barium sulfate with 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, so that the temperature rise at 6.5-8.9 ℃ can be realized.
Example 12
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 120mL of ethanol to prepare 20mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 2.4g of ferric chloride hexahydrate in 100mL of deionized water to prepare 24mg/mL of ferric chloride solution for later use;
(3) 280. Mu.L of pyrrole monomer solution was dissolved in 100mL of water to prepare a 2.7mg/mL pyrrole solution for further use.
(4) Mixing the prepared ferric chloride solution and pyrrole solution according to a ratio of 1:1 was added to 30mL each of the barium sulfate ethanol dispersion with stirring, and 40 μl of concentrated hydrochloric acid solution was added thereto with stirring for 2 hours.
(5) Centrifuging the mixed solution at 5000r/min for 90min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) placing the cleaned precipitate in a baking oven at 37 ℃ for drying overnight to obtain the barium sulfate with the photothermal conversion surface layer. The temperature rise of the light-heat conversion surface layer at 11.1-14.4 ℃ can be realized after the barium sulfate with the concentration of 200 mug/mL is irradiated by 808nm near infrared laser for 20 min.
Example 13
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 120mL of ethanol to prepare 20mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 2.4g of ferric chloride hexahydrate in 100mL of deionized water to prepare 24mg/mL of ferric chloride solution for later use;
(3) 280. Mu.L of pyrrole monomer solution was dissolved in 100mL of water to prepare a 2.7mg/mL pyrrole solution for further use.
(4) Mixing the prepared ferric chloride solution and pyrrole solution according to a ratio of 1:1 was added to 30mL each of the barium sulfate ethanol dispersion with stirring, and 40 μl of concentrated hydrochloric acid solution was added thereto with stirring for 4 hours.
(5) Centrifuging the mixed solution at 5000r/min for 120min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in an oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, and irradiating the obtained barium sulfate with 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, so that the temperature rise at 16.3-18.5 ℃ can be realized.
Example 14
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 120mL of ethanol to prepare 20mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 2.4g of ferric chloride hexahydrate in 100mL of deionized water to prepare 24mg/mL of ferric chloride solution for later use;
(3) 280. Mu.L of pyrrole monomer solution was dissolved in 100mL of water to prepare a 2.7mg/mL pyrrole solution for further use.
(4) Mixing the prepared ferric chloride solution and pyrrole solution according to a ratio of 1:1 was added to 30mL each of the barium sulfate ethanol dispersion with stirring, and 40 μl of concentrated hydrochloric acid solution was added thereto with stirring for 8 hours.
(5) Centrifuging the mixed solution at 5000r/min for 120min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) placing the cleaned precipitate in a baking oven at 37 ℃ for drying overnight to obtain the barium sulfate with the photothermal conversion surface layer. The schematic diagram of the barium sulfate with the photothermal conversion surface layer prepared in the example is shown in fig. 1, the raman diagram of fig. 2 shows that polypyrrole exists in the barium sulfate with the photothermal conversion surface layer, the real-time infrared heating curve of fig. 3 shows that the temperature of the barium sulfate with the photothermal conversion surface layer is obviously improved after illumination, and the temperature of the obtained barium sulfate can be increased by about 23.4-26.8 ℃ after irradiation of 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, namely the barium sulfate with the photothermal conversion surface layer has a photothermal effect. After stopping illumination for 20min, the barium sulfate with the light-heat conversion surface layer is cooled to room temperature, and a repeated cyclic heating and cooling curve has consistency, which shows that the light-heat effect of the barium sulfate with the light-heat conversion surface layer has stronger stability.
Example 15
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 120mL of ethanol to prepare 20mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 2.4g of ferric chloride hexahydrate in 100mL of deionized water to prepare 24mg/mL of ferric chloride solution for later use;
(3) 280. Mu.L of pyrrole monomer solution was dissolved in 100mL of water to prepare a 2.7mg/mL pyrrole solution for further use.
(4) Mixing the prepared ferric chloride solution and pyrrole solution according to a ratio of 1:1 was added to 30mL each of the barium sulfate ethanol dispersion with stirring, and 40 μl of concentrated hydrochloric acid solution was added thereto with stirring for 12 hours.
(5) Centrifuging the stirred mixed solution at 8000r/min for 40min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in an oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, and irradiating the obtained barium sulfate with 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, so that the temperature rise at 26.1-29.5 ℃ can be realized.
Example 16
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 80mL of ethanol to prepare 30mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 2.4g of ferric chloride hexahydrate in 100mL of deionized water to prepare 24mg/mL of ferric chloride solution for later use;
(3) 280. Mu.L of pyrrole monomer solution was dissolved in 100mL of water to prepare a 2.7mg/mL pyrrole solution for further use.
(4) Mixing the prepared ferric chloride solution and pyrrole solution according to a ratio of 1:1 was added to 30mL each of the barium sulfate ethanol dispersion with stirring, and 40 μl of concentrated hydrochloric acid solution was added thereto with stirring for 1 hour.
(5) Centrifuging the stirred mixed solution at 5000r/min for 60min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in a baking oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, and irradiating the obtained barium sulfate with 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, so that the temperature rise at 8.2-10.1 ℃ can be realized.
Example 17
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 80mL of ethanol to prepare 30mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 2.4g of ferric chloride hexahydrate in 100mL of deionized water to prepare 24mg/mL of ferric chloride solution for later use;
(3) 280. Mu.L of pyrrole monomer solution was dissolved in 100mL of water to prepare a 2.7mg/mL pyrrole solution for further use.
