CN111494343A - Gold-polydopamine composite hollow ellipsoid drug carrier with photothermal effect and preparation method thereof - Google Patents

Gold-polydopamine composite hollow ellipsoid drug carrier with photothermal effect and preparation method thereof Download PDF

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CN111494343A
CN111494343A CN202010586871.1A CN202010586871A CN111494343A CN 111494343 A CN111494343 A CN 111494343A CN 202010586871 A CN202010586871 A CN 202010586871A CN 111494343 A CN111494343 A CN 111494343A
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gold
composite hollow
polydopamine
drug carrier
hollow ellipsoid
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方群玲
熊青山
段劲宇
许可珠
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Hefei University of Technology
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5107—Excipients; Inactive ingredients
    • A61K9/513—Organic macromolecular compounds; Dendrimers
    • A61K9/5146—Organic macromolecular compounds; Dendrimers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, polyamines, polyanhydrides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy

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Abstract

The invention discloses a gold-poly dopamine composite hollow ellipsoid drug carrier with photothermal effect and a preparation method thereof, and the drug carrier is fusiform Fe2O3The nano particles are used as a template and react with Tris solution and Na dissolved with dopamine3C6H5O7·2H2O and AuCl3·HCl·4H2Carrying out ultrasonic reaction on the O solution at room temperature, and forming a polydopamine film on the template by utilizing the self-polymerization of dopamine under an alkaline condition; reuse of Fe2O3The solid obtained is soaked in an acid solution for reaction, so that the gold-polydopamine composite hollow ellipsoid drug carrier is obtained. The synthetic method of the invention is simple, the reaction condition is mild, the production cost is low, and the obtained targetThe product can be used as a photo-thermal treatment reagent, and the cavity structure of the product can be used for carrying medicaments, so that the product has good application prospects in the biomedical fields of medicament loading, photo-thermal treatment and the like.

Description

Gold-polydopamine composite hollow ellipsoid drug carrier with photothermal effect and preparation method thereof
Technical Field
The invention belongs to the field of biomedical materials, and particularly relates to a gold-poly dopamine composite hollow ellipsoid drug carrier with a photothermal effect and a preparation method thereof.
Background
The hollow structure nano material is a nano material with a special appearance, wherein the nano material is a nano material with a special appearance, and the nano material is characterized in that a geometric structure is constructed on the basis of a conventional nano material, so that one or more large internal cavities are generated inside particles, and a hollow shell layer is formed around the cavities. Compared with common nanoparticles, the hollow structure material has a special internal cavity structure, so that the hollow structure material has the unique advantages of low density, large specific surface area, internal storage space and the like. For example mesoporous SiO2Has very good biocompatibility and large specific surface area, and has important potential application value in the field of drug carriers. Based on the unique physical and chemical properties of the nano-structure, the hollow nano-structure has attracted great research interest in the existing and emerging fields, and has wide application prospects in the fields of catalysis, biomedicine, photoelectricity, environment and the like.
Polydopamine (PDA), which is a major pigment component in natural melanin (eumelanin), exhibits many outstanding properties in the fields of optics, electricity, magnetism, etc., and has excellent biocompatibility. PDA incorporates many functional groups such as catechol, amino groups, and imino groups into its chemical structure, thus conferring its ability to build a wide variety of composite materials. PDA is not only limited to coating materials, but also has very wide application prospect in a plurality of fields such as chemistry, biology, medical treatment, material science, applied scientific engineering and technology. Currently, biomedical is one of the most important fields of application for a range of materials based on PDA. PDA not only has excellent biocompatibility and affinity, but also can generate secondary reaction with a plurality of molecules, thereby providing a material basis for preparing various mixed materials with special functions. The gold nanoparticles have wide application prospect in the field of biological medical treatment (mainly comprising photo-thermal ablation of cancer cells, drug delivery, photo-acoustic imaging and the like) due to good biocompatibility and excellent photoelectric performance. The composite alloy and polydopamine are used for preparing the nano hollow structure, and have important research value.
