CN115381945B - Mn-In 2 S 3 InOOH nano-particle, preparation method and application - Google Patents

Mn-In 2 S 3 InOOH nano-particle, preparation method and application Download PDF

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CN115381945B
CN115381945B CN202211016719.5A CN202211016719A CN115381945B CN 115381945 B CN115381945 B CN 115381945B CN 202211016719 A CN202211016719 A CN 202211016719A CN 115381945 B CN115381945 B CN 115381945B
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李翔
张田
傅译可
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Abstract

The application discloses Mn-In 2 S 3 InOOH nano-particles, a preparation method and application thereof, wherein the preparation method comprises the following steps: mnCl is added to 2 ·4H 2 O、In(NO 3 ) 3 Adding the solution to Na 2 S, in the solution, regulating the pH value by using a dilute nitric acid solution to obtain a precursor solution; adding the precursor solution into a hydrothermal reaction kettle for reaction, and centrifugally washing after the reaction to obtain Mn-In 2 S 3 InOOH nanoparticles. The nanoparticle has the advantages that the efficiency of the sound-sensitive agent is greatly improved through two methods of heterojunction and metal ion doping, the sound-dynamic activity is stronger, and the problems of fewer sound-sensitive agent types, poor sound-sensitive agent structural design and low sound-dynamic efficiency can be effectively solved.

Description

Mn-In 2 S 3 InOOH nano-particle, preparation method and application
Technical Field
The application belongs to the field of biological nano materials, and In particular relates to Mn-In 2 S 3 InOOH nano-particles, a preparation method and application thereof.
Background
Malignant tumors remain one of the most fatal diseases threatening the health of humans. In the last decades, ROS-mediated tumor therapy has been widely used for the development of tumor therapeutic agents due to its minimally invasive, space-time controllable and targeted properties and activation at specific locations. Among them, ultrasound dynamic therapy (SDT) has shown great potential in tumor therapy as a novel non-invasive therapeutic approach. Ultrasound is a typical non-invasive source of radiation, which has low tissue attenuation efficiency, can penetrate deeper body tissues, and has no significant energy loss, in addition, ultrasound can control the activation of the sonophore spatially and spatially, thereby ensuring the biological safety of SDT in treatment. SDT induces bubble collapse through cavitation effect of ultrasound, and high temperature and high pressure generated in bubble collapse process can induce sonoluminescence, pyrolysis and other phenomena, so that the sonosensitizer which activates tumor site specificity accumulation generates ROS to cause oxidative stress inside tumor cells to kill cells, and tumor ablation is caused. In the SDT process, the existence of the sound sensitive agent and the efficiency of the sound sensitive agent play a critical role. In the last decades of research, research on organic and inorganic sonosensitizers has increased greatly. Traditional organic sound-sensitive agents (such as chlorophyll derivatives, ATX-70, porphyrin, etc.) have the characteristics of hydrophobicity, low bioavailability, high skin sensitivity, etc., which greatly limit the application of the agents. In contrast, inorganic sound-sensitive agents have a wide application prospect in the biomedical field due to the unique physicochemical properties, inherent biological effects, high stability, low photosensitivity and other characteristics. Among them, various types of semiconductor materials are increasingly studied for ultrasonic power treatment due to the sonoluminescence property of ultrasound. Under ultrasonic irradiation, the semiconductor material can absorb ultrasonic energy to cause electron transition on a valence band, and generate activated electrons and holes, so that oxidation-reduction reaction is carried out on the active oxygen species with reactants in the environment. And electron-hole recombination is an undesirable reaction in this process. In order to promote separation of electron and hole and increase quantum yield, heterojunction design and doping of metal ions are rational and efficient approaches.
Accordingly, in carrying out the present application, the inventors have found that there are at least the following problems in the prior art: less types of sound-sensitive agents, poor structural design of the sound-sensitive agents, low sound power efficiency and the like.
