CN115120747B - Hydroxyapatite-loaded ferroferric oxide nanorod and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a hydroxyapatite-loaded ferroferric oxide nano rod and a preparation method thereof. The nano rod prepared by the invention has regular shape, the length is about 50-55nm, the width is close to 2+/-0.5 nm, and the nano rod has good dispersibility, and is an iron-containing magnetic nano composite material. The preparation method comprises the following steps: respectively dissolving calcium chloride and ammonium dihydrogen phosphate in ethanol and distilled water, mixing, adding oleic acid, oleylamine and prepared ferroferric oxide nanoparticles, and transferring the obtained mixture into an autoclave lined with polytetrafluoroethylene with proper ethanol and water ratio. The autoclave was placed in an oven for heating. After the reaction, the mixture was cooled, washed with absolute ethanol and acetone, centrifuged, and dispersed in cyclohexane. In addition, useF-127 is used for carrying out surface modification on the composite material, so that the nanocomposite material can be endowed with good biocompatibility. The composite material prepared by surface modification has nuclear magnetic resonance enhancement effect and potential as a photo-thermal conversion agent.
Description
Technical Field
The invention relates to a preparation method of a nano composite material, in particular to hydroxyapatite-loaded ferroferric oxide (Fe) 3 O 4 HAp) nanorods, and a preparation method and application thereof, wherein the method is simple and stable and can be widely applied to the fields of biology and medicine.
Background
Cancer has long become one of the most life threatening diseases to humans on earth, leading to death of millions of people in the 20 th century. In order to address the threat of cancer to humans, scientists have made numerous attempts in recent years to initiate a variety of treatments. However, due to tumor heterogeneity and a part of complications, patient survival is not high. To solve these problems, scientists have introduced nanomedicines.
In recent years, the combination of nano-drugs with cancer therapy has become a major trend in the development of tumor diagnosis and treatment, and some nano-drugs have been approved into the market. The nanoscale therapeutic system becomes a model for the alternative diagnosis and treatment of tumors, has good targeting and small side effects, and overcomes the limitations of the traditional therapy.
Molecular imaging techniques have been invented and widely used as techniques that can accurately diagnose and detect tumors, including Magnetic Resonance Imaging (MRI), ultrasound imaging (US), computed Tomography (CT), and the like. Among them, the Magnetic Resonance Imaging (MRI) has excellent soft tissue recognition ability and high resolution due to its non-ionizing radiation, and is one of the most widely used techniques for early diagnosis and detection of tumors. The nuclear magnetic resonance contrast agent (contrast agent) can improve imaging resolution and increase imaging contrast of normal and pathological tissues, thereby improving sensitivity and specificity of nuclear magnetic resonance diagnosis of tumors. Gadolinium (Gd) -based contrast agents have long been approved for use by the U.S. Food and Drug Administration (FDA) and european drug administration, but in recent years there have been some clinical data and studies showing that gadolinium contrast agents, which have been widely used, have some renal toxicity and can cause renal-derived systemic fibrotic diseases. To overcome the above drawbacks, researchers have developed iron (Fe) -based nuclear magnetic resonance contrast agents (Iqbal, m.z., ma, x., chen, t., zhang, l., ren, w.,Xiang,L.,Wu,A.,2015.Silica-coated super-paramagnetic iron oxide nanoparticles(SPIONPs):a new type contrast agent of T 1 magnetic Resonance Imaging (MRI). J.mate.chem.b 3, 5172-5181), although it can be an excellent iron supplement, the imaging contrast is less excellent than gadolinium contrast.
In the novel cancer treatment method, photodynamic therapy is noninvasive and has good curative effect, and clinical acceptance is obtained. Compared with the traditional photosensitizer, the SF and Ce6 loaded nanocomposite has high photo-thermal conversion efficiency, low toxicity and excellent stability.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a hydroxyapatite-loaded ferroferric oxide nanocomposite with nuclear magnetic resonance enhancement effect and photodynamic therapeutic effect and a preparation method thereof.
