CN114767857A - FePc modified Ti3C2TxPreparation and application of Rh-loaded nano enzyme - Google Patents
FePc modified Ti3C2TxPreparation and application of Rh-loaded nano enzyme Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
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- A61K41/0028—Disruption, e.g. by heat or ultrasounds, sonophysical or sonochemical activation, e.g. thermosensitive or heat-sensitive liposomes, disruption of calculi with a medicinal preparation and ultrasounds
- A61K41/0033—Sonodynamic cancer therapy with sonochemically active agents or sonosensitizers, having their cytotoxic effects enhanced through application of ultrasounds
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- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
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Abstract
The invention introduces a FePc modified Ti3C2TxPreparation and application of Rh-loaded nano enzyme, wherein the main component of the Rh-loaded nano enzyme is Rh-FePc-Ti3C2TxRh-FePc-Ti3C2TxThe preparation raw materials comprise FePc and Ti3C2TxAnd RhCl3·3H2And O. The preparation method comprises the following steps: FePc and Ti3C2TxContinuously performing ultrasonic treatment after mixing; washing and drying to obtain FePc-Ti3C2Tx(ii) a In FePc-Ti3C2TxAdding RhCl3·3H2Dissolving O in polyethylene glycol; ultrasonically dispersing and transferring the mixture into a reaction kettle; cooling, washing and centrifuging; drying and grinding to obtain Rh-FePc-Ti3C2TxAnd (3) compounding the nano enzyme. The invention loads FePc and metal Rh to two-dimensional Ti in sequence3C2TxOn the nano-chip, synthesized material Rh-FePc-Ti3C2TxAs a novel composite nano enzyme, the compound nano enzyme is used for regulating and controlling a complex tumor microenvironment of osteosarcoma cells and generating ROS, relieving the hypoxia problem of the tumor cells, and simultaneously provides a new research platform for the synergistic treatment of osteosarcoma through photodynamic therapy and sonodynamic therapy.
Description
Technical Field
The invention belongs to the field of tumor drug preparation, and particularly relates to FePc modified Ti3C2TxPreparation and application of Rh-loaded nano enzyme.
Background
Currently, osteosarcoma is the most common primary osteosarcoma, is usually diagnosed and found in adolescents, is one of the most threatening malignant tumors, has poor prognosis treatment effect, seriously affects the normal life quality of patients, has low oxygen and weak acidity in tumor microenvironment, and has overhigh hydrogen peroxide concentration. The reactive oxygen ROS mainly comprises reactive superoxide anions, hydroxyl free radicals, singlet oxygen and the like, the ROS level in a tumor environment is increased, and the oxidative stress of cancer cells is enhanced to cause the damage and apoptosis of the tumor cells. Therefore, regulation of the complex tumor microenvironment to generate ROS-mediated therapies is a feasible approach to treatment of osteosarcoma, such as photodynamic therapy PDT and photodynamic therapy SDT.
The clinical treatment method of osteosarcoma mainly comprises surgical resection, radiotherapy and chemotherapy assistance and the like, and has poor treatment effect and uncontrollable prognosis. In recent years, some nanocatalysis therapies can be used for treating tumors, and are a novel treatment means based on nanoenzymes. The nanometer enzyme is an artificial mimic enzyme with the unique performance of nanometer materials and the catalytic function, and is widely applied in the fields of medicine, chemical engineering, environment and the like due to the advantages of economy, stability and durability. Titanium carbide (Ti)3C2Tx) Is a good nano carrier load, can be used for loading nano enzyme, and Chinese patent CN112903763A discloses a Ti3C2Preparation method of Tx-based ammonia sensor, application of Tx-based ammonia sensor under optical assistance, and Ti3C2TxThe preparation process of the ammonia sensor comprises Ti synthesis3C2TxHydrothermal synthesis of TiO2/Ti3C2TxAnd preparing the composite film sensor for detecting the volatile gas components of the meat by a screen printing process. The gas sensor can obtain better performance in the application of ammonia gas detection by means of ultraviolet light assistance, is expected to be applied to meat freshness monitoring, realizes volatile gas identification and concentration detection of fresh meat, and has important practical significance for guaranteeing the food safety of meat.
