CN110538331B - Method for preparing magnetic nano-particles with improved dispersibility and particle uniformity - Google Patents
Method for preparing magnetic nano-particles with improved dispersibility and particle uniformity Download PDFInfo
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- A61K49/1827—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles coated or functionalised microparticles or nanoparticles coated or functionalised nanoparticles having a (super)(para)magnetic core, being a solid MRI-active material, e.g. magnetite, or composed of a plurality of MRI-active, organic agents, e.g. Gd-chelates, or nuclei, e.g. Eu3+, encapsulated or entrapped in the core of the coated or functionalised nanoparticle
- A61K49/1851—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles coated or functionalised microparticles or nanoparticles coated or functionalised nanoparticles having a (super)(para)magnetic core, being a solid MRI-active material, e.g. magnetite, or composed of a plurality of MRI-active, organic agents, e.g. Gd-chelates, or nuclei, e.g. Eu3+, encapsulated or entrapped in the core of the coated or functionalised nanoparticle having a (super)(para)magnetic core coated or functionalised with an organic macromolecular compound, i.e. oligomeric, polymeric, dendrimeric organic molecule
- A61K49/1854—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles coated or functionalised microparticles or nanoparticles coated or functionalised nanoparticles having a (super)(para)magnetic core, being a solid MRI-active material, e.g. magnetite, or composed of a plurality of MRI-active, organic agents, e.g. Gd-chelates, or nuclei, e.g. Eu3+, encapsulated or entrapped in the core of the coated or functionalised nanoparticle having a (super)(para)magnetic core coated or functionalised with an organic macromolecular compound, i.e. oligomeric, polymeric, dendrimeric organic molecule the organic macromolecular compound being obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. poly(meth)acrylate, polyacrylamide, polyvinylpyrrolidone, polyvinylalcohol
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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Abstract
The invention relates to a method for preparing magnetic nano particles with improved dispersity and particle uniformity, which comprises the following steps: preparation of mesoporous silica-coated Fe3O4Nanoparticles; silica-Fe for preparing surface modified photosensitizer3O4A nano-core particle; magnetic nanoparticles with improved dispersibility are prepared. The method of the invention combines the macromolecular polymerization inhibitor and the ultrasonic dispersion, effectively prevents the mutual agglomeration of the nano particles, thereby preparing the magnetic nano particles with good dispersibility.
Description
Technical Field
The invention belongs to the technical field of magnetic resonance nano materials, and particularly relates to a preparation method of magnetic nano particles for magnetic resonance imaging.
Background
In 1973, since Lauterbour first applied Magnetic Resonance Imaging (MRI) to human body diagnosis, the technology has been rapidly developed and widely applied in the fields of biology, medicine and the like. MRI has been widely used for imaging the head, nervous system, abdomen and blood vessels of the human body, is particularly effective for detecting tissue necrosis, ischemia and various malignant lesions, and enables early diagnosis and monitoring of the metabolism of the circulatory system of the human body.
Magnetic nanomaterials have found wide application in magnetic recording, magnetic probes, etc. due to their unique magnetic properties on a nanoscale. In recent years, the application of magnetic nanoparticles has been expanded to medical fields such as magnetic resonance imaging, bio-separation, and magnetic hyperthermia.
Patent document CN201910230788.8 discloses a core-shell type magnetic nanomaterial, which is prepared according to the following principle: methacrylic acid and the surface of the Fe3O4 nano particle form a coordination reaction, methacrylic acid is anchored on the surface of the Fe3O4 particle, konjac glucomannan, methacrylic acid, a cross-linking agent, an initiator and a template are added, and the micro-spherical magnetic particle is directly polymerized by a graft copolymerization method. When the Fe3O4 magnetic nanoparticles are surface-polymerized with high molecular materials, the biocompatibility of the nanoparticles can be improved, but the finally formed spherical particles influence the high relaxation rate.
Photodynamic Therapy (PDT) is a new technology for disease diagnosis and treatment using Photodynamic effect, and its action is based on Photodynamic effect. This is a photosensitizing reaction with biological effects involving oxygen molecules. The process is that the laser irradiation with specific wavelength excites the photosensitizer absorbed by the tissue, the photosensitizer in excited state transfers the energy to the surrounding oxygen to generate singlet oxygen with strong activity, and the singlet oxygen makes the adjacent biological macromolecules generate oxidation reaction to generate cytotoxicity, thereby causing cell damage and death. Until now, a plurality of hospitals adopt photodynamic therapy to diagnose and treat tumors clinically, and the photodynamic therapy is closer to minimally invasive therapy, so that the photodynamic therapy is more suitable for treating brain tumors.
