CN116036270B - Preparation method and application of diagnosis and treatment integrated composite magnetic semiconductor nanomaterial - Google Patents
Preparation method and application of diagnosis and treatment integrated composite magnetic semiconductor nanomaterial Download PDFInfo
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Classifications
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- 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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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/26—Iron; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/0002—General or multifunctional contrast agents, e.g. chelated agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/04—X-ray contrast preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
Abstract
The invention belongs to the technical field of tumor diagnosis and treatment, and in particular relates to a preparation method and application of a diagnosis and treatment integrated composite magnetic semiconductor nanomaterial, wherein Bi (NO 3 ) 3 •5H 2 O、Fe 3 O 4 Mixing with mannitol, adding into water, stirring while adding acetic acid, stirring at room temperature for 30 min, adding NaI solution, stirring for 3 hr, aging for 1.5 hr, centrifuging to obtain precipitate, i.e. BiOI/Fe 3 O 4 . BiOI/Fe prepared by the method 3 O 4 The preparation method is simple, efficient, controllable in morphology and particle size, and the imaging agent and the therapeutic agent are integrated into one system, so that the system has a stable structure and shows a photo-thermal enhanced CDT treatment effect, hydroxyl free radicals are generated efficiently, tumors are killed by thermal ablation and active oxygen, and meanwhile, under the guidance of two imaging modes of MRI and CT, the treatment process and final curative effect evaluation of the CDT are monitored, so that the diagnosis and treatment integration of the tumors is realized.
Description
Technical Field
The invention belongs to the technical field of tumor diagnosis and treatment, and particularly relates to a preparation method and application of a diagnosis and treatment integrated composite magnetic semiconductor nanomaterial.
Background
Glioblastoma (GBM) is the most common primary tumor in the brain, accounting for 82% of brain Glioblastoma, and is a serious hazard to social health. The serious side effects and limited curative effect of the traditional cancer treatment mode further increase the treatment difficulty. Chemotherapy (chemodynamic therapy, CDT) is an emerging tumor treatment strategy that is defined as an in situ treatment that uses the fenton reaction or similar to the fenton reaction to generate reactive oxygen species at the tumor site. Briefly, iron-based nanomaterials dissolve ferrous ions under weakly acidic conditions of the tumor microenvironment, utilizing hydrogen peroxide (hydrogen peroxide, H) that is overproduced in the tumor microenvironment 2 O 2 ) Fenton's reaction is initiated to generate highly toxic hydroxyl radicals (hydroxyl radicals,. OH) to trigger apoptosis and inhibit tumor growth. Photothermal therapy (photothermal therapy, PTT) is an effective treatment strategy that utilizes photothermal agents to generate localized thermal energy under near infrared laser irradiation to ablate malignant tumors. The generated heat energy can also promote drug release/activation, gene expression, immune activation, fenton reaction and the like, so that the synergistic effect of cancer treatment is realized. In addition, imaging contrast agents such as magnetic resonance imaging (magnetic resonance imaging, MRI), computed tomography (computed tomography, CT) and the like and therapeutic agents such as CDT, PTT and the like are integrated into the same system, and the integration of diagnosis and therapy by monitoring the biodistribution of the drugs, the accurate diagnosis of tumors and the evaluation of therapeutic effects in real time has been the mainstream of research.
In the continuous development of numerous diagnostic agents, transition metal materials show great potential in terms of multi-modality imaging diagnosis of cancer (photoacoustic imaging, computed tomography, magnetic resonance imaging, positron emission tomography, etc.) and cancer treatment (chemotherapy, photothermal treatment, radiation treatment, photodynamic therapy, chemical kinetic treatment) due to their intensive near infrared absorption, excellent photothermal conversion efficiency, strong X-ray attenuation and magnetic properties. Based on this, the semiconductor nanomaterial prepared by controlling morphology and particle size will play an increasingly important role in cancer diagnosis and treatment.
Disclosure of Invention
The invention aims to develop an economical, safe and efficient multifunctional nano diagnosis and treatment agent, namely a composite magnetic semiconductor nano material, which has enhanced hydroxyl radical generation performance and photo-thermal conversion performance and is used for enhancing treatment of tumors.
The invention also aims to realize the application of the composite magnetic semiconductor nanomaterial in diagnosis and treatment integration, develop an MRI/CT bimodal imaging platform and a synergistic tumor treatment mode of photo-thermal enhanced chemical kinetics treatment so as to realize tumor diagnosis optimization and treatment effect maximization.
