CN114931638A - BFO-Zein/EC magnetic composite membrane material and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the technical field of composite materials, and discloses a BFO-Zein/EC magnetic composite film material and a preparation method and application thereof. The barium ferrite nanoparticles of the present invention are modified with oleic acid, then mixed and stirred with the modified zein fibers, dispersed evenly, put into a mold for die-casting to form a film, and magnetized to obtain a BFO-Zein/EC magnetic film . Oleic acid modification improved the dispersion of barium ferrite nanoparticles and promoted their better binding to modified zein fibers. Compared with traditional exogenous magnetic field-induced targeting materials, the magnetic film material of the present invention greatly simplifies treatment steps and costs, has good biocompatibility, self-degradability, stable structure and magnetic properties, and can be applied to medicine drug targeting in the field.

Description

A kind of BFO-Zein/EC magnetic composite film material and its preparation method and application

technical field

The invention relates to the technical field of composite materials, in particular to a BFO-Zein/EC magnetic composite film material and a preparation method and application thereof.

Background technique

Magnetic drug targeted therapy is a treatment method that uses a magnetic field to gather magnetically responsive drugs at the target site, increase the concentration of the drug at the target site, and reduce the toxicity and side effects of the drug to normal tissues. At present, magnetic drug targeting in vivo is mostly induced by in vitro strong magnetic field, but in vitro induction by strong magnetic field has problems such as cumbersome treatment steps, complicated equipment, and expensive treatment costs. Spontaneous magnetic field induction of targeted membrane materials is expected to eliminate or improve the defects of in vitro strong magnetic field induction therapy. Therefore, the development of spontaneous magnetic field-induced targeting membrane materials and their use in magnetic drug targeting has become an urgent need in the art.

SUMMARY OF THE INVENTION

In view of this, the present invention provides a BFO-Zein/EC magnetic composite membrane material, a preparation method and application, and solves the problem of blanks in the current research on spontaneous magnetic field-induced targeting membrane materials.

In order to achieve the above object, the present invention adopts the following technical solutions:

The invention provides a preparation method of a BFO-Zein/EC magnetic composite film material, comprising the following steps:

S1: mixing ferric chloride, barium chloride, sodium hydroxide, oleic acid and water, separating the precursor nanoparticles from the obtained mixed solution and calcining to obtain BaFe ₁₂ O ₁₉ nanoparticles;

S2: mixing zein, ethyl cellulose and an aqueous ethanol solution, and performing irradiation modification to obtain modified zein fibers;

S3: mixing BaFe ₁₂ O ₁₉ nanoparticles and modified zein fibers, and magnetizing to obtain a BFO-Zein/EC magnetic composite film;

Step S1 and step S2 have no sequence requirement.

Preferably, in the step S1, the mixing method of ferric chloride, barium chloride, sodium hydroxide, oleic acid and water is as follows: first, ferric chloride, barium chloride and water are mixed, sodium hydroxide is added, and then After stirring and mixing for 3 to 5 hours, oleic acid was added.

Preferably, in the step S1, the molar ratio of barium chloride and ferric chloride is 1:9 to 14, the volume concentration of oleic acid in the mixed solution is 5 to 50 mL/L, and the sodium hydroxide in the mixed solution The mass concentration of 20 ~ 200g/L.

Preferably, in the step S1, sodium hydroxide is added at 40-80°C.

Preferably, in the step S1, the calcination temperature is 700-1100°C, and the calcination time is 1-3 hours.

Preferably, in the step S2, the mass ratio of zein and ethyl cellulose is 2-4:1, the mass-volume ratio of zein and the aqueous ethanol solution is 1-3 g: 10 mL, and the ethanol in the aqueous ethanol solution is 1-3 g: 10 mL. The volume concentration of 60 to 80%.

Preferably, in the step S2, the irradiation modification is performed under a protective gas, the protective gas is nitrogen or hydrogen, and the irradiation dose is 50-100 KGy.

Preferably, in the step S3, the mass ratio of the BaFe ₁₂ O ₁₉ nanoparticles and the modified zein fibers is 1-3:1; before magnetization, the BaFe ₁₂ O ₁₉ nanoparticles and the modified zein fibers are The mixture obtained by mixing the fibers is die-casted; the magnetic field strength for magnetization is 0.5-5T.

The present invention also provides a BFO-Zein/EC magnetic composite film material prepared by the method for preparing the BFO-Zein/EC magnetic composite film material.

The invention also provides the application of the BFO-Zein/EC magnetic composite film material in the preparation of magnetic medicine.