Patent document CN201510351730.0 discloses a core-shell structured nanocomposite, which uses a BaGdF5 nanocrystal as a core and mesoporous silica as a shell, and modifies a photosensitizer dihydroxysilicon phthalocyanine and a targeting agent hyaluronic acid on the surface of the mesoporous silica. The nano composite material has the functions of nuclear magnetic angiography, CT angiography, photothermal therapy and photodynamic therapy.
The inventor provides a magnetic nano material in another patent application, wherein a photosensitive material is connected to the surface of a Fe3O4 nano particle with the surface coated with mesoporous silica, and a gold nano particle with a certain particle size is embedded on the surface of the mesoporous silica material, and the gold nano particle can enhance the photodynamic therapy effect under the excitation light with a certain wavelength.
However, the nanoparticles prepared by the method have the defects of poor particle dispersity (adhesion phenomenon) and low particle size uniformity, so that the performance of the nanoparticles in application is insufficient.
This is because the prepared nanoparticles have an agglomeration phenomenon in the process of preparing the nanocomposite because of the large specific surface and high surface energy of the nanoparticles. Although the surface of the nano particles is coated by adopting a surface coating modification method, the agglomeration effect of the nano particles is weakened; however, steric repulsion is generated by the coating, which is not enough to achieve the purpose of preventing agglomeration.
Therefore, only by solving the problem of particle agglomeration of the nano material, the nano material has excellent dispersibility and particle uniformity, the special nano effect can be fully exerted in the application, and the performance of the nano material can be greatly improved.
Disclosure of Invention
The object of the present invention is to provide a method for preparing magnetic nanoparticles with improved dispersibility and particle uniformity; so as to solve the problem of particle agglomeration of the nano material, and ensure that the nano material has excellent dispersibility and particle uniformity.
The purpose of the invention is realized by the following technical scheme.
A method for preparing magnetic nanoparticles with improved dispersibility and particle uniformity comprises the following steps.
(1) Preparation of mesoporous silica-coated Fe3O4Nanoparticle:
mixing Fe3O4Dispersing nano particles in 0.05-0.1 wt% hydroxyethyl cellulose water solution at 50-60 deg.C, regulating pH value to 8.5-9.0, adding tetraethyl orthosilicate and ethyl acetate under stirring, stirring until dissolving, adding 3-aminopropyl-triethoxysilane, keeping the temperature of the reaction solution at 60-65 deg.C, stirring to react for 16-24 hours, cooling the product, centrifuging, washing with ethanol to obtain Fe coated with mesoporous silica on the surface3O4Nanoparticles.
Wherein the volume ratio of tetraethyl orthosilicate to ethyl acetate to 3-aminopropyl-triethoxysilane is 10-15:20-40: 1.
(2) silica-Fe for preparing surface modified photosensitizer3O4Nano-core particles:
fe with surface coated with mesoporous silica3O4Dispersing the nano particles in a hydroxyethyl cellulose solution to form a dispersion liquid; dispersing photosensitizer in DMF under the condition of keeping out of the sun, combining the photosensitizer with DMF solution of EDC and NHS, oscillating and activating at room temperature, and adding methacryloxypropyl trimethoxy silane and Fe with surface coated with mesoporous silica into an activation system3O4A nanoparticle-hydroxyethylcellulose dispersion; oscillating for reaction overnight, centrifuging and discarding supernatant, washing with deionized water, and drying to obtain Fe of the mesoporous silica surface modified photosensitizer3O4Nanoparticles.
Wherein the concentration of the hydroxyethyl cellulose aqueous solution is 0.05-0.1 wt%.
Preferably, the specific preparation process packageComprises the following steps: dissolving photosensitizer hematoporphyrin in N, N-dimethylformamide under the condition of keeping out of the sun, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) for activation for 3-4 hours, and adding Fe coated with mesoporous silica dispersed in hydroxyethyl cellulose solution into an activation system3O4Nanoparticles, the hydroxyethyl cellulose concentration of the hydroxyethyl cellulose solution being 0.05-0.1 wt%; oscillating for reaction overnight, centrifuging and discarding supernatant, washing with clear water, and drying to obtain Fe of the mesoporous silica surface modified photosensitizer3O4Nanoparticles.
(3) Preparation of magnetic nanoparticles with improved dispersibility:
preparing PVA/PVP composite dispersion liquid; dispersing gold nanoparticles in DMF, combining with DMF solution of EDC and NHS, oscillating and activating for 4 hours at room temperature, adding Fe dispersed in mesoporous silica surface modification photosensitizer of PVA/PVP composite dispersion liquid into an activation system3O4Nanoparticles; and (3) oscillating for reaction overnight, centrifuging to remove supernatant, washing with deionized water, ultrasonically dispersing in the deionized water for 15-20min, centrifuging, and drying to obtain the magnetic nanoparticles.