Chinese patent CN110974978A discloses a nano-catalyst for tumor treatment and a preparation method and application thereof. The provided nano catalyst comprises an erythrocyte membrane, and a composite nano enzyme and a photosensitizer which are coated in the erythrocyte membrane; the composite nano enzyme comprises glucose oxidase and iron nano particles wrapped in the inner cavity of the glucose oxidase. The nano catalyst is preferentially accumulated at a target tumor site through targeted biomimetic delivery, and the release of the composite nano enzyme is realized under the irradiation of near infrared light; glucose oxidase converts glucose into H based on high glucose uptake and weak acid environment of tumor part2O2Inducing the iron nano particles to start an in-situ Fenton reaction, sequentially catalyzing the reaction to generate hydroxyl free radicals, inducing the tumor cells to be oxidized and damaged, and further killing the tumor cells. The device isThe nano-catalyst can realize the high-efficiency loading of the catalyst, effectively prolong the circulation time in vivo, realize the accurate and sustained release at the tumor focus part and provide a new idea and platform for the tumor treatment.
However, some of the existing nanoenzymes have many problems, such as complex preparation process, large size and other disadvantages, and the nanoenzymes themselves have many difficulties, are difficult to prepare, have poor water solubility and low biocompatibility.
Disclosure of Invention
In order to solve the problems, the nano enzyme which has good water solubility, small size, uniform dispersion, easy preparation and higher in-vivo biocompatibility is prepared, so that the complex tumor microenvironment of osteosarcoma cells is changed, ROS is generated, tumor hypoxia is relieved, and the effect of treating osteosarcoma is achieved.
In order to achieve the effect, the invention designs a FePc modified Ti3C2TxPreparation and application of Rh-loaded nano enzyme.
FePc modified Ti3C2TxPreparation and application of Rh-loaded nano enzyme, wherein the main component of the Rh-loaded nano enzyme is Rh-FePc-Ti3C2TxRh-FePc-Ti3C2TxThe preparation raw materials comprise FePc and Ti3C2TxNanosheets and RhCl3·3H2O; the FePc and Ti3C2TxThe mass ratio of the nano sheets is 2-8: 1-4, preferably 2: 1.
FePc modified Ti3C2TxThe preparation method of the Rh-loaded nano enzyme and the application thereof comprises the following steps:
s1, FePc and Ti3C2TxContinuously performing ultrasonic treatment after mixing;
s2, washing and drying to obtain FePc-Ti3C2Tx；
S3 in FePc-Ti3C2TxAdding RhCl3·3H2O, and dissolving in polyethylene glycol together;
s4, ultrasonically dispersing and transferring to a reaction kettle;
s5, cooling, washing and centrifuging;
s6, drying and grinding to obtain Rh-FePc-Ti3C2TxAnd (3) compounding the nano enzyme.
Preferably, in the step S1, FePc and Ti3C2TxThe mixture ratio of the materials required by mixing is 10-40mg of FePc: 5-20mg of Ti3C2Tx: 6-10ml of ultrapure water.
Preferably, in the step S1, the continuous ultrasonic condition after mixing is 4-8h at room temperature.
Preferably, in the step S2, the washing and drying are performed by washing with absolute ethanol, centrifuging twice, placing in a vacuum drying oven for 12-24 hours, and performing FePc-Ti3C2TxAnd (4) collecting.
Preferably, in the step S3, FePc-Ti3C2Tx、RhCl3·3H2The proportion of the O and the polyethylene glycol is 8-12mg of FePc-Ti3C2Tx: 3-6mL RhCl with concentration of 2mg/mL3·3H2O: 20-40ml of polyethylene glycol having a number average molecular weight of 200.
Preferably, in the ultrasonic dispersion in the step S4, the ultrasonic time is 1-2h until the solution is uniformly dispersed.
Preferably, the reaction time in the reaction kettle of the step S4 is 12-16h, and the reaction temperature is 160-200 ℃.
Preferably, the washing material of the step S5 is absolute ethanol, and the number of centrifugation is three.
Preferably, in the step S6, the drying is specifically performed by placing in a vacuum drying oven for drying for 12-24 h.
The application has the advantages and effects as follows:
1. the invention loads FePc and metal Rh to two-dimensional Ti in sequence3C2TxComposite nano material Rh-FePc-Ti synthesized on nano sheet3C2TxAs a novel composite nano enzyme, the nano enzyme has the advantages of small size, high stability and uniform dispersionAnd the photo-thermal performance is good.