In order to solve the technical problems, the invention firstly provides a hydroxyapatite-loaded ferroferric oxide nano material (Fe 3 O 4 HAp nanorods), comprising the steps of:
1) Fe is added to 3 O 4 The nanoparticles are dispersed in cyclohexane;
2) Calcium chloride (CaCl) 2 ) Dissolving in ethanol to obtain solution A, and adding ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) Dissolving in distilled water to prepare solution B; adding a certain volume of oleic acid and oleylamine into a container, and uniformly mixing to obtain a C solution; pouring the solution A and the solution B into the solution C respectively, and then adding the Fe obtained in the step 1) 3 O 4 A nanoparticle dispersion; transferring the obtained mixed solution into a hydrothermal kettle, adding ethanol and water, reacting for a certain time in the hydrothermal kettle, and centrifugally washing after the reaction is finished to obtain Fe 3 O 4 HAp nanorods.
As an alternative to the present invention, the Fe 3 O 4 The nanoparticles can be selected from commercial products or prepared by methods already reported in the prior art, and the invention is specific to Fe 3 O 4 The nanoparticle is not limited. Preferred Fe 3 O 4 Preparation method of nanoparticleReference (M.Z.Iqbal, X.Ma, T.Chen, L.Zhang, W.Ren, L.Xiang, A.Wu), silica-coated super-paramagnetic iron oxide nanoparticles (SPIONPs): a new type contrast agent of T 1 Magnetic Resonance Imaging (MRI), j.mate.chem.b.3 (2015) 5172-5181).
As an alternative scheme of the invention, the mass ratio of calcium chloride to ethanol in the solution A in the step 2) is 3:35-3:40, the mass ratio of ammonium dihydrogen phosphate to distilled water in the solution B is 3:100-4:100, the volume ratio of oleic acid to oleylamine in the solution A to the solution B is 0.5:1-1:0.5, the volume ratio of oleic acid to oleylamine in the solution C is 0.5:1-1:0.5, and the volume ratio of the solution A to the solution C is 1:3-5.
As an alternative scheme of the invention, after ethanol and water are added into a hydrothermal kettle, the volume ratio of the ethanol to the water is 3:1; the reaction temperature is 150-260 ℃ and the reaction time is 4-8 h.
As an alternative to the present invention, fe in the step 2) 3 O 4 The ratio of the total volume of the nanoparticle dispersion liquid and the mixed liquid is 3:70-3:90.
The invention also provides a deviceF-127 coated Fe 3 O 4 HAp nanorods, the preparation method of which comprises the following steps:
1) Fe prepared by the method of any one of claims 1 to 4 3 O 4 Dispersing HAp nanorods in cyclohexane to obtain Fe 3 O 4 -HAp nanorod dispersion;
2) Will beF-127 was dissolved in chloroform to obtain Fe 3 O 4 -HAp nanorod dispersion was added thereto and stirred at room temperature; adding distilled water for rotary evaporation, evaporating chloroform to obtain +.>F-127 coated Fe 3 O 4 HAp nanorods.
As the inventionIn a clear alternative, in said step 2)The mass ratio of F-127 to chloroform is 1:13-1:16, fe 3 O 4 The concentration of the HAp nanorod dispersion liquid is 5 mg/mL-10 mg/mL; fe (Fe) 3 O 4 HAp nanorod dispersionThe mass ratio of F-127 is 1:140-1:150.
The invention also provides a hydroxyapatite-loaded ferroferric oxide nanorod composite material, and the preparation method comprises the following steps:
3) The silk fibroin solution is mixed with the obtained silk fibroin solutionF-127 coated Fe 3 O 4 Stirring and mixing HAp nano rod dispersion liquid to obtain silk fibroin loaded Fe 3 O 4 -HAp nanorod dispersion;
4) Under dark condition and 4 ℃, the Ce6 solution is loaded with Fe of the silk fibroin of the step 3) 3 O 4 Stirring and mixing HAp nano rod dispersion liquid, centrifuging the obtained mixture, and finally obtaining a product; or further dispersing the product in distilled water, and preserving at 4deg.C for use.
As a preferable mode of the invention, in the step 1), the mass percentage concentration of the silk fibroin solution is 4%, and the silk fibroin solution are mixedF-127 coated Fe 3 O 4 Mixing HAp nano rod dispersion liquid in the volume ratio of 1:5-1:9, stirring for 8-18 h at 4 ℃, centrifuging the mixture at 10000 revolutions per minute for 10min to obtain Silk Fibroin (SF) -loaded Fe 3 O 4 HAp nanorod (MHNRs-SF) dispersion.