The technical scheme of the invention is as follows:
the invention provides a preparation method of a diagnosis and treatment integrated composite magnetic semiconductor nanomaterial, which adopts a chemical coprecipitation method to synthesize the composite magnetic semiconductor nanomaterial, wherein the composite magnetic semiconductor nanomaterial is BiOI/Fe 3 O 4 。
Further, the preparation method comprises the following steps: bi (NO) 3 ) 3 •5H 2 O、Fe 3 O 4 Mixing with mannitol, adding into water, stirring while adding acetic acid, stirring at room temperature for 30 min, adding NaI solution into the suspension, stirring for 3 hr, aging for 1.5 hr, centrifuging to obtain precipitate, i.e. BiOI/Fe 3 O 4 。
Further, the Bi (NO 3 ) 3 •5H 2 O and Fe 3 O 4 And the mass ratio of 1:0.5 to 2.
Further, bi (NO 3 ) 3 •5H 2 O, mannitol 0.5g, water 100mL, acetic acid 10mL, naI solution 10mL, and NaI 0.7 g/mL.
Further, the Fe 3 O 4 The preparation method of the (C) comprises the following steps: sodium citrate, naOH and NaNO 3 Adding water and heating to 105 ℃ to form a clear solution, then adding 4mmol FeSO 4 •7H 2 Adding 2mL of O solution into the clarified solution, heating at 100deg.C for 2 hr, naturally cooling to room temperature, centrifuging, and washing with ultrapure water to obtain Fe 3 O 4 。
The invention provides a BiOI/Fe prepared by a preparation method of a diagnosis and treatment integrated composite magnetic semiconductor nano material 3 O 4 。
The BiOI/Fe 3 O 4 For one or more uses selected from the group consisting of:
(1) Preparing chemical kinetics and photo-thermal medicines for tumor treatment;
(2) Preparing an imaging contrast agent for tumor magnetic resonance imaging and/or CT;
(3) Preparing a tumor multi-mode diagnosis and treatment integrated medicament;
further, the tumor is glioblastoma.
Bismuth oxyiodide (bisi) has been attracting attention as a novel layered photocatalytic semiconductor in which the band gap is the narrowest (eg=1.8 to 1.9 eVm) and its excellent photocatalytic properties are used for degradation of pollutants. Bismuth and iodine have strong X-ray attenuation capability, and BiOI is widely used for radiation therapy enhancement due to the radiation enhancement effect of high Z element, while BiOI is an excellent computed tomography material. Bismuth compounds are very low toxic compared to other heavy metals such as mercury and lead, however, bismuth complexes generally have low solubility in aqueous solutions, which greatly limits their clinical use in CT imaging. In addition, the application of layered bisoi is greatly limited because photogenerated electrons and holes are easily recombined.
Fe 3 O 4 The nano particles have larger surface area, good superparamagnetism, low cost, good photochemical stability and other excellent physical and biological characteristics, and can be applied to magnetic resonance imaging, targeted drug delivery, cell separation, cancer treatment (thermotherapy and chemical kinetics treatment) and the like.
Thus, the first and second substrates are bonded together,the composite magnetic semiconductor material in the invention comprises bismuth oxyiodide (BiOI) and ferroferric oxide (Fe) 3 O 4 ) Fe is added with 3 O 4 The BiOI is introduced to form a composite material, and the morphology, the particle size and the like of the composite magnetic semiconductor nanomaterial are controlled to form the composite magnetic semiconductor nanomaterial, so that the difficulty that the photo-generated electrons and holes of the BiOI are easy to compound is overcome, the photo-thermal effect is utilized to accelerate the reaction rate, the performance advantages of each component are enhanced, and the application of the composite magnetic semiconductor nanomaterial in tumor diagnosis and combined treatment is realized.
The beneficial effects of the invention are as follows:
the composite magnetic semiconductor nano material BiOI/Fe prepared by the invention 3 O 4 The preparation method is simple, efficient, controllable in morphology and particle size, and the imaging agent and the therapeutic agent are integrated into one system, so that the system has a stable structure and shows a photo-thermal enhanced CDT treatment effect, hydroxyl free radicals are generated efficiently, tumors are killed by thermal ablation and active oxygen, and meanwhile, under the guidance of two imaging modes of MRI and CT, the treatment process and final curative effect evaluation of the CDT are monitored, so that the diagnosis and treatment integration of the tumors is realized.