As can be seen from the above-mentioned technical solutions, compared with the prior art, the beneficial effects of the present invention are as follows:

The BaFe ₁₂ O ₁₉ of the present invention has good magnetic properties, stability and safety, can be uniformly dispersed in the film after being modified by oleic acid, and is tightly bound; while zein (Zein) and ethyl cellulose ( EC), as a natural polymer material, has good biocompatibility and film-forming properties, and then through the cross-linking modification treatment, the loading capacity is greatly increased, and the structure can be kept stable;

The invention adopts the electron beam irradiation method to carry out the cross-linking modification treatment on the material, and the method has the advantages of environmental friendliness, continuous operation, batch processing, low cost, little damage to the substrate, etc., and can also achieve the effect of sterilization, Saves a lot of steps;

The magnetic film material structure obtained by the method of the invention can maintain stable magnetic properties for a long time, has obvious adsorption and aggregation effect on ferromagnetic particles, has positive significance for the development of endogenous magnetic targeting, and can be used for chronic In vivo sustained drug targeting of disease.

Description of drawings

In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only It is an embodiment of the present invention. For those of ordinary skill in the art, other drawings can also be obtained according to the provided drawings without creative work.

Fig. 1 is the XRD pattern of the material obtained in Example 1 of the present invention and Comparative Examples 1-2;

2 is the SEM images of the materials obtained in Example 1 and Comparative Examples 1 to 2 of the present invention, wherein (a) is the SEM image of the BFONPs obtained in Comparative Example 2, and (b) is the SEM image of the BFO-Zein/EC magnetic film, (c) is the SEM image of the BFO-Zein magnetic film;

3 is a VSM diagram of the materials obtained in Example 1 and Comparative Examples 1-2 of the present invention.

Detailed ways

The invention provides a preparation method of a BFO-Zein/EC magnetic composite film material, comprising the following steps:

S1: mixing ferric chloride, barium chloride, sodium hydroxide, oleic acid and water, separating the precursor nanoparticles from the obtained mixed solution and calcining to obtain BaFe ₁₂ O ₁₉ nanoparticles;

S2: mixing zein, ethyl cellulose and an aqueous ethanol solution, and performing irradiation modification to obtain modified zein fibers;

S3: mixing BaFe ₁₂ O ₁₉ nanoparticles and modified zein fibers, and magnetizing to obtain a BFO-Zein/EC magnetic composite film;

Step S1 and step S2 have no sequence requirement.

In the present invention, in the step S1, centrifugal drying is performed before the precursor nanoparticles are calcined; the rotational speed of the centrifugal drying is preferably 4000-12000 r/min, more preferably 8000-11000 r/min; the temperature of the centrifugal drying is preferably The temperature is 55-90°C, more preferably 58-85°C; the centrifugal drying time is preferably 10-14h, more preferably 11-13h.

In the present invention, in the step S1, the mixing method of ferric chloride, barium chloride, sodium hydroxide, oleic acid and water is as follows: first, ferric chloride, barium chloride and water are mixed, and sodium hydroxide is added. , and then stir and mix for 3 to 5 hours and then add oleic acid;

The stirring and mixing time is preferably 3.5-4.5 h, more preferably 220-250 min.

In the present invention, in the step S1, the ferric chloride is preferably ferric chloride containing crystal water, more preferably FeCl ₃ ·6H ₂ O; the barium chloride is preferably barium chloride containing crystal water, further BaCl ₂ ·2H ₂ O is preferred.

In the present invention, in the step S1, the molar ratio of barium chloride and ferric chloride is preferably 1:9-14, more preferably 1:10-13; the volume concentration of oleic acid in the mixed solution is preferably 5 ~50mL/L, more preferably 10~40mL/L; the mass concentration of sodium hydroxide in the mixed solution is preferably 20~200g/L, more preferably 50~150g/L.

In the present invention, in the step S1, sodium hydroxide is preferably added at 40-80°C, more preferably sodium hydroxide is added at 50-70°C.

In the present invention, in the step S1, the calcination temperature is preferably 700-1100°C, more preferably 800-1000°C; the calcination time is preferably 1-3h, more preferably 1.5-2.5h.

In the present invention, in the step S2, the mass ratio of zein and ethyl cellulose is preferably 2-4:1, more preferably 2.5-3.5:1; the mass volume of zein and ethanol aqueous solution The ratio is preferably 1-3 g:10 mL, more preferably 1.5-2.5 g:10 mL; the volume concentration of ethanol in the ethanol aqueous solution is preferably 60-80%, more preferably 65-75%.

In the present invention, in the step S2, the irradiation modification is carried out under a protective gas, and the protective gas is preferably nitrogen or hydrogen, more preferably nitrogen; the irradiation dose is preferably 50-100KGy, more preferably 60- 80KGy.