Disclosure of Invention
The application aims to overcome the defects In the prior art and provide Mn-In 2 S 3 InOOH nano particles, a preparation method and application thereof are provided, so as to solve the problems of less types of sound-sensitive agents, poor structural design of the sound-sensitive agents and low sound power efficiency in the related technology.
The aim of the application is realized by the following technical scheme: mn-In 2 S 3 A method of preparing InOOH nanoparticles comprising:
MnCl is added to 2 ·4H 2 O、In(NO 3 ) 3 Adding the mixture into water, and performing ultrasonic dispersion to obtain Mn and In source solutions;
na is mixed with 2 S is added into water, and ultrasoundDispersing to obtain Na 2 S, solution;
drop Mn and In source solutions to Na 2 S, forming a uniform light yellow solution in the solution;
dropping dilute nitric acid solution into the pale yellow solution, and adjusting pH to below 3 to obtain Mn-In with no stable particles 2 S 3 An InOOH precursor solution;
Mn-In which has not yet formed stable particles 2 S 3 Transferring the InOOH precursor solution into a hydrothermal reaction kettle for reaction, and centrifugally washing after the reaction to obtain Mn-In 2 S 3 InOOH solution.
Preferably, in the Mn and In source solution, mnCl 2 ·4H 2 O concentration is 0-3.5mg/ml, in (NO) 3 ) 3 Is 12-24mM.
Preferably, the Na 2 In S solution, na 2 The concentration of S is 30-60mM.
Preferably, the Mn and In source precursor solution is added dropwise to Na 2 In the S precursor solution, the dropping speed is 0.5-2ml/min.
Preferably, the pH is adjusted to 2.6-3.
Preferably, the reaction temperature of the reaction in the hydrothermal reaction kettle is 180 ℃, and the reaction time is 12-24 hours.
Preferably, the Mn-In 2 S 3 InOOH nanometer particle with particle size of 10-30nm, irregular shape and good dispersivity and stability.
The application also provides Mn-In prepared by the preparation method 2 S 3 InOOH nanoparticles.
The application also provides the Mn-In 2 S 3 Use of InOOH nanoparticles for the preparation of an photodynamic therapy formulation.
The application has the beneficial effects that: the application uses a one-step hydrothermal method to make In 2 S 3 The metal ion Mn is doped into the composite material in the process, which is favorable for the absorption of the material to ultrasound in the acoustic power process, promotes the separation of electron holes and greatlyThe efficiency of sound power is improved to a certain extent, and a good tumor inhibition effect is achieved.
The application synthesizes Mn-In by a one-step hydrothermal method 2 S 3 InOOH nanoparticles. Mn-In the present application 2 S 3 In the InOOH nano-particles, the formation of heterojunction promotes the absorption of ultrasonic waves by the composite material. In under ultrasonic irradiation 2 S 3 And InOOH can absorb ultrasonic wave to realize transition of electrons from valence band to conduction band, and due to formation of heterojunction and In 2 S 3 Fermi level different from InOOH, in according to the energy minima principle 2 S 3 Electrons on the conduction band migrate to the conduction band of InOOH; holes on the InOOH valence band will be oriented towards In 2 S 3 And thereby promotes separation of electron and hole, and improves quantum yield. In addition, the metal ion Mn can be doped In 2 S 3 And forming a defect energy level near the conduction band of InOOH, thereby capturing the activated electrons in the process of transition of the activated electrons to the valence band, further reducing the recombination of electron holes and promoting the separation of the electron holes. The activated electrons can adsorb O with the surface 2 Reduction reaction occurs to produce toxic O 2 · - And 1 O 2 thereby killing the tumor cells. Such a design verifies Mn-In 2 S 3 The feasibility of InOOH as the sound sensitizer provides guidance for the application of heterojunction and metal ion doping in the field of tumor treatment. In the present application, mn-doped In is synthesized by a one-step hydrothermal method 2 S 3 The InOOH heterostructure realizes an efficient acoustic power treatment means. To date, a Mn-In based technology has not been developed In the art 2 S 3 An InOOH nanoparticle. The application fills the gap. The preparation method is simple, has good dispersity and stability, and has a wide application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