Disclosure of Invention
The invention provides a gold-poly dopamine composite hollow ellipsoid drug carrier with a photothermal effect and a preparation method thereof, and aims to solve the problems that: and (3) screening appropriate reaction raw materials and appropriate reaction conditions, and preparing a large amount of gold-poly dopamine composite hollow ellipsoids with stable properties.
In order to solve the technical problem, the invention adopts the following technical scheme:
a preparation method of a gold-polydopamine composite hollow ellipsoid drug carrier with a photothermal effect comprises the following steps:
5-15mg of monodisperse fusiform Fe2O3Adding nanoparticles and 0.2-1m L APTES into a beaker, adding 15-45m L alcoholic solution, ultrasonically dispersing at room temperature for 30-60min, centrifuging to obtain solid, adding the obtained solid into the beaker filled with 15-45m L alcoholic solution, ultrasonically dispersing uniformly, rapidly adding 30-90m L Tris solution containing 30-90mg dopamine hydrochloride and 5-15mg Na3C6H5O7·2H2O and AuCl with a concentration of 0.1g/m L from 10 to 80. mu. L3·HCl·4H2Continuing ultrasonic treatment of the solution O for 2.5-3h at room temperature; after the reaction is finished, centrifuging, washing and drying to obtain Fe2O3@ Au @ PDA composite nanoparticles;
taking 5-10mg of the Fe2O3Putting the @ Au @ PDA composite nano particles into a beaker, adding 30-45m L deionized water, performing ultrasonic dispersion uniformly, adding 5-20m L acid solution, performing soaking reaction at room temperature for 48-72h, and after the reaction is finished, centrifuging, washing and drying to obtain the target product, namely the gold-polydopamine composite hollow ellipsoid.
Further, the monodisperse fusiform Fe2O3The nano particles are prepared by the following steps: FeCl is added3·6H2O and NaH2PO4·2H2Dispersing O in water by ultrasonic in a mass ratio of 80-90:1 uniformly, adding the mixture into a reaction kettle, and reacting for three days at 98 ℃; after the reaction is finished, naturally cooling to room temperature, centrifuging, washing and drying to obtain the monodisperse fusiform Fe2O3Nanoparticles.
Furthermore, the gold-polydopamine composite hollow ellipsoid is an ellipsoidal nano particle, the polydopamine is used as a shell, the gold nano particle is embedded or attached to the polydopamine shell, and the interior of the shell is of a full hollow structure or contains fusiform Fe2O3A semi-hollow structure of nanoparticles.
Furthermore, the thickness of the shell layer of the gold-poly dopamine composite hollow ellipsoid is changed within the range of 5-50nm by regulating the dosage of dopamine hydrochloride.
Further, the hollow structure inside the gold-poly dopamine composite hollow ellipsoid is regulated and controlled to be a full hollow structure or contain fusiform Fe by regulating and controlling the dosage of the acid solution and the time of the soaking reaction2O3A semi-hollow structure of nanoparticles.
Further, in each step, the centrifugal rotating speed is 8000-10000 r/min; the washing is alternately cleaned by deionized water and absolute ethyl alcohol; the drying is vacuum drying at 35-45 ℃.
Further, the alcohol solution is an ethanol solution.
Further, the acid solution is at least one of hydrochloric acid, sulfuric acid and nitric acid.
The preparation method of the invention is spindle-shaped Fe2O3The nano particles are used as a template and react with Tris solution and Na dissolved with dopamine3C6H5O7·2H2O、AuCl3·HCl·4H2Carrying out ultrasonic reaction on the O solution at room temperature, and forming a polydopamine film on the template by utilizing the self-polymerization of dopamine under an alkaline condition; reuse of Fe2O3The solid obtained is soaked in an acid solution for reaction, so that the gold-polydopamine composite hollow ellipsoid drug carrier is obtained.