As a preferable mode of the present invention, in the step 2), 1mg/mL of Ce6 solution and MHNRs-SF dispersion are mixed in a volume ratio of 1:8 to 1:12Stirring for 8-18 h under dark condition and at 4 ℃; after the reaction was completed, the mixture was centrifuged at 10000 rpm for 20min, and redispersed in 10mL of distilled water to obtain Ce 6-and Silk Fibroin (SF) -supported Fe 3 O 4 HAP nanorod (MHNRs-SF-Ce 6) dispersion, and storing at 4 ℃ for later use.
The invention also provides application of the hydroxyapatite-loaded ferroferric oxide nanocomposite in preparation of nuclear magnetic resonance imaging contrast agents and tumor photodynamic therapy medicaments.
Compared with the prior art, the invention has the beneficial effects that:
(1) The hydroxyapatite loaded ferroferric oxide (Fe) 3 O 4 HAp nanorods) nanocomposite, r 1 Relaxation rate of 1.9mM -1 s -1 ，r 2 Relaxation rate of 7.6mM -1 s -1 Has potential application in nuclear magnetic resonance imaging contrast agents;
(2) Ce 6-loaded Fe 3 O 4 The Hap nanorods also show effective light synergism in vitro and have a certain photodynamic killing effect on tumor cells;
(3) The method has low requirement on experimental instruments, is simple and easy to operate, and the obtained nano particles have uniform shape and size and good dispersibility.
Drawings
FIG. 1 is a transmission electron microscope image of the product obtained in example 1 of the present invention.
FIG. 2 is a transmission electron microscope image of the product obtained in example 1 of the present invention (different from the position in FIG. 1).
FIG. 3 is an X-ray spectroscopy (EDS) image of the product obtained in example 1 of the present invention.
FIG. 4 shows the MRI image and the T1, T2 relaxation rate ratios of the product obtained in example 1 of the present invention.
FIG. 5 is a confocal image of the product of example 1 of the invention taken in 4T1 cells, the scale bar being 2 microns.
FIG. 6 shows the results of the live-dead experiment of 4T1 cells with the product of example 1 of the present invention, the scale of which is 100. Mu.m.
Detailed Description
The following examples are presented to those of ordinary skill in the art to make and evaluate the invention and are merely exemplary of the disclosure and are not intended to limit the scope. Although efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), some errors and deviations should be accounted for. Unless otherwise indicated, temperatures are in units of degrees celsius or at ambient temperature.
Example 1
Fe is added to 3 O 4 NPs were dispersed in 10mL cyclohexane. 60mg of calcium chloride (CaCl) 2 ) Dissolved in 1mL of ethanol to prepare solution a. Likewise, 34mg of monoamine phosphate (NH) 4 H 2 PO 4 ) Solution B was prepared by dissolving in 1mL of distilled water. Then, 2mL of oleic acid was taken in the flask, solutions A and B were poured in, and 300. Mu.L of Fe was then added 3 O 4 NCs and 2mL oleylamine. The solution was stirred for 10 minutes, poured into a 50mL polytetrafluoroethylene tube and transferred to another 100mL polytetrafluoroethylene tube lined with a stainless steel autoclave containing ethanol-water in a 3:1 volume ratio. The reaction was carried out in an autoclave at 200℃for 6 hours. After the reaction, MHNCs were precipitated by centrifugation at 11000rpm for 10min and repeated washing with a mixture of ethanol and acetone. Finally, MHNCs are dispersed in cyclohexane for further use.
700mgPF-127 was dissolved in 70mL chloroform. After sonication for 10 minutes, 1mL of synthesized MHNCs (Fe 3 O 4 HAp nanorods) was gently added to the mixture and kept stirring for 4h. Distilled water was added to the mixture, and chloroform was evaporated using a rotary evaporator. In addition, the MHNCs mixture was centrifuged and redispersed in distilled water to eliminate the excess PF-127.
1mL of a 4% SF solution and 7mL of a PF-127 coated MHNCs dispersion were stirred overnight at 4℃at 100rpm to couple SF to PF-127 coated MHNCs. Then, the mixture was centrifuged at 10000 rpm for 10 minutes, dispersed in 8mL of distilled water, and stored at 4 ℃.
1mg/mL of Ce6 solution was mixed with 10mL of SF-containing MHNCs dispersion and stirred at 100rpm and 4℃overnight. The mixture was then centrifuged at 10000 rpm for 20min, redispersed in 5mL of PBS and stored at 4 ℃ for further use.