FIG. 1 shows In with different Mn doping concentrations In the present application 2 S 3 A transmission electron microscope image of the InOOH nano-particles, (a) is an undoped image, (b) is a 1% doped image, and (c) is a 5% doped image;
FIG. 2 shows In with different Mn doping concentrations In the present application 2 S 3 XRD pattern of InOOH nanoparticles;
FIG. 3 shows In with different Mn doping concentrations In the present application 2 S 3 Degradation patterns of the InOOH nano-particles on DPBF after different ultrasonic irradiation time, (a) is a Control (DPBF itself) pattern, (b) is an undoped pattern, (c) is a 1% doped pattern, and (d) is a 5% doped pattern;
FIG. 4 is a graph showing the degradation percentage of DPBF for different materials in the present application;
FIG. 5 shows the solid diffuse reflection spectrum of different materials, (a) is a solid diffuse reflection spectrum, and (b) is a solid diffuse reflection conversion curve;
FIG. 6 is an AC impedance spectrum of different materials according to the present application;
FIG. 7 is a graph showing cytotoxicity of different materials according to the present application after 24 hours of incubation;
FIG. 8 is a graph showing apoptosis detection by flow cytometry in different groups of the present application;
FIG. 9 is a graph of ROS levels in various groups of the present application, (a) is a graph of ROS fluorescence, and (b) is a graph of flow cytometry ROS level.
Detailed Description
Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, the same numbers in different drawings refer to the same or similar elements, unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the application. Rather, they are merely examples of apparatus and methods consistent with aspects of the application as detailed in the accompanying claims.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any or all possible combinations of one or more of the associated listed items.
The application will be further described with reference to the accompanying drawings and specific examples.
It is to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the application, since numerous insubstantial modifications and variations will be apparent to those skilled in the art in light of the above disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
Mn-In 2 S 3 The preparation method of the InOOH nano-particles can comprise the following steps:
step (1), mnCl is added 2 4H 2 O、In(NO 3 ) 3 Adding the solution into ultrapure water, and performing ultrasonic dispersion to obtain Mn and In source solutions;
specifically, 3.5mg of MnCl was weighed out 2 ·4H 2 O and 72mg of In (NO) 3 ) 3 (24 mM) was dissolved in 10ml of ultrapure water, and the solution was dispersed in an ultrasonic cleaner for 10 minutes to give a uniform clear and transparent solution.
Step (2), na is added 2 S is added into ultrapure water, and is dispersed by ultrasonic to obtain Na 2 S, solution;
specifically, 144mg of Na was weighed 2 S, dissolving in 10ml of ultrapure water, and dispersing for 10min by an ultrasonic cleaner to obtain a uniform, clear and transparent solution.
Step (3), mn and In source solutions are added dropwise to Na 2 S, forming a uniform light yellow solution in the solution;
specifically, a homogeneous transparent clear solution after mixing Mn and In sources is slowly added dropwise to Na 2 S solutionThe dripping speed is 2ml/min, and the mixture is stirred uniformly to form a pale yellow solution.
Step (4), dripping dilute nitric acid solution into the light yellow solution, and regulating the pH value to be less than 3 to obtain Mn-In 2 S 3 An InOOH precursor solution;
specifically, dilute nitric acid (10% by weight of concentrated nitric acid) was slowly added dropwise to the above mixed solution, and the pH change of the solution was detected in real time with a pH meter. Adjusting the pH of the solution to 2.67, and then continuing stirring at room temperature for 10min to obtain Mn-In 2 S 3 InOOH precursor solution.