Drawings
FIG. 1A shows BiOI/Fe prepared in example 1 of the present invention 3 O 4 FIG. 1B is a TEM image of BiOI/Fe prepared in example 2 of the present invention 3 O 4 FIG. 1C is a TEM image of BiOI/Fe prepared in example 3 of the present invention 3 O 4 FIG. 1D is a TEM image of BiOI/Fe prepared in example 3 of the present invention 3 O 4 Is an X-ray diffraction pattern of (2).
FIG. 2A is a BiOI/Fe prepared in example 3 of the present invention 3 O 4 FIG. 2B shows the effect of hydroxyl radicals generated under different pH conditions, for BiOI/Fe prepared in example 3 of the present invention 3 O 4 At pH 5.4 and H 2 O 2 The hydroxyl radical effect is generated under the condition.
FIG. 3A is a BiOI/Fe prepared in example 3 of the present invention 3 O 4 FIG. 3B is a photo-thermal transformation performance chart of BiOI/Fe prepared in example 3 of the present invention 3 O 4 Is a photo-thermal enhanced CDT performance map.
FIG. 4A is a schematic illustration of a magnetic composite semiconductor nanomaterial made in accordance with example 3 of the present inventionBiOI/Fe 3 O 4 FIG. 4B is a graph showing the MR signal intensity of the magnetic composite semiconductor nanomaterial BiOI/Fe prepared in example 3 of the present invention 3 O 4 CT signal intensity map of (c).
FIG. 5 shows a magnetic composite semiconductor nanomaterial BiOI/Fe prepared in example 3 of the present invention 3 O 4 Is a graph of the effect of entering cells.
FIG. 6 shows a magnetic composite semiconductor nanomaterial BiOI/Fe prepared in example 3 of the present invention 3 O 4 Is a graph of the effect of fluorescent staining on the production of hydroxyl radicals in cells.
Detailed Description
The following detailed description of the present invention is provided to facilitate understanding of the technical solution of the present invention, but is not intended to limit the scope of the present invention.
The composite magnetic semiconductor nanomaterial has good biocompatibility, no other invalid components are introduced, no further purification is needed, and ultrapure water is used in the whole process.
1. Preparation of BiOI:
the preparation method of the BiOI comprises the following steps: 0.486 g Bi (NO) 3 )3•5H 2 O and 0.455g mannitol were mixed and dissolved in 25mL deionized water, dispersed by sonication for 10 minutes, and 5mL of saturated NaI solution was slowly added to the stirred mixture with a syringe to form a homogeneous white suspension. Dispersing the mixture by ultrasonic treatment for 10 minutes, transferring the mixture into a stainless steel high-temperature reaction kettle with the volume of 50mL, heating the mixture for 3 hours at 160 ℃, naturally cooling the mixture, centrifuging the mixture, washing the mixture with ultrapure water for several times, freezing the mixture in a refrigerator with the temperature of-80 ℃, taking the frozen mixture out, and freeze-drying the frozen mixture overnight in a freeze dryer to obtain solid BiOI, and dissolving the solid in ultrapure water for later use.
2. Fe (Fe) 3 O 4 Is prepared from
Fe 3 O 4 The preparation method of the (C) comprises the following steps: 0.35 g sodium citrate, 0.20 g NaOH and 20 g NaNO 3 Dissolved in 25mL of ultrapure water and the mixture was heated to 105℃to form a clear solution. Then, the mixture contains 4mmol FeSO 4 •7H 2 O2 mL solution (i.e., 4mmol FeSO) 4 •7H 2 O is dissolved into 2mL of ultrapure water to form a solution), the solution is quickly dispersed into the above clarified solution, ultrasonic treatment is carried out for 10 minutes to disperse the solution, then the mixture is transferred into a stainless steel high-temperature reaction kettle with the volume of 50mL, the mixture is kept to be heated for 2 hours at the temperature of 100 ℃, naturally cooled to room temperature, centrifuged, washed by ultrapure water for a plurality of times, frozen in a refrigerator with the temperature of minus 80 ℃, taken out and freeze-dried overnight in a freeze dryer to obtain solid Fe 3 O 4 The ultrapure water is dissolved for subsequent use.
3. The invention relates to a diagnosis and treatment integrated composite magnetic semiconductor nano material (BiOI/Fe) 3 O 4 ) Is prepared from
Example 1: bi (NO) in this example 3 ) 3 •5H 2 O and Fe 3 O 4 The mass ratio of (2) is 1:0.5
The preparation method of the diagnosis and treatment integrated composite magnetic semiconductor nanomaterial comprises the following steps: 0.5g of Bi (NO) 3 ) 3 •5H 2 O,0.25 g of Fe 3 O 4 After 0.5g of mannitol (which plays a freeze-drying stabilizing role) was mixed, the mixture was dispersed in 100mL of ultrapure water by ultrasonic wave, and stirred vigorously while 10mL of acetic acid was added to the solution by syringe, and stirred at room temperature for 30 minutes. 10mL of a solution containing 0.7g of NaI was added to the above suspension, stirred for 3 hours and aged for 1.5 hours. Centrifuging, collecting precipitate, washing with pure water for 3 times to obtain BiOI/Fe 3 O 4 。
Example 2: bi (NO) in this example 3 ) 3 •5H 2 O and Fe 3 O 4 The mass ratio of (2) is 1:1
Substantially the same as in example 1, except that Bi (NO 3 ) 3 •5H 2 O is 0.5g, fe 3 O 4 0.5 g.
Example 3: bi (NO) in this example 3 ) 3 •5H 2 O and Fe 3 O 4 The mass ratio of (2) is 1:2
Substantially the same as in example 1, except that Bi (NO 3 ) 3 •5H 2 O is 0.5g, fe 3 O 4 1.0 g. BiOI/Fe prepared in this example 3 O 4 After being frozen in a refrigerator at the temperature of minus 80 ℃, the mixture is taken out and freeze-dried overnight in a freeze dryer, and the mixture is dissolved in ultrapure water (the dissolution proportion is 1mg of the composite magnetic semiconductor nano material is 1mL of the ultrapure water) for subsequent use.
BiOI/Fe prepared in example 3 3 O 4 The final bismuth and iron content needs to be determined. The method comprises the following steps: a digestion solution containing a mixture of concentrated nitric acid and hydrogen peroxide was prepared at a volume ratio of 4:1, and 500. Mu.l of the digestion solution was mixed with 20. Mu.l of BiOI/Fe 3 O 4 Digestion was done in a fume hood for 72 hours, and the centrifuge tube was manually shaken every other hour. The sample was filtered through a 0.22um filter before testing and the volume was set to 8 ml with ultra pure water. Standards were diluted 7 concentrations at a fold ratio of 200ng/mL to 0ng/mL, detected using inductively coupled mass spectrometry (ICP-MS), and the elemental Bi and Fe contents were calculated from the fold ratios. The Bi content in example 3 was 120. Mu.g/mL and the iron content was 300. Mu.g/mL.
The specific experimental parameters listed above are merely examples of the present disclosure, and the actual experiment should be reasonably changed according to actual needs, such as the oscillation time and the centrifugation time.
FIG. 1A shows BiOI/Fe prepared in example 1 of the present invention 3 O 4 FIG. 1B is a TEM image of BiOI/Fe prepared in example 2 of the present invention 3 O 4 FIG. 1C is a TEM image of BiOI/Fe prepared in example 3 of the present invention 3 O 4 Is a TEM image of (1). FIG. 1D shows BiOI/Fe prepared in example 3 of the present invention 3 O 4 Is an X-ray diffraction pattern of (2).
As can be seen from FIG. 1A, B, C, biOI/Fe 3 O 4 The composite magnetic semiconductor nanostructure is loaded with Fe from bulk BiOI 3 O 4 Is composed of and is along with Fe 3 O 4 The BiOI can load more Fe with the increase of the content 3 O 4 (black part). This indicates that in Bi (NO 3 ) 3 •5H 2 O and Fe 3 O 4 BiOI/Fe prepared at a molar ratio of 1:2 3 O 4 Is beneficial to the fast generation of chargesThe rapid transfer enhances the catalytic activity of the material, meets the imaging requirement, and provides guarantee for biological application of the composite magnetic semiconductor nano material. FIG. 1D shows BiOI/Fe prepared in example 3 of the present invention 3 O 4 The characteristic peaks of (B) and BiOI standard card (JCPDS No. 10-0445) and Fe can be seen 3 O 4 (JCPDS No. 19-0629) matches well, indicating successful sample preparation.