The transmission electron microscope pictures of the product obtained in example 1 are shown in fig. 1 and 2, the X-ray energy spectrum analysis (EDS) picture of the obtained product is shown in fig. 3, and the nuclear magnetic resonance imaging picture and the T1, T2 relaxation ratios of the obtained product are shown in fig. 4, for example. As can be seen from fig. 1 and 2, the resulting hydroxyapatite-supported ferroferric oxide (Fe 3 O 4 HAp nanorods) has good dispersibility and uniform and stable particle size; as can be seen from FIG. 3, the resulting hydroxyapatite-supported ferroferric oxide (Fe 3 O 4 HAp nanorods) the nanocomposite does contain Ca and Fe elements; as can be seen from fig. 4, hydroxyapatite-supported ferroferric oxide (Fe 3 O 4 HAp nanorods) the nanocomposite has excellent nuclear magnetic resonance enhancing effect.
FIG. 5 shows the hydroxyapatite-supported ferroferric oxide (Fe 3 O 4 The HAp nanorod) nanocomposite was co-cultured with 4T1 (mouse breast cancer cells) cells for 12h, and then the cell membrane and nuclei were stained with DiI and DAPI dyes, respectively, to find out that hydroxyapatite-loaded ferroferric oxide (Fe) was migrated over a period of time 3 O 4 HAp nanorods) the nanocomposite can enter the cytoplasm and be dispersed uniformly.
FIG. 6 shows the loading of hydroxyapatite with different concentrations of ferroferric oxide (Fe 3 O 4 HAp nanorods) and 4T1 (mouse breast cancer cells) cells are co-cultured, and then after the laser irradiation of 808nm wavelength for different time, most cells are found to die through cell death by dying, so that the photodynamic therapy effect of the nanocomposite is proved to be good.
Example two
Fe is added to 3 O 4 NPs were dispersed in 10mL cyclohexane. 60mg of calcium chloride (CaCl) 2 ) Dissolved in 1mL of ethanol to prepare solution a. Likewise, 34mg of monoamine phosphate (TBA) was dissolved in 1mL of distilled water to prepare solution B. Then, 4mL of oleic acid was taken in the flask, solutions A and B were poured in, and 300. Mu. LFe was then added 3 O 4 NCs and 4mL oleylamine. The solution was stirred for 10 minutes, poured into a 50mL polytetrafluoroethylene tube and transferred to another 100mL polytetrafluoroethylene tube lined with a stainless steel autoclave containing ethanol-water in a 3:1 volume ratio. The reaction was carried out in an autoclave at 200℃for 6 hours. After the reaction, MHNCs were precipitated by centrifugation at 11000rpm for 10min and repeated washing with a mixture of ethanol and acetone. Finally, MHNCs are dispersed in cyclohexane for further use.
800mgPF-127 was dissolved in 80mL of chloroform. After sonication for 10 minutes, 1mL of synthesized MHNCs (Fe 3 O 4 HAp nanorods) was gently added to the mixture and kept stirring for 4h. Distilled water was added to the mixture, and chloroform was evaporated using a rotary evaporator. In addition, the MHNCs mixture was centrifuged and redispersed in distilled water to eliminate the excess PF-127.
1mL of a 4% SF solution and 7mL of a PF-127 coated MHNCs dispersion were stirred overnight at 4℃at 100rpm to couple SF to PF-127 coated MHNCs. Then, the mixture was centrifuged at 10000 rpm for 10 minutes, dispersed in 8mL of distilled water, and stored at 4 ℃.
1mg/mL of Ce6 solution was mixed with 10mL of SF-containing MHNCs dispersion and stirred at 100rpm and 4℃overnight. The mixture was then centrifuged at 10000 rpm for 20min, redispersed in 5mL of PBS and stored at 4 ℃ for further use. The MHNRs-SF-Ce6 dispersion prepared in example 2 has a similar photodynamic therapy effect as in example 1.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.