Step (5), mn-In 2 S 3 Transferring the InOOH precursor solution into a hydrothermal reaction kettle for reaction, and centrifugally washing after the reaction to obtain Mn-In 2 S 3 InOOH solution;
specifically, the obtained solution is transferred into a hydrothermal reaction kettle with the volume of 50ml for sealing, the reaction kettle is placed into a baking oven with the temperature of 180 ℃ for reaction for 12 hours, naturally cooled to room temperature, centrifugally washed for 3-4 times, and Mn-In is obtained after washing 2 S 3 InOOH nanoparticles (1-MISO). After the reaction, solid-liquid separation was carried out by high-speed centrifugation at 12000rpm for 8min. The washing mode is to wash with ultrapure water, and the washed product is redispersed in the ultrapure water.
Example 2
Mn-In 2 S 3 The preparation method of the InOOH nano-particles can comprise the following steps:
step (1), mnCl is added 2 4H 2 O、In(NO 3 ) 3 Adding the solution into ultrapure water, and performing ultrasonic dispersion to obtain Mn and In source solutions;
specifically, 17.5mg of MnCl was weighed out 2 ·4H 2 O and 72mg of In (NO) 3 ) 3 (24 mM) was dissolved in 10ml of ultrapure water, and the solution was dispersed in an ultrasonic cleaner for 10 minutes to give a uniform clear and transparent solution.
Step (2), na is added 2 S is added into ultrapure water, and is dispersed by ultrasonic to obtain Na 2 S, solution;
specifically, 144mg of Na was weighed 2 S, dissolving in 10ml of ultra-pure waterDispersing for 10min by using an acoustic cleaner to obtain a uniform, clear and transparent solution.
Step (3), mn and In source solutions are added dropwise to Na 2 S, forming a uniform light yellow solution in the precursor solution;
specifically, a homogeneous transparent clear solution after mixing Mn and In sources is slowly added dropwise to Na 2 In the solution S, the dropping speed is 2ml/min, and the solution S is stirred uniformly to form a pale yellow solution.
Step (4), dripping dilute nitric acid solution into the light yellow solution, and regulating the pH value to be less than 3 to obtain Mn-In 2 S 3 An InOOH precursor solution;
specifically, dilute nitric acid (10% by weight of concentrated nitric acid) was slowly added dropwise to the above mixed solution, and the pH change of the solution was detected in real time with a pH meter. Adjusting the pH of the solution to 2.67, and then continuing stirring at room temperature for 10min to obtain Mn-In 2 S 3 InOOH precursor solution.
Step (5), mn-In 2 S 3 Transferring the InOOH precursor solution into a hydrothermal reaction kettle for reaction, and centrifugally washing after the reaction to obtain Mn-In 2 S 3 InOOH solution;
specifically, the obtained solution is transferred into a hydrothermal reaction kettle with the volume of 50ml for sealing, the reaction kettle is placed into a baking oven with the temperature of 180 ℃ for reaction for 12 hours, naturally cooled to room temperature, centrifugally washed for 3-4 times, and Mn-In is obtained after washing 2 S 3 InOOH nanoparticles (5-MISO). After the reaction, solid-liquid separation was carried out by high-speed centrifugation at 12000rpm for 8min. The washing mode is to wash with ultrapure water, and the washed product is redispersed in the ultrapure water.
Example 3
In (In) 2 S 3 The preparation method of the InOOH nano-particles can comprise the following steps:
step (1), in (NO) 3 ) 3 Adding the solution into ultrapure water, and performing ultrasonic dispersion to obtain an In source solution;
specifically, 72mg of In (NO 3 ) 3 (24 mM), dissolving in 10ml of ultra-pure water, dispersing for 10min by an ultrasonic cleaner to obtain a uniform clear and transparent solution。
Step (2), na is added 2 S is added into ultrapure water, and is dispersed by ultrasonic to obtain Na 2 S, solution;
specifically, 144mg of Na was weighed 2 S, dissolving in 10ml of ultrapure water, and dispersing for 10min by an ultrasonic cleaner to obtain a uniform, clear and transparent solution.