FIG. 2A is a composite magnetic semiconductor nanomaterial BiOI/Fe prepared in accordance with example 3 of the present invention 3 O 4 FIG. 2B shows the effect of hydroxyl radicals generated under different pH conditions, and the composite magnetic semiconductor nanomaterial BiOI/Fe prepared in example 3 of the present invention 3 O 4 Hydroxyl radical effects occur at a pH of 5.4. To explore the Fenton reaction conditions of the present invention, biOI/Fe prepared in example 3 3 O 4 The substrates were oxidized by OH and showed strong light absorption in the spectral range of 430nm using colorless substrates terephthalic acid (terephthalic acid, TA) as an indicator by dissolution with phosphate buffers having pH 2, 4, 5.4, 6.8, 7.4. BiOI/Fe at different pH values 3 O 4 After reaction with TA in the dark, the absorbance at 430nm was measured. As can be seen from FIG. 2A, biOI/Fe at pH 5.4 3 O 4 The number of hydroxyl radicals produced is the greatest and very low at pH 7.4, indicating BiOI/Fe 3 O 4 The nano material can play the maximum role in the tumor slightly acidic environment, generates hydroxyl free radicals to kill tumor cells, and has small toxic and side effects under normal physiological conditions. Based on this, when TA and a different material are combined with H at pH 5.4 2 O 2 After light-shielding incubation, the fluorescence intensity is utilized to react the generation level of hydroxyl radicals in different solutions, thereby further reacting BiOI/Fe 3 O 4 CDT performance of (c). Compared with the control group, biOI/Fe 3 O 4 Exhibits a Jiang Yingguang peak at 430nm, indicating BiOI/Fe 3 O 4 Under acidic environment and H 2 O 2 Fenton reaction occurs, H is 2 O 2 Further decomposed into virulent OH and magnetic composite semiconductor BiOI/Fe 3 O 4 Superior in thatCDT performance of BiOI/Fe 3 O 4 Chemokinetic treatment in tumors provides support.
FIG. 3A is a diagram illustrating the preparation of a magnetic composite semiconductor nanomaterial BiOI/Fe according to example 3 3 O 4 Is a photo-thermal property map of (a). BiOI, fe 3 O 4 And BiOI/Fe 3 O 4 Disperse in water and transfer to a small tube at 1W/cm 2 808nm NIR laser irradiation for 10min (Fe 3 O 4 The concentration is 150 mug mL -1 BiOI concentration of 60. Mu.g mL -1 ) The thermal infrared imager is used to record the heating effect at different times to evaluate and compare the photo-thermal efficiency. As can be seen from the figure, compared to the bisi and Fe alone 3 O 4 ，BiOI/Fe 3 O 4 After 10min, the temperature finally rises to more than 50 ℃, which shows that the excellent photo-thermal conversion efficiency is enough to strengthen CDT and start photo-thermal treatment, thereby laying a foundation for the application of photo-thermal and photodynamic combined treatment. FIG. 3B is a BiOI/Fe prepared in example 3 3 O 4 Is a graph of the photo-thermal enhancement effect of hydroxyl radical generation. The temperature factor has a significant effect on the catalytic activity of the Fenton reagent. BiOI/Fe was also used as an indicator 3 O 4 Dispersed in water and incubated with TA in a tube at 1W/cm 2 Irradiation is carried out for 10min under 808nm NIR laser, and BiOI/Fe is measured by ultraviolet spectrophotometer 3 O 4 Absorbance at 430 nm. As can be seen from the figure, biOI/Fe without laser irradiation 3 O 4 In contrast, biOI/Fe 3 O 4 The + laser group showed significantly higher catalytic activity, which can be attributed to its superior photo-thermal effect accelerating the reaction Fenton rate, embodying the enhancement effect of temperature rise on Fenton reaction, thus confirming the feasibility of photo-thermal enhanced chemical kinetics treatment.
FIGS. 4A and 4B are BiOI/Fe, respectively 3 O 4 MR imaging and CT imaging signal intensity maps of (c). Clinically, MRI is always combined with CT to overcome the drawbacks of CT alone or MRI alone, resulting in higher disease detection sensitivity. Due to the diagnosis and treatment agent BiOI/Fe prepared in example 3 3 O 4 Fe and Bi are doped to make the dual modeBoth MRI and CT imaging are possible. First, different concentrations of BiOI/Fe were evaluated on a small animal 9.4T MRI scanner 3 O 4 MRIT2 values for aqueous studies. As can be seen from FIG. 4A, biOI/Fe 3 O 4 Clearly exhibiting a concentration-dependent MRI performance, which means that a sufficiently high concentration will contribute to a stronger MR signal. Meanwhile, biOI/Fe was tested using small animal PET-CT 3 O 4 CT characteristics of semiconductor material, FIG. 4B shows BiOI/Fe 3 O 4 Shows a concentration-dependent signal enhancement. Thus, biOI/Fe 3 O 4 The material can be used as an imaging agent to assist in cancer diagnosis. In addition, monitoring the course of treatment by imaging techniques is an important way to determine whether the treatment is effective.