Wherein the concentration of the PVA dispersion liquid is 0.1-0.5 wt%.
Wherein the PVP dispersion concentration is 0.05-0.3 wt%.
Preferably, the PVP dispersion concentration is between 0.05 and 0.1 wt%.
Preferably, the particle size of the gold nanoparticles is 1-5 nm.
Further preferably, the particle size of the gold nanoparticles is 2-5 nm.
In another aspect of the present invention, there is provided a use of the magnetic nanoparticle as a nuclear magnetic resonance contrast agent, comprising: imaging and positioning the brain tumor, and performing photodynamic therapy on the brain tumor by taking the nuclear magnetic imaging as guidance.
The invention has the technical effects that:
(1) fe for preparing surface coated mesoporous silicon dioxide3O4When the nano particles are used, hydroxyethyl cellulose is used as a barrierThe polymerization agent is used as organic macromolecular hydroxyethyl cellulose which is adsorbed on silicon dioxide particles to generate steric hindrance, and effectively prevents the further aggregation of the nano particles, thereby obviously improving the formed silicon dioxide-Fe3O4Dispersibility and uniformity of the nanoparticles; and a good matrix particle foundation is laid for the final preparation of the magnetic nanoparticles.
(2) When the final magnetic particle product is prepared, a PVA (polyvinyl alcohol)/PVP (polyvinyl pyrrolidone) composite polymerization inhibitor is adopted, wherein a large amount of free polar hydroxyl groups in PVA and metal particles form a bonding effect of chelate bonds and are tightly coated around the metal particles, so that a three-dimensional surrounding shape structure limited by organic molecule long chains is formed, the size of the formed nanoparticles is limited, and the purposes of improving the particle size uniformity and preventing adhesion are achieved.
(3) In addition, PVA and PVP molecules, especially PVP molecules, coordinate with surface atoms of the formed magnetic nanoparticles through nitrogen atoms and oxygen atoms, so that long alkane chains of molecules which are not coordinated extend to the periphery of the particles, mutual agglomeration among the nanoparticles is effectively prevented, and the magnetic nanoparticles with good dispersibility are prepared.
Drawings
FIG. 1 Fe prepared in example 13O4TEM photograph of nanoparticles
FIG. 2 TEM photograph of magnetic nanoparticles prepared in example 3
FIG. 3 TEM photograph of magnetic nanoparticles prepared in comparative example
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of mesoporous silica-coated Fe3O4Nanoparticles
Mixing 10-15nm Fe3O4Dispersing 1mmol of nano particles in 100mL of 0.1 wt% hydroxyethyl cellulose aqueous solution at 50 ℃, adjusting the pH value to 9.0, adding tetraethyl orthosilicate 10mL and ethyl acetate 25mL under the stirring state, stirring for 10min to dissolve, adding 3-aminopropyl-triethoxysilane 1.5mL, keeping the temperature of the reaction solution at 65 ℃, stirring for reaction for 24 hours, cooling and centrifuging the product, washing with ethanol for 6 times to obtain Fe with the surface coated with mesoporous silica3O4Nanoparticles dispersed in water for use.
Example 2
Silicon dioxide-Fe 3O4 nano-core particle for preparing surface modified photosensitizer
Dissolving 5.4g hematoporphyrin photosensitizer in 100mL DMF under the condition of keeping out of the sun, weighing 4.2g EDC, dissolving in 100mL DMF, weighing 7.2g NHS, dissolving in 100mL DMF, combining the above DMF solutions, vibrating and activating at room temperature for 4 hours, adding 2.5g methyl propionyl oxypropyl trimethoxy silane and 6mmol Fe dispersed in the solution for preparing the surface-coated mesoporous silica into the activation system3O4Nanoparticles, the dispersion solution being a 0.1 wt% aqueous solution of hydroxyethyl cellulose; oscillating for reaction overnight, centrifuging and discarding supernatant, washing with deionized water, and drying to obtain Fe of the mesoporous silica surface modified photosensitizer3O4Nanoparticles.
Example 3
Preparation of magnetic nanoparticles with improved dispersibility
Dispersing 1mmol of gold nanoparticles of 3-5nm in 20mL of DMF, weighing 1.2g of EDC, dissolving in 40mL of DMF, weighing 2.0g of NHS, dissolving in 40mL of DMF, combining the DMF solutions, vibrating and activating at room temperature for 4 hours, adding Fe of mesoporous silica surface modification photosensitizer into the activated system3O4The PVA/PVP composite dispersion liquid of the nano particles, wherein the concentration of PVA in the dispersion liquid is 0.2 wt%, and the concentration of PVP in the dispersion liquid is 0.05 wt%; and (3) oscillating for reaction overnight, centrifuging to remove supernatant, washing with deionized water, ultrasonically dispersing in the deionized water for 15min, and centrifuging to obtain the magnetic nanoparticles.
And performing TEM characterization on the prepared magnetic nanoparticles. As can be seen from the characterization result of FIG. 2, the prepared nanoparticles have an obvious core-shell structure, are spherical, have a particle size of about 50nm and are uniformly distributed as a whole; the nano particles are uniformly dispersed, no obvious adhesion occurs in the visual field, and no large-scale aggregation phenomenon occurs; exhibit good dispersibility.
Comparative example 1
S1: dissolving 2.7g hematoporphyrin in 50mL DMF under the condition of keeping out of the sun, weighing 2.1g EDC and dissolving in 50mL DMF, weighing 3.6g NHS and dissolving in 50mL DMF, combining the DMF solutions, vibrating and activating for 4 hours at room temperature, adding Fe with surface coated mesoporous silica into the activated system3O43mmol of nano particles, shaking for reaction overnight, centrifuging, discarding supernatant, washing with clear water, and drying to obtain Fe of the mesoporous silica surface modified photosensitizer3O4Nanoparticles;
s2: dispersing 0.5mmol of gold nanoparticles with the particle size of 3-5nm in 10mL of DMF, weighing 0.6g of EDC, dissolving in 20mL of DMF, weighing 1.0g of NHS, dissolving in 20mL of DMF, combining the DMF solutions, vibrating and activating at room temperature for 4 hours, adding the prepared Fe of the mesoporous silica surface modification photosensitizer into an activation system3O4And (3) carrying out oscillation reaction on the nano particles overnight, centrifuging, discarding supernatant, washing with clear water, and drying to obtain the magnetic nano particles.
The prepared magnetic nanoparticles were characterized, and FIG. 3 shows TEM photographs of the magnetic nanoparticles, from which it can be seen that although the prepared nanoparticles are Fe3O4The mesoporous silicon dioxide coated on the surfaces of the nanoparticles has an obvious core-shell structure and relatively uniform particle size; however, the nanoparticles have obvious adhesion and development, are in an aggregation state and have poor dispersibility.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (3)
1. A method for preparing magnetic nanoparticles with improved dispersibility and particle uniformity, the method comprising the steps of:
(1) preparation of mesoporous silica-coated Fe3O4Nanoparticle:
mixing Fe3O4Dispersing nano particles in 0.05-0.1 wt% hydroxyethyl cellulose water solution at 50-60 deg.C, regulating pH value to 8.5-9.0, adding tetraethyl orthosilicate and ethyl acetate under stirring, stirring until dissolving, adding 3-aminopropyl-triethoxysilane, keeping the temperature of the reaction solution at 60-65 deg.C, stirring to react for 16-24 hours, cooling the product, centrifuging, washing with ethanol to obtain Fe coated with mesoporous silica on the surface3O4Nanoparticles;
(2) silica-Fe for preparing surface modified photosensitizer3O4Nano-core particles:
s1 Fe with surface coated with mesoporous silica3O4Dispersing the nano particles in a hydroxyethyl cellulose solution to form a dispersion liquid;
s2 dissolving photosensitizer hematoporphyrin in N, N-dimethylformamide under dark condition, adding EDC and NHS for activation for 3-4 h, adding Fe coated with mesoporous silica dispersed in hydroxyethyl cellulose solution into the activation system3O4Nanoparticles, the hydroxyethyl cellulose concentration of the hydroxyethyl cellulose solution being 0.05-0.1 wt%; oscillating for reaction overnight, centrifuging and discarding supernatant, washing with clear water, and drying to obtain Fe of the mesoporous silica surface modified photosensitizer3O4Nanoparticles;
(3) preparation of magnetic nanoparticles with improved dispersibility:
preparing PVA/PVP composite dispersion liquid, wherein the concentration of the PVA dispersion liquid is 0.1-0.5 wt%; the PVP dispersion solution has the concentration of 0.05-0.1 wt%; dispersing gold nanoparticles in DMF, mixing with DMF solution of EDC and NHS, and shaking and activating at room temperature for 4 hrThen, Fe of the mesoporous silica surface modification photosensitizer dispersed in the PVA/PVP composite dispersion liquid is added into an activation system3O4A nanoparticle dispersion liquid; and (3) oscillating for reaction overnight, centrifuging to remove supernatant, washing with deionized water, ultrasonically dispersing in the deionized water for 15-20min, centrifuging, and drying to obtain the magnetic nanoparticles.
2. The method according to claim 1, wherein in step (1), tetraethyl orthosilicate, ethyl acetate and 3-aminopropyl-triethoxysilane are added in a volume ratio of 10-15:20-40: 1.
3. The method according to claim 1, wherein in the step (3), the gold nanoparticles have a particle size of 2-5 nm.
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