Step (3), the In source solution is dripped into Na 2 S, forming a uniform light yellow solution in the precursor solution;
specifically, a uniform transparent clear solution after mixing the In source was slowly dropped to Na 2 In the solution S, the dropping speed is 2ml/min, and the solution S is stirred uniformly to form a pale yellow solution.
Step (4), dripping dilute nitric acid solution into the light yellow solution, and regulating the pH value to be less than 3 to obtain In 2 S 3 An InOOH precursor solution;
specifically, dilute nitric acid (10% by weight of concentrated nitric acid) was slowly added dropwise to the above mixed solution, and the pH change of the solution was detected in real time with a pH meter. Adjusting pH of the solution to 2.67, and stirring at room temperature for 10min to obtain In 2 S 3 InOOH precursor solution.
Step (5), in 2 S 3 Transferring the InOOH precursor solution into a hydrothermal reaction kettle for reaction, and centrifugally washing after the reaction to obtain In 2 S 3 InOOH solution;
specifically, the obtained solution is transferred into a hydrothermal reaction kettle with the volume of 50ml for sealing, the reaction kettle is placed into a 180 ℃ oven for reaction for 12 hours, naturally cooled to room temperature, centrifugally washed for 3-4 times, and washed to obtain In 2 S 3 InOOH nanoparticles (0-MISO). After the reaction, solid-liquid separation was carried out by high-speed centrifugation at 12000rpm for 8min. The washing mode is to wash with ultrapure water, and the washed product is redispersed in the ultrapure water.
Example 4
This example differs from example 1 In that 36mg of In (NO) was added In step (1) 3 ) 3 (12 mM) to obtain a Mn and In source solution; adding 72mg of Na to the mixture obtained in the step (2) 2 S (30 mM) gave Na2S solution.
Example 5
This example differs from example 1 in that the drop acceleration in step (3) was 0.5ml/min.
Example 6
This example differs from example 1 In that In step (4) a dilute nitric acid solution was added dropwise to the above pale yellow solution, and the pH was adjusted to 3.0 to obtain In 2 S 3 InOOH precursor solution.
Example 7
This example differs from example 1 in that in the hydrothermal reaction in step (5), the reaction time was 24 hours.
Mn-In 2 S 3 The InOOH nanoparticles were prepared by a one-step hydrothermal process. In FIG. 1, the graphs (a), (b) and (c) are respectively In with different Mn doping concentrations 2 S 3 According to the transmission electron microscope pictures of the InOOH nano-particles, the appearance of the nano-particles is not changed due to different doping concentrations, the size is about 20nm, and the shape is irregular.
FIG. 2 is an XRD pattern for In2S3/InOOH nanoparticles doped with different Mn concentrations. It can be seen that In was successfully synthesized 2 S 3 InOOH nano-particles with crystalline phase of tetragonal beta-In 2 S 3 (JCPDS 25-0390) and InOOH phase (JCPDS 17-0549), and the crystallization condition is good; the JCPDS 25-0390 is PDF card number. In addition, it can be seen that the doping of Mn affects In the composite material 2 S 3 And InOOH, less Mn doping (1-MISO) relative to undoped nanoparticles (0-MISO), na 0.6 MnO 2 Phase appearance (JCPLDS 69-0060), more Mn doped In (5-MISO) 2 S 3 Is reduced In proportion and significant In (OH) appears at 22.26 DEG 3 Peaks of the phases (JCPDS 01-85-1338).
Example 8
This example provides Mn-In prepared In the above example 2 S 3 Use of InOOH nanoparticles in acoustic power therapy of tumors.