Claims (8)
1. The preparation method of the hydroxyapatite-loaded ferroferric oxide nanorod composite material is characterized by comprising the following steps of:
1) Fe is added to 3 O 4 The nanoparticles are dispersed in cyclohexane;
2) Dissolving calcium chloride in ethanol to prepare solution A, and dissolving ammonium dihydrogen phosphate in distilled water to prepare solution B; adding a certain volume of oleic acid and oleylamine into a container, and uniformly mixing to obtain a C solution; pouring the solution A and the solution B into the solution C respectively, and then adding the Fe obtained in the step 1) 3 O 4 A nanoparticle dispersion; transferring the obtained mixed solution into a hydrothermal kettle, adding ethanol and water, reacting for a certain time in the hydrothermal kettle, and centrifugally washing after the reaction is finished to obtain Fe 3 O 4 -HAp nanorods;
3) Fe to be prepared 3 O 4 Dispersing HAp nanorods in cyclohexane to obtain Fe 3 O 4 -HAp nanorod dispersion;
4) Pluronic is used for preparing the medicine ® F-127 was dissolved in chloroform to obtain Fe 3 O 4 -HAp nanorod dispersion was added thereto and stirred at room temperature; adding distilled water, rotary evaporating to obtain chloroform, and obtaining Pluronic ® F-127 coated Fe 3 O 4 -HAP nanorods;
5) The prepared silk fibroin solution and Pluronic ® F-127 coated Fe 3 O 4 Stirring and mixing HAp nano rod dispersion liquid, centrifuging the mixed liquid, and dispersing in distilled water to obtain silk fibroin loaded Fe 3 O 4 -HAP nanorod MHNRs-SF dispersion;
6) Mixing Ce6 solution with MHNRs-SF dispersion liquid, stirring overnight under dark and 4 ℃; obtaining MHNRs-SF-Ce6 solution after the reaction is finished, centrifuging the MHNRs-SF-Ce6 solution, and dispersing the solution in distilled water to obtain Ce6 and silk fibroin loaded Fe 3 O 4 HAP nanorod MHNRs-SF-Ce6 dispersion liquid at 4 DEG CAnd (5) storing for standby.
2. The preparation method of claim 1, wherein the mass ratio of calcium chloride to ethanol in the liquid a in the step 2) is 3:35-3:40, the mass ratio of ammonium dihydrogen phosphate to distilled water in the liquid B is 3:100-4:100, the volume ratio of oleic acid to oleylamine in the liquid C is 0.5:1-1:0.5, and the volume ratio of liquid a to liquid C is 1:3-5.
3. The preparation method according to claim 1, wherein after adding ethanol and water into the hydrothermal kettle, the volume ratio of the ethanol to the water is 3:1; the reaction temperature is 150-260 ℃ and the reaction time is 4-8 hours.
4. The method according to claim 1, wherein Fe in the step 2) 3 O 4 The ratio of the total volume of the nanoparticle dispersion liquid and the mixed liquid is 3:70-3:90.
5. The preparation method of claim 1, wherein the mass ratio of Pluronic F-127 to chloroform in the step 4) is 1:13-1:16, and Fe 3 O 4 The concentration of the HAp nano rod dispersion liquid is 5 mg/mL-10 mg/mL; fe (Fe) 3 O 4 HAp nanorod dispersion and Pluronic ® The mass ratio of F-127 is 1:140-1:150.
6. The method according to claim 1, wherein in the step 5), the concentration of the silk fibroin solution is 4% by mass, and the silk fibroin solution and Pluronic are mixed ® F-127 coated Fe 3 O 4 Mixing HAp nanorod dispersion liquid in a volume ratio of 1:5-1:9, stirring at 4 ℃ for 8-18 h, centrifuging the mixture at 10000 revolutions/minute for 10min to obtain silk fibroin SF-loaded Fe 3 O 4 -HAp nanorod MHNRs-SF dispersion.
7. The method of claim 1, wherein the steps areIn the step 6), mixing 1mg/mL of Ce6 solution with MHNRs-SF dispersion liquid in a volume ratio of 1:8-1:12, and stirring for 8-18 h under dark conditions and at 4 ℃; after the reaction is completed, centrifuging the mixture at 10000 revolutions per minute for 20min, and dispersing the mixture in 10mL distilled water to obtain Ce6 and silk fibroin SF-loaded Fe 3 O 4 -HAP nanorod MHNRs-SF-Ce6 dispersion, and preserving at 4 ℃ for later use.
8. The use of the hydroxyapatite-loaded ferroferric oxide nanorod composite material prepared by the method of claim 1 in the preparation of magnetic resonance imaging contrast agents and tumor photodynamic therapy medicaments.
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