The invention has the beneficial effects that:
1. the invention utilizes low-toxic Fe2O3The nano particles are taken as a template material and then are compounded with PDA and gold nano particles to prepare the drug carrier gold-polydopa with photo-thermal effectThe amine composite hollow ellipsoid can be used as a photo-thermal treatment reagent, and the cavity structure of the hollow ellipsoid can be used for carrying medicaments, so that the hollow ellipsoid has good application prospects in the biomedical fields of medicament loading, photo-thermal therapy and the like.
2. The synthesis method is simple, the reaction condition is mild, the production cost is low, the shell thickness and the particle size of the obtained target product are controllable, and the dispersibility and the biocompatibility are good.
Drawings
FIG. 1 is a TEM image of a gold-polydopamine composite hollow ellipsoid obtained in example 1 of the present invention;
FIG. 2 is a TEM image of a gold-polydopamine composite hollow ellipsoid obtained in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and examples. The scope of protection of the invention is not limited to the following examples.
Example 1
In this example, a gold-polydopamine composite hollow ellipsoid drug carrier was prepared as follows:
step 1, weighing 270mg FeCl3·6H2O and 3.2mg NaH2PO4·2H2Placing O in a 100m L beaker, adding 50m L deionized water, performing ultrasonic dispersion uniformly, transferring to a reaction kettle, reacting for three days at 98 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging for 10min at 8000r/min by using a centrifuge, alternately washing a centrifugation substrate for 4 times by using the deionized water and ethanol, and drying for 12h at 40 ℃ in a vacuum drying oven to obtain monodisperse fusiform Fe2O3Nanoparticles.
Step 2, 10mg of monodisperse fusiform Fe2O3Adding nanoparticles and 0.5m L APTES into a 100m L beaker, adding 30m L ethanol solution, ultrasonically dispersing for 30min at room temperature, centrifuging to obtain solid, adding the obtained solid into a 100m L beaker filled with 30m L ethanol solution, ultrasonically dispersing uniformly, and rapidly adding 40m L Tris solution containing 60mg dopamine hydrochloride and 10mg Na3C6H5O7·2H2O and 40. mu. L concentration was 0.1g/m LOf AuCl3·HCl·4H2Continuing ultrasonic treatment for 3 hours at room temperature for the solution O; after the reaction is finished, centrifuging for 10min at the rotating speed of 8000r/min by using a centrifuge, alternately washing the centrifugal substrate for 4 times by using deionized water and ethanol, and drying for 12h at the temperature of 40 ℃ in a vacuum drying oven to obtain Fe2O3@ Au @ PDA composite nanoparticles.
Step 3, taking 10mg of monodisperse Fe2O3Putting the @ Au @ PDA composite nanoparticles into a 100m L beaker, adding 45m L deionized water, performing ultrasonic dispersion uniformly, adding 5m L hydrochloric acid, performing soaking reaction at room temperature for 72h, centrifuging for 10min at 8000r/min by using a centrifuge after the reaction is finished, alternately washing a centrifugal substrate for 4 times by using the deionized water and ethanol, and drying for 12h at 40 ℃ in a vacuum drying oven to obtain a target product, namely a gold-polydopamine composite hollow ellipsoid.
FIG. 1 is a TEM image of a gold-polydopamine composite hollow ellipsoid obtained in this example, from which it can be seen that the obtained product has a uniform morphology and is an ellipsoidal nanoparticle, the polydopamine is used as a shell, the gold nanoparticle is embedded or attached to the polydopamine shell, and the interior of the shell contains spindle-shaped Fe2O3A semi-hollow structure of nanoparticles. The structure can be used as a drug carrier with excellent performance, and the gold nanoparticles are compounded to have excellent photo-thermal effect.