The application comprises: in under ultrasonic irradiation 2 S 3 Can absorb ultrasonic waves (US) with InOOHRealizing the transition of electrons from valence band to conduction band due to the formation of heterojunction and In 2 S 3 Fermi level different from InOOH, in according to the energy minima principle 2 S 3 Electrons on the conduction band migrate to the conduction band of InOOH; holes on the InOOH valence band will be oriented towards In 2 S 3 And thereby promotes separation of electron and hole, and improves quantum yield. In addition, the metal ion Mn can be doped In 2 S 3 And forming a defect energy level near the conduction band of InOOH, thereby capturing the activated electrons in the process of transition of the activated electrons to the valence band, further reducing the recombination of electron holes and promoting the separation of the electron holes. The activated electrons can adsorb O with the surface 2 Reduction reaction occurs to produce toxic O 2 · - And 1 O 2 thereby killing the tumor cells.
The MISO nanoparticles in examples 1, 2, 3 were characterized by the following examples.
Example 9
A typical ROS detection probe DPBF was used to detect ROS generating ability of MISO nanoparticles under ultrasonic irradiation. Reactive oxygen species (ROS, including O) generated during acoustic power 2 · - ， 1 O 2 Etc.) can degrade DPBF, reducing the characteristic absorption peak of DPBF at 415 nm. Mu.l of DPBF (2 mM) was added to 3ml of MISO hydroalcoholic mixed solution (50. Mu.g/ml), and the mixture was then exposed to ultrasound (1.0 MHz, 1.0W/cm) in the dark 2 ) The absorbance change (every two minutes) at different irradiation times was measured using the uv-vis spectrum.
FIG. 3 shows In with different Mn doping concentrations 2 S 3 Acoustic power degradation curve of the InOOH nanoparticles versus DPBF. It can be seen that MISO is able to effectively degrade DPBF under ultrasonic irradiation (US), which suggests the sonodynamic properties of MISO. Fig. 4 is a graph of the percent degradation of DPBF by different materials. The degradation percentages of Control,0-MISO,1-MISO,5-MISO were found to be 16.68%,53.94%,100% and 96.51%, respectively, within 10 min. Of these, 1-MISO exhibits the strongest acoustic power efficiency. This indicates In 2 S 3 iso/InOOHThe mass junction has promotion effect on ultrasonic power; mn doping is beneficial to improving In 2 S 3 Sound power efficiency of InOOH. Too much doping reduces its activity.
Example 10
To scientifically investigate the reasons for the different properties of MISO nanoparticles, the present study used solid diffuse reflectance spectroscopy to calculate the band gap of MISOs at different Mn doping concentrations.
FIG. 5 (a) shows the diffuse reflectance spectrum of the solid of MISO, and (b) shows the conversion curve calculated from FIGS. 5 (a) and Tauc's equation. As can be seen from fig. 5 (a), mn doping is beneficial to improve the absorption of ultrasonic waves by the material. From FIG. 5 (b), the band gaps of the different materials were calculated, and it was found that the band gaps of 0-MISO,1-MISO,5-MISO were 3.72eV, 2.677eV, 3.2398eV, respectively. The band gap of 0-MISO confirms that heterojunction formation favors electron hole generation. Whereas the effect of Mn doping on the bandgap means that the metal ions act as defect levels. However, increasing doping concentrations does not continuously decrease their band gap. Meanwhile, the present study also uses Electrochemical Impedance Spectroscopy (EIS) to evaluate charge transfer capability and carrier separation efficiency of MISOs. Fig. 6 shows that the EIS Nyquist plot of the Mn-doped nanoparticle shows a smaller semicircle than 0-MISO, demonstrating that its charge transfer resistance becomes smaller, mn doping can induce higher electron hole separation efficiency, further confirming the effect of metal ion Mn doping as a defect level that can trap electrons of transition and promote separation of electrons and holes. Therefore, it can be presumed that the mechanism is: first, inOOH has a bandgap of 3.75eV, in 2 S 3 With a bandgap of 2.12eV, both semiconductors can cause separation of electrons and holes upon absorption of ultrasonic energy, and the compatibility of the two can be such that upon absorption of ultrasonic energy by both, a transition of the respective electron from valence to conduction band is caused due to In 2 S 3 And InOOH fermi level, so that In 2 S 3 Electrons on the conduction band migrate to the conduction band of InOOH, and holes on the valence band of InOOH migrate to In 2 S 3 Is arranged on the price band of the (c). On the other hand, the doping of Mn causes defect energy levels to exist near In2S3 and InOOH conduction bands, and can captureElectrons in the electron-hole recombination process. The heterojunction and doping cooperate to reduce the recombination of electrons and holes in the material and improve the quantum yield. Furthermore, it is desirable that the redistributed activated electrons be able to drive the reduction of dissolved oxygen molecules present in the environment, producing toxic O 2 · - 、 1 O 2 。
Example 11
The experiment shows the application of the material in tumor treatment through killing effect on the cell level. The cells used were mouse breast cancer cells (4T 1) and the material used was 1-MISO. 4T1 cells were co-cultured with 50. Mu.g/ml of 1-MISO and the cell viability after 24h of culture with or without ultrasonic irradiation was determined. As shown in fig. 7, the ultrasound itself and the material itself have no killing effect on cells, while the 4T1 cells have significantly reduced survival rate of the 4T1 cells under the combined action of the material and the ultrasound, and represent remarkable acoustic power efficiency.
The experiment further verifies the acoustic power effect of the material by using a flow cytometer through the Annexin V-fluorescein isothiocyanate (Annexin-FTIC) and PI double staining principle. As shown in fig. 8, most cells were killed by miso+us treatment, indicating the high ultrasound toxicity of MISO to cells with ultrasound assistance. The method has good biocompatibility.
The ability of the material to generate ROS within the cell was verified by oxidation of the sensitive probe 2',7' -dichlorofluorescein diacetate (DCFH-DA). The probe can be oxidized to Dichlorofluorescein (DCF) in the presence of ROS, exhibiting green fluorescence. FIG. 9 (a) is a fluorescence image of cells after they have been treated with different groups, and it can be seen that MISO+US treated cells exhibit enhanced fluorescence, demonstrating that MISO is capable of producing ultrasound-induced ROS. Whereas US itself and MISO itself do not exhibit significant DCF fluorescence. FIG. 9 (b) quantitatively determines the ROS levels in the cells after the various groups of treatments using a flow cytometer, further corroborating the above conclusions.

Claims (5)

1. A method for preparing Mn-In2S3/InOOH nanoparticles, comprising:
weighing 3.5mg of MnCl2.4H2O and 72mg of In (NO 3) 3 with the concentration of 24mM, dissolving In 10ml of ultrapure water, and dispersing for 10 minutes by an ultrasonic cleaner to obtain a uniform, clear and transparent solution;
144mg of Na2S is weighed and dissolved in 10ml of ultrapure water, and the solution is uniformly clarified and transparent after being dispersed for 10min by an ultrasonic cleaner;
slowly dripping a uniform transparent clear solution obtained by mixing Mn and In sources into a Na2S solution at the dripping speed of 2ml/min, and uniformly stirring to form a pale yellow solution;
slowly dripping 10% by weight of concentrated nitric acid into the mixed solution, and detecting the real-time pH change of the solution by using a pH meter; adjusting the pH value of the solution to 2.67, and then continuing stirring at room temperature for 10min to obtain Mn-In2S3/InOOH precursor solution;
transferring the obtained solution into a hydrothermal reaction kettle with the volume of 50ml, sealing, placing the reaction kettle In a 180 ℃ oven for reaction for 12 hours, naturally cooling to room temperature, centrifugally washing for 3-4 times, and washing to obtain Mn-In2S3/InOOH nano particles; after the reaction is finished, solid-liquid separation is carried out by using 12000rpm high-speed centrifugation for 8min; the washing mode is to wash with ultrapure water, and the washed product is redispersed in the ultrapure water.
2. A method for preparing Mn-In2S3/InOOH nanoparticles, comprising:
17.5mg of MnCl2.4H2O and 72mg of In (NO 3) 3 with the concentration of 24mM are weighed and dissolved In 10ml of ultrapure water, and a uniform, clear and transparent solution is obtained after dispersion for 10 minutes by an ultrasonic cleaner;
144mg of Na2S is weighed and dissolved in 10ml of ultrapure water, and the solution is uniformly clarified and transparent after being dispersed for 10min by an ultrasonic cleaner;
slowly dripping a uniform transparent clear solution obtained by mixing Mn and In sources into a Na2S solution at the dripping speed of 2ml/min, and uniformly stirring to form a pale yellow solution;
slowly dripping 10% by weight of concentrated nitric acid into the mixed solution, and detecting the real-time pH change of the solution by using a pH meter; adjusting the pH value of the solution to 2.67, and then continuing stirring at room temperature for 10min to obtain Mn-In2S3/InOOH precursor solution;
transferring the obtained solution into a hydrothermal reaction kettle with the volume of 50ml, sealing, placing the reaction kettle into a 180 ℃ oven for reaction for 12 hours, naturally cooling to room temperature, centrifugally washing for 3-4 times, and washing to obtain Mn-In2S3/InOOH nano particles; after the reaction is finished, solid-liquid separation is carried out by using 12000rpm high-speed centrifugation for 8min; the washing mode is to wash with ultrapure water, and the washed product is redispersed in the ultrapure water.
3. The method for preparing Mn-In2S3/InOOH nano-particles according to claim 1 or 2, wherein the Mn-In2S3/InOOH nano-particles have a particle size of 20nm and are irregularly shaped.
4. A Mn-In2S3/InOOH nanoparticle prepared by the preparation method of any one of claims 1-3.
5. Use of Mn-In2S3/InOOH nanoparticles according to claim 4 for the preparation of an photodynamic therapy formulation.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109338391A (en) * 2018-10-18 2019-02-15 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of substrate for optical electro-chemistry hydrogen production by water decomposition and products thereof and application
CN109967092A (en) * 2019-05-05 2019-07-05 中国科学技术大学 A kind of metal-doped indium sulfide nanometer sheet, preparation method and application
CN109999836A (en) * 2019-04-28 2019-07-12 大连工业大学 A kind of preparation of indium oxide/indium sulfide heterojunction semiconductor material and photochemical catalyst purposes and solar energy fixed nitrogen application
CN111871437A (en) * 2020-06-14 2020-11-03 盐城师范学院 Application method of carbon-nitrogen-doped indium oxide semiconductor photocatalytic material in preparation of hydrogen
CN113332427A (en) * 2021-05-13 2021-09-03 浙江大学杭州国际科创中心 Fe2O3@ Pt multifunctional nano-particle and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109338391A (en) * 2018-10-18 2019-02-15 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of substrate for optical electro-chemistry hydrogen production by water decomposition and products thereof and application
CN109999836A (en) * 2019-04-28 2019-07-12 大连工业大学 A kind of preparation of indium oxide/indium sulfide heterojunction semiconductor material and photochemical catalyst purposes and solar energy fixed nitrogen application
CN109967092A (en) * 2019-05-05 2019-07-05 中国科学技术大学 A kind of metal-doped indium sulfide nanometer sheet, preparation method and application
CN111871437A (en) * 2020-06-14 2020-11-03 盐城师范学院 Application method of carbon-nitrogen-doped indium oxide semiconductor photocatalytic material in preparation of hydrogen
CN113332427A (en) * 2021-05-13 2021-09-03 浙江大学杭州国际科创中心 Fe2O3@ Pt multifunctional nano-particle and preparation method and application thereof

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