FIG. 5 is a magnetic composite semiconductor nanomaterial BiOI/Fe prepared in example 3 3 O 4 The cell uptake effect of (2) was demonstrated using glioblastoma U87 cell line as tumor cells. U87 cells were cultured in 10cm dishes overnight, and 100. Mu.g mL -1 BiOI/Fe 3 O 4 The cells were collected after incubation for 6, 12, 24 hours, respectively, and the amount of iron taken up in the U87 cells was analyzed by ICP-MS (the method was the same as the method for determining iron in the material described above). FIG. 5 shows glioblastoma U87 cell line pair BiOI/Fe with increasing incubation time 3 O 4 Is significantly increased, indicating that BiOI/Fe 3 O 4 Can be well taken up by cells, and is BiOI/Fe 3 O 4 Lays a foundation for in vivo and in vitro biological application.
FIG. 6 is a magnetic composite semiconductor nanomaterial BiOI/Fe prepared in example 3 3 O 4 Graph of the effect of active oxygen production in cells. Fluorescence was monitored with an inverted fluorescence microscope using active oxygen probe 2, 7-dichlorofluorescein diacetate (DCFH-DA) as an indicator. As shown in FIG. 6, with BiOI/Fe 3 O 4 After incubation, glioblastoma U87 cell lines exhibited green fluorescence, indicating intracellular production of reactive oxygen species. In addition, green fluorescence is further enhanced under laser irradiation. These results effectively confirm BiOI/Fe 3 O 4 Can be used as Fenton reagent by inducing the generation of intracellular active oxygenDynamic cancer chemical kinetics treatment, the near infrared light triggered photo-thermal effect can further promote the Fenton reaction rate, increase the generation of active oxygen in cells, and indicate that the semiconductor composite material BiOI/Fe 3 O 4 The application potential of the combination of photothermal therapy and chemical kinetic therapy for treating tumors.
The above-described embodiments are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention, so that all equivalent changes or modifications of the structure, characteristics and principles described in the claims should be included in the scope of the present invention.
Claims (5)
1. The preparation method of the diagnosis and treatment integrated composite magnetic semiconductor nanomaterial is characterized by synthesizing the composite magnetic semiconductor nanomaterial by adopting a chemical coprecipitation method, wherein the composite magnetic semiconductor nanomaterial is BiOI/Fe 3 O 4 The composite magnetic semiconductor nanostructure is loaded with Fe from bulk BiOI 3 O 4 Constructing;
the preparation method comprises the following steps: bi (NO) 3 ) 3 •5H 2 O、Fe 3 O 4 Mixing with mannitol, adding into water, stirring, adding HAc, stirring at room temperature for 30 min, adding NaI solution, stirring for 3 hr, aging for 1.5 hr, centrifuging to obtain precipitate, i.e. BiOI/Fe 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The Bi (NO) 3 ) 3 •5H 2 O and Fe 3 O 4 The mass ratio of (2) is 1:1 to 2;
bi per gram (NO) 3 ) 3 •5H 2 O, mannitol 0.5g, water 100mL, acetic acid 10mL, naI solution 10mL, and NaI 0.7 g/mL.
2. The method for preparing a diagnosis and treatment integrated composite magnetic semiconductor nanomaterial according to claim 1, characterized in that the Fe 3 O 4 The preparation method of the (C) comprises the following steps: sodium citrate, naOH and NaNO 3 Adding waterAnd heated to 105℃to form a clear solution, then a solution containing 4mmol of FeSO 4 •7H 2 Adding 2mL of O solution into the clarified solution, heating at 100deg.C for 2 hr, naturally cooling to room temperature, centrifuging, and washing with ultrapure water to obtain Fe 3 O 4 。
3. The diagnosis and treatment integrated composite magnetic semiconductor nanomaterial prepared by the method for preparing the diagnosis and treatment integrated composite magnetic semiconductor nanomaterial according to any of claims 1-2.
4. Use of a composite magnetic semiconductor nanomaterial integrated with diagnosis and treatment according to claim 3, characterized by one or more uses selected from the group consisting of:
(1) Preparing chemical kinetics and photo-thermal medicines for tumor treatment;
(2) Preparing an imaging contrast agent for tumor magnetic resonance imaging and/or CT;
(3) Preparing the tumor multi-mode diagnosis and treatment integrated medicine.
5. The use according to claim 4, wherein the tumor is glioblastoma.
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