In the present invention, in the step S3, the mass ratio of BaFe ₁₂ O ₁₉ nanoparticles and modified zein fibers is preferably 1-3:1, more preferably 1.5-2.5:1; The mixture obtained by mixing ₁₂ O ₁₉ nanoparticles and modified zein fibers is subjected to die casting; the magnetic field strength for magnetization is preferably 0.5-5T, more preferably 1-4T.

The present invention also provides a BFO-Zein/EC magnetic composite film material prepared by the method for preparing the BFO-Zein/EC magnetic composite film material.

The invention also provides the application of the BFO-Zein/EC magnetic composite film material in the preparation of magnetic medicine.

The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the protection scope of the present invention.

Example 1

Dissolve 16.2g FeCl ₃ ·6H ₂ O and 1.465g BaCl ₂ ·2H ₂ O in 100mL deionized water, add 10g sodium hydroxide at 60°C and continue stirring for 4h, then add 2mL oleic acid and continue stirring for 1h to obtain the precursor; The obtained precursor was centrifuged and dried at 5000 r/min at 80 °C for 12 h, and then calcined at 900 °C for 2 h to obtain BaFe ₁₂ O ₁₉ nanoparticles;

2g of zein and 0.5g of ethyl cellulose were dissolved in 10 mL of 70% ethanol aqueous solution, filled with _N2 , bagged and irradiated with an absorbed dose of 80 kGy, and then precipitated to obtain modified corn gliadin fibers;

2g BaFe ₁₂ O ₁₉ nanoparticles and 1g modified zein fibers were mixed and stirred for 30 minutes, and then put into a mold for uniform dispersion and die-casting into a 40mm×40mm×1mm film body, and magnetized at 2T magnetic field intensity to obtain BFO- Zein/EC Magnetic Film.

Example 2

Dissolve 15g FeCl ₃ ·6H ₂ O and 1.1g BaCl ₂ ·2H ₂ O in 100mL deionized water, add 8g sodium hydroxide at 70°C and continue stirring for 4h, then add 1.5mL oleic acid and continue stirring for 1h to obtain the precursor; The obtained precursor was centrifuged and dried at 9000 r/min at 75 °C for 11 h, and then calcined at 1000 °C for 2.5 h to obtain BaFe ₁₂ O ₁₉ nanoparticles;

2.5g of zein and 1g of ethyl cellulose were dissolved in 10mL of 80% ethanol aqueous solution, filled with _N2 , bagged and irradiated with an absorbed dose of 60kGy, and then precipitated to obtain modified corn gliadin fibers;

1g BaFe ₁₂ O ₁₉ nanoparticles and 1g modified zein fibers were mixed and stirred for 30 minutes, and then put into a mold to be die-casted into a 40mm×40mm×1mm film body after uniform dispersion, and magnetized under 2T magnetic field intensity to obtain BFO- Zein/EC Magnetic Film.

Comparative Example 1

Dissolve 16.2g FeCl ₃ ·6H ₂ O and 1.465g BaCl ₂ ·2H ₂ O in 100mL deionized water, add 10g sodium hydroxide at 60°C and continue stirring for 4h, then add 2mL oleic acid and continue stirring for 1h to obtain the precursor; The obtained precursor was centrifuged and dried at 5000 r/min at 80 °C for 12 h, and then calcined at 900 °C for 2 h to obtain BaFe ₁₂ O ₁₉ nanoparticles;

Dissolve 2.5g of zein in 10mL of an aqueous ethanol solution with a volume concentration of 70%, fill it with N, bag it, and carry out irradiation modification, the absorbed dose is _80kGy , and then separate it out to obtain modified zein fibers;

2g of BaFe ₁₂ O ₁₉ nanoparticles and 1g of modified zein fibers were stirred for 30min, dispersed uniformly and then put into a mold for die casting into a 40mm×40mm×1mm film body, and magnetized to obtain a BFO-Zein magnetic film.

Comparative Example 2

Dissolve 16.2 g FeCl ₃ ·6H ₂ O and 1.465 g BaCl ₂ ·2H ₂ O in 100 mL of deionized water, add 10 g of sodium hydroxide at 60°C and continue stirring for 4 hours, then add 2 mL of oleic acid and continue stirring for 1 hour to obtain the precursor ; The obtained precursor was centrifuged and dried at 5000 r/min at 80 °C for 12 h, and then calcined at 900 °C for 2 h to obtain BaFe ₁₂ O ₁₉ nanoparticles, which were denoted as BFONPs.

The materials obtained in Example 1 and Comparative Examples 1-2 were tested, and the obtained results are shown in Figures 1-3.