(4) Mixing the prepared ferric chloride solution and pyrrole solution according to a ratio of 1:1 was added to 30mL each of the barium sulfate ethanol dispersion with stirring, and 40 μl of concentrated hydrochloric acid solution was added thereto with stirring for 8 hours.
(5) Centrifuging the stirred mixed solution at 8000r/min for 60min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in an oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, and irradiating the obtained barium sulfate with 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, so that the temperature rise at 16.8-19.5 ℃ can be realized.
Example 18
(1) Uniformly stirring 2.4g of barium sulfate, and ultrasonically dispersing in 80mL of ethanol to prepare 30mg/mL of barium sulfate ethanol dispersion liquid for later use;
(2) Dissolving 2.4g of ferric chloride hexahydrate in 100mL of deionized water to prepare 24mg/mL of ferric chloride solution for later use;
(3) 280. Mu.L of pyrrole monomer solution was dissolved in 100mL of water to prepare a 2.7mg/mL pyrrole solution for further use.
(4) Mixing the prepared ferric chloride solution and pyrrole solution according to a ratio of 1:1 was added to 30mL each of the barium sulfate ethanol dispersion with stirring, and 40 μl of concentrated hydrochloric acid solution was added thereto with stirring for 12 hours.
(5) Centrifuging the stirred mixed solution at 12000r/min for 30min, pouring out supernatant, washing precipitate with deionized water, and repeating for 2-3 times;
(6) And (3) drying the cleaned precipitate in an oven at 37 ℃ overnight to obtain the barium sulfate with the photothermal conversion surface layer, and irradiating the obtained barium sulfate with 808nm near infrared laser for 20min when the concentration of the obtained barium sulfate is 200 mug/mL, so that the temperature rise at 20.9-24.6 ℃ can be realized.
Claims (9)
1. The barium sulfate material with the photothermal conversion surface layer is characterized by comprising barium sulfate and a polymer coating with a photothermal effect, wherein the barium sulfate is coated by the polymer coating with the thickness of 10-20 nm; the polymer coating with the photo-thermal effect is one or more of polydopamine or polypyrrole; the preparation method of the material comprises the following steps of the method (1) or (2):
adding barium sulfate ethanol dispersion liquid into polydopamine solution (PDA), dripping Tris-HCl buffer solution to titrate until the pH value is 8.5, stirring, centrifuging, cleaning and drying to obtain the barium sulfate material with the photothermal conversion surface layer;
adding ferric chloride and pyrrole solution with equal volume into barium sulfate ethanol dispersion liquid, adding concentrated hydrochloric acid, stirring, centrifuging, cleaning and drying to obtain the barium sulfate material with the photothermal conversion surface layer;
the barium sulfate ethanol dispersion liquid is obtained by stirring barium sulfate in ethanol uniformly and performing ultrasonic dispersion.
2. The barium sulfate material having a photothermal conversion surface layer according to claim 1, wherein the barium sulfate is a particle having a diameter of 500nm to 5 μm.
3. A method for producing the barium sulfate material having a photothermal conversion surface layer according to claim 1 or 2, comprising the steps of the following method (1) or (2):
adding barium sulfate ethanol dispersion liquid into polydopamine solution (PDA), dripping Tris-HCl buffer solution to titrate until the pH value is 8.5, stirring, centrifuging, cleaning and drying to obtain the barium sulfate material with the photothermal conversion surface layer;
adding ferric chloride and pyrrole solution with equal volume into barium sulfate ethanol dispersion liquid, adding concentrated hydrochloric acid, stirring, centrifuging, cleaning and drying to obtain the barium sulfate material with the photothermal conversion surface layer.
4. The method for producing a barium sulfate material having a photothermal conversion surface layer according to claim 3, wherein the concentration of the barium sulfate ethanol dispersion in the method (1) or (2) is 10mg/mL to 300mg/mL.
5. The method for preparing a barium sulfate material having a photothermal conversion surface layer according to claim 3, wherein the centrifugal speed in the method (1) or (2) is 5000-12000r/min, the time is 20min-1h, the deionized water washing is repeated at least three times, and the drying in an oven is carried out at 37 ℃.
6. The method for preparing a barium sulfate material having a photothermal conversion surface layer according to claim 3, wherein the PDA concentration in the method (1) is 2-30mg/mL, the Tris-HCl buffer concentration is 1-10mol/mL, and the stirring time is 0.5h-24h.
7. The method for preparing a barium sulfate material with a photothermal conversion surface layer according to claim 3, wherein in the method (2), the concentrations of ferric chloride and pyrrole solution are respectively 20mg/mL to 300mg/mL and 9mg/mL to 100mg/mL, concentrated hydrochloric acid with the volume ratio of 5:3 to 1:2 to the pyrrole solution is added, and the stirring time is 0.5h to 24h.
8. Use of the barium sulfate material having a photothermal conversion surface layer according to claim 1 or 2 for preparing a photothermal conversion material.
9. The use according to claim 8, characterized in that: the photo-thermal conversion material comprises photo-thermal nano particles and a photo-thermal film.
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| 邓春晖 等著.第2.5.1小节，第2.8.6小节.《磁性微纳米材料在蛋白质组学中的应用》.复旦大学出版社,2017, * |
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