2. Rh-FePc-Ti prepared by the application3C2TxThe composite nanoenzyme has catalase-like activity and peroxidase activity, has good biocompatibility, regulates and changes a complex tumor microenvironment of osteosarcoma cells, and generates ROS to further relieve tumor hypoxia.
3. Rh-FePc-Ti prepared by the application3C2TxThe compound nanoenzyme can be used as a novel light/sound sensitive agent, ROS is generated under the catalysis of photodynamic therapy and photodynamic therapy in a tumor microenvironment, hypoxia of tumor cells can be relieved, the tumor microenvironment is regulated and controlled by the compound nanoenzyme, the ROS is generated, and a novel research platform is provided for synergistic treatment of osteosarcoma through the photodynamic therapy and the photodynamic therapy.
The foregoing description is only an overview of the technical solutions of the present application, so that the technical means of the present application can be clearly understood, and the present application can be implemented according to the content of the description, and the foregoing and other objects, features, and advantages of the present application can be more clearly understood.
The above and other objects, advantages and features of the present application will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 shows a composite nano-enzyme Rh-FePc-Ti provided by the invention3C2TxA composite nano enzyme preparation flow chart;
FIG. 2 shows Rh-FePc-Ti provided by the present invention3C2TxHigh Resolution Transmission Electron Microscopy (HRTEM) images of the solid;
FIG. 3 shows Rh-FePc-Ti provided by the present invention3C2TxA catalase-like activity detection map of (1);
FIG. 4 shows Rh-FePc-Ti provided by the present invention3C2TxPeroxidase activity assay of (a);
FIG. 5 shows Rh-FePc-Ti provided by the present invention3C2TxA biocompatibility detection map of;
FIG. 6 shows Rh-FePc-Ti provided by the present invention3C2TxKilling 143B tumor cells by photodynamic therapy and sonodynamic therapy;
FIG. 7 shows Rh-FePc-Ti provided by the present invention3C2TxGraph of the effect of the ability to generate ROS in cells.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. In the following description, specific details such as specific configurations and components are provided only to help the embodiments of the present application be fully understood. Accordingly, it will be apparent to those skilled in the art that various changes and modifications may be made to the embodiments described herein without departing from the scope and spirit of the present application. In addition, descriptions of well-known functions and constructions are omitted in the embodiments for clarity and conciseness.
It should be appreciated that reference throughout this specification to "one embodiment" or "the embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present application. Thus, the appearances of the phrase "one embodiment" or "the present embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
Further, the present application may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
The term "and/or" herein is merely an association describing an associated object, meaning that three relationships may exist, e.g., a and/or B, may mean: a exists alone, B exists alone, and A and B exist at the same time, and the term "/and" is used herein to describe another association object relationship, which means that two relationships may exist, for example, A/and B, may mean: a alone, and both a and B alone, and further, the character "/" in this document generally means that the former and latter associated objects are in an "or" relationship.
The term "at least one" herein is merely an association relationship describing an associated object, and means that there may be three relationships, for example, at least one of a and B, may mean: a exists alone, A and B exist simultaneously, and B exists alone.
It is further noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion.
Example 1
This example mainly describes a FePc modified Ti3C2TxPreparation and application of Rh-loaded nano enzyme.
Composite nano enzyme Rh-FePc-Ti3C2TxThe main component of the material is Rh-FePc-Ti3C2TxRh-FePc-Ti3C2TxThe preparation raw materials comprise FePc and Ti3C2TxAnd RhCl3·3H2O。
Composite nano enzyme Rh-FePc-Ti3C2TxReferring to fig. 1, fig. 1 shows a specific process of preparing the composite nano-enzyme Rh-FePc-Ti according to the present invention3C2TxA preparation flow chart; the preparation method comprises the following steps:
s1, FePc and Ti3C2TxContinuously performing ultrasonic treatment after mixing;
s2, washing and drying to obtain FePc-Ti3C2Tx；
S3 in FePc-Ti3C2TxAdding RhCl3·3H2O, and dissolving in polyethylene glycol together;
s4, ultrasonically dispersing and transferring to a reaction kettle;
s5, cooling, washing and centrifuging;
s6, drying and grinding to obtain Rh-FePc-Ti3C2TxAnd (3) compounding the nano enzyme.