It can be seen from Figure 1 that the BFO NPs have obvious characteristic diffraction peaks at 2θ=30.3, 32.2, 34.1, 37.1, 40.3, 42.4, 55.1, 56.3, 56.6, 63.1, corresponding to BaFe ₁₂ O ₁₉ nanoparticles; The diffraction peaks of the BFO-Zein/EC magnetic film are also very significant in the spectrum, indicating that the magnetic particles account for a large proportion in the magnetic film and have good magnetic properties.

It can be seen from Figure 2 that after the modification with oleic acid, the size distribution of barium ferrite nanoparticles is uniform and the dispersibility is good. ) and the superparamagnetic critical size (14nm) range; ridges of about 200nm are formed on the surface of the magnetic film after cellulose modification, which makes the material superhydrophobic, thereby greatly improving the water stability of the film, while barium ferrite The body is evenly distributed on the magnetic film. It shows that the BFO-Zein/EC magnetic film obtained in the present invention has better stability and magnetic properties than BFO-Zein magnetic film and BFO NPs.

It can be seen from Figure 3 that the saturation magnetization of the BFO-Zein/EC magnetic film obtained by the present invention is 44.75emu/g, the remanence is 24.84emu/g, and the coercivity is -4.8k; while the saturation magnetization of the BFO NPs is 65.19emu/g g, the remanence is 33.32emu/g, the coercivity is -4.8k; the saturation magnetization of the BFO-Zein magnetic film is 43.32emu/g, the remanence is 23.41emu/g, and the coercivity is -4.8k.

The BFO-Zein/EC magnetic film obtained by the invention not only has excellent magnetic properties, but also has high stability. The development of magnetic targeting has positive implications for sustained drug targeting of chronic diseases in vivo.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a BFO-Zein/EC magnetic composite film material is characterized by comprising the following steps:

s1: mixing ferric chloride, barium chloride, sodium hydroxide, oleic acid and water, separating precursor nano particles from the obtained mixed solution, and calcining to obtain BaFe ₁₂ O ₁₉ A nanoparticle;

s2: mixing zein, ethyl cellulose and an ethanol aqueous solution, and carrying out irradiation modification to obtain modified zein fibers;

s3: mixing BaFe ₁₂ O ₁₉ Mixing the nano particles and the modified Zein fiber, and magnetizing to obtain a BFO-Zein/EC magnetic composite membrane;

step S1 and step S2 have no sequential requirement.

2. The method for preparing the BFO-Zein/EC magnetic composite membrane material according to claim 1, wherein in step S1, the mixing manner of iron chloride, barium chloride, sodium hydroxide, oleic acid and water is: firstly, mixing ferric chloride, barium chloride and water, adding sodium hydroxide, stirring and mixing for 3-5 h, and then adding oleic acid.

3. The preparation method of the BFO-Zein/EC magnetic composite film material according to claim 2, wherein in step S1, the molar ratio of barium chloride to ferric chloride is 1: 9-14, wherein the volume concentration of oleic acid in the mixed solution is 5-50 mL/L, and the mass concentration of sodium hydroxide in the mixed solution is 20-200 g/L.

4. The preparation method of the BFO-Zein/EC magnetic composite film material as claimed in claim 3, wherein in step S1, sodium hydroxide is added at 40-80 ℃.

5. The preparation method of the BFO-Zein/EC magnetic composite film material as claimed in claim 1 or 2, wherein in the step S1, the calcination temperature is 700-1100 ℃, and the calcination time is 1-3 h.

6. The preparation method of the BFO-Zein/EC magnetic composite film material as claimed in claim 5, wherein in step S2, the mass ratio of Zein to ethyl cellulose is 2-4: 1, the mass-volume ratio of the zein to the ethanol water solution is 1-3 g: 10mL, and the volume concentration of ethanol in the ethanol water solution is 60-80%.

7. The preparation method of the BFO-Zein/EC magnetic composite film material as claimed in claim 6, wherein in the step S2, irradiation modification is performed under a protective gas, the protective gas is nitrogen or hydrogen, and the irradiation dose is 50-100 KGy.

8. The preparation method of the BFO-Zein/EC magnetic composite film material as claimed in any one of claims 1-4, wherein in the step S3, BaFe ₁₂ O ₁₉ The mass ratio of the nano particles to the modified zein fibers is 1-3: 1; before magnetizing, to BaFe ₁₂ O ₁₉ The mixture obtained by mixing the nano particles and the modified zein fiber is subjected to die-casting forming; the magnetizing magnetic field intensity is 0.5-5T.

9. The BFO-Zein/EC magnetic composite membrane material prepared by the method for preparing the BFO-Zein/EC magnetic composite membrane material as claimed in any one of claims 1-8.

10. The use of the BFO-Zein/EC magnetic composite membrane material of claim 9 in the preparation of magnetic pharmaceuticals.

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