Example 2
In this example, a gold-polydopamine composite hollow ellipsoid drug carrier was prepared as follows:
step 1, weighing 270mg FeCl3·6H2O and 3.2mg NaH2PO4·2H2Placing O in a 100m L beaker, adding 50m L deionized water, performing ultrasonic dispersion uniformly, transferring to a reaction kettle, reacting for three days at 98 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging for 10min at 8000r/min by using a centrifuge, alternately washing a centrifugation substrate for 4 times by using the deionized water and ethanol, and drying for 12h at 40 ℃ in a vacuum drying oven to obtain monodisperse fusiform Fe2O3Nanoparticles.
Step 2, 15mg of monodisperse fusiform Fe2O3The nanoparticles and 0.75m L APTES were added to a 100m L beaker, followed by 45m L ethanolUltrasonically dispersing the solution at room temperature for 30min, centrifuging to obtain solid, adding the obtained solid into 250m L beaker filled with 45m L ethanol solution, ultrasonically dispersing uniformly, and rapidly adding 60m L Tris solution containing 90mg dopamine hydrochloride and 15mg Na3C6H5O7·2H2O and 60 μ L AuCl at a concentration of 0.1g/m L3·HCl·4H2Continuing ultrasonic treatment for 3 hours at room temperature for the solution O; after the reaction is finished, centrifuging for 10min at the rotating speed of 8000r/min by using a centrifuge, alternately washing the centrifugal substrate for 4 times by using deionized water and ethanol, and drying for 12h at the temperature of 40 ℃ in a vacuum drying oven to obtain Fe2O3@ Au @ PDA composite nanoparticles.
Step 3, taking 10mg of monodisperse Fe2O3Putting the @ Au @ PDA composite nanoparticles into a 100m L beaker, adding 30m L deionized water, performing ultrasonic dispersion uniformly, adding 20m L hydrochloric acid, performing soaking reaction at room temperature for 72h, centrifuging for 10min at 8000r/min by using a centrifuge after the reaction is finished, alternately washing a centrifugal substrate for 4 times by using the deionized water and ethanol, and drying for 12h at 40 ℃ in a vacuum drying oven to obtain a target product, namely a gold-polydopamine composite hollow ellipsoid.
FIG. 2 is a TEM image of a gold-polydopamine composite hollow ellipsoid obtained in this example, from which it can be seen that the obtained product has a uniform morphology and is an ellipsoidal nanoparticle, the polydopamine is used as a shell, the gold nanoparticle is embedded or attached to the polydopamine shell, and the interior of the shell does not contain spindle-shaped Fe2O3The nano particles are in a full hollow structure. The structure can be used as a drug carrier with excellent performance, and the gold nanoparticles are compounded to have excellent photo-thermal effect.
The above is merely a preferred embodiment of the present invention and is not intended to limit the present invention, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a gold-polydopamine composite hollow ellipsoid drug carrier with a photothermal effect is characterized by comprising the following steps:
5-15mg of monodisperse fusiform Fe2O3Adding nanoparticles and 0.2-1m L APTES into a beaker, adding 15-45m L alcoholic solution, ultrasonically dispersing at room temperature for 30-60min, centrifuging to obtain solid, adding the obtained solid into the beaker filled with 15-45m L alcoholic solution, ultrasonically dispersing uniformly, rapidly adding 30-90m L Tris solution containing 30-90mg dopamine hydrochloride and 5-15mg Na3C6H5O7·2H2O and AuCl with a concentration of 0.1g/m L from 10 to 80. mu. L3·HCl·4H2Continuing ultrasonic treatment of the solution O for 2.5-3h at room temperature; after the reaction is finished, centrifuging, washing and drying to obtain Fe2O3@ Au @ PDA composite nanoparticles;
taking 5-10mg of the Fe2O3Putting the @ Au @ PDA composite nano particles into a beaker, adding 30-45m L deionized water, performing ultrasonic dispersion uniformly, adding 5-20m L acid solution, performing soaking reaction at room temperature for 48-72h, and after the reaction is finished, centrifuging, washing and drying to obtain the target product, namely the gold-polydopamine composite hollow ellipsoid.
2. The preparation method of the gold-polydopamine composite hollow ellipsoid drug carrier according to claim 1, characterized in that: said monodisperse fusiform Fe2O3The nano particles are prepared by the following steps:
FeCl is added3·6H2O and NaH2PO4·2H2Dispersing O in water by ultrasonic in a mass ratio of 80-90:1 uniformly, adding the mixture into a reaction kettle, and reacting for three days at 98 ℃; after the reaction is finished, naturally cooling to room temperature, centrifuging, washing and drying to obtain the monodisperse fusiform Fe2O3Nanoparticles.
3. The preparation method of the gold-polydopamine composite hollow ellipsoid drug carrier according to claim 1, characterized in that: the gold-polydopamine composite hollow ellipsoid is an ellipsoid-shaped nano particle, polydopamine is used as a shell, the gold nano particle is embedded or attached to the polydopamine shell, and the interior of the shell is of a full hollow structure or contains fusiform Fe2O3A semi-hollow structure of nanoparticles.
4. The method for preparing the gold-polydopamine composite hollow ellipsoid drug carrier according to claim 1 or 3, characterized in that: the shell thickness of the gold-poly dopamine composite hollow ellipsoid is changed within the range of 5-50nm by regulating and controlling the dosage of dopamine hydrochloride.
5. The method for preparing the gold-polydopamine composite hollow ellipsoid drug carrier according to claim 1 or 3, characterized in that: the hollow structure in the gold-polydopamine composite hollow ellipsoid is regulated and controlled to be a full hollow structure or contain fusiform Fe by regulating and controlling the dosage of the acid solution and the soaking reaction time2O3A semi-hollow structure of nanoparticles.
6. The method for preparing the gold-polydopamine composite hollow ellipsoid drug carrier according to claim 1 or 2, characterized in that: the centrifugal rotating speed is 8000-10000 r/min; the washing is alternately cleaned by deionized water and absolute ethyl alcohol; the drying is vacuum drying at 35-45 ℃.
7. The method for preparing the gold-polydopamine composite hollow ellipsoid drug carrier according to claim 1 or 2, characterized in that: the alcohol solution is an ethanol solution.
8. The method for preparing the gold-polydopamine composite hollow ellipsoid drug carrier according to claim 1 or 2, characterized in that: the acid solution is at least one of hydrochloric acid, sulfuric acid and nitric acid.
9. A gold-polydopamine composite hollow ellipsoid prepared by the preparation method of any one of claims 1-8.
10. The gold-polydopamine composite hollow ellipsoid of claim 9, wherein: the gold-polydopamine composite hollow ellipsoid is a drug carrier with photothermal effect.
CN202010586871.1A 2020-06-24 2020-06-24 Gold-polydopamine composite hollow ellipsoid drug carrier with photothermal effect and preparation method thereof Pending CN111494343A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104740653A (en) * 2015-03-26 2015-07-01 中国科学院长春应用化学研究所 Hollow mesoporous silica-DNA composite material and preparation method and application thereof
US20190079014A1 (en) * 2016-03-24 2019-03-14 Nanyang Technological University Core-shell plasmonic nanogapped nanostructured material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104740653A (en) * 2015-03-26 2015-07-01 中国科学院长春应用化学研究所 Hollow mesoporous silica-DNA composite material and preparation method and application thereof
US20190079014A1 (en) * 2016-03-24 2019-03-14 Nanyang Technological University Core-shell plasmonic nanogapped nanostructured material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
XU ET AL.: "Magnetically separable h-Fe3O4@Au/polydopamine nanosphere with a hollow interior: A versatile candidate for nanocatalysis and metal ion adsorption", 《CHEMICAL ENGINEERING JOURNAL》 *
王殿杰 等: "不同结构磁性四氧化三铁纳米材料的介电特性和微波吸收性能", 《表面技术》 *
黄景科: ""复合金磁性γ-Fe2O3纳米粒子的制备研究"", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 *

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Application publication date: 20200807