Further, in the step S1, FePc and Ti3C2Tx10-40mg of FePc and 5-20mg of Ti are used as the materials required by mixing3C2TxAnd 6-10ml of ultrapure water.
Further, in the step S1, the continuous ultrasonic condition after mixing is 4 to 8 hours at room temperature.
Further, in the step S2, the washing and drying are specifically washing with absolute ethyl alcohol, centrifuging twice, placing in a vacuum drying oven for 12-24 hours, and then performing FePc-Ti3C2TxAnd (6) collecting.
Further, in the step S3, the FePc-Ti3C2TxThe mass is 8-12mg, the RhCl3·3H2O is 3-6ml, and the polyethylene glycol is 20-40 ml.
Further, in the ultrasonic dispersion of the step S4, the ultrasonic time is 1-2h until the solution is uniformly dispersed.
Further, the reaction time in the reaction kettle of the step S4 is 12-16h, and the reaction temperature is 160-200 ℃.
Further, the washing material in the step S5 is absolute ethyl alcohol, and the number of centrifugation times is three.
Further, in the step S6, a specific drying method is to dry the substrate in a vacuum drying oven for 12 to 24 hours.
The invention loads FePc and metal Rh to two-dimensional Ti in sequence3C2TxThe composite nano material synthesized on the nano sheet as a novel composite nano enzyme has the advantages of small size, uniform dispersion, high stability, good photo-thermal performance and the like.
Rh-FePc-Ti prepared by the application3C2TxThe composite nanoenzyme has catalase-like activity and peroxidase activity, has good biocompatibility, can regulate and control a complex tumor microenvironment of osteosarcoma cells, generates ROS, and relieves tumor hypoxia.
Rh-FePc-Ti prepared by the application3C2TxThe compound nanoenzyme can be used as a novel light/sound sensitive agent, ROS is generated under the catalysis of photodynamic therapy and photodynamic therapy in a tumor microenvironment, hypoxia of tumor cells can be relieved, the tumor microenvironment is regulated and controlled by the compound nanoenzyme, ROS is generated, and a novel research platform is provided for synergistic treatment of osteosarcoma through the photodynamic therapy and the photodynamic therapy. In addition, the compound can be used as a photo-acoustic sensitizer, can regulate and control the complex microenvironment of tumors under the irradiation of near infrared light and ultrasonic waves, and decomposes hydrogen peroxide to generate O2And OH-, relieving tumor hypoxia environment.
Example 2
Based on the above example 1, this example mainly introduces Rh-FePc-Ti3C2TxAnd (5) verifying the effect of the composite nano enzyme.
FIG. 2 shows Rh-FePc-Ti provided by the present invention3C2TxHigh Resolution Transmission Electron Microscopy (HRTEM) images of the solid; the morphology, size and distribution of the nano material are observed by a high-resolution transmission electron microscope (HRTEM), and the result shows that the nano material is nano particles which are uniformly distributed and have the size of about 5 nm.
FIG. 3Rh-FePc-Ti for the invention3C2TxA catalase-like activity detection map of (4); the detection of the activity of the catalase-like enzyme of the nanoenzyme by an oxygen dissolving instrument shows that the nanoenzyme Rh-FePc-Ti has the concentration of 40ug/mL3C2TxThe concentration of oxygen generated by decomposing hydrogen peroxide can reach 19mg/L, which is higher than FePc-Ti under the same concentration3C2TxAnd Ti3C2TxThe component decomposes hydrogen peroxide to produce a concentration of oxygen. And concentration dependence exists, which shows that the nano enzyme has good catalase-like activity.
FIG. 4 shows Rh-FePc-Ti provided by the present invention3C2TxPeroxidase activity assay of (a); evaluation of the decomposition of Hydrogen peroxide by Nanolase to OH by peroxidase Activity test Using TMB as Probe-The ability of the nano enzyme Rh-FePc-Ti can be seen3C2TxThe lowest absorption peak at wavelength 652nm at 21min, evidencing OH generation-Is most powerful and time dependent. The result shows that the nano enzyme has good peroxidase activity.
FIG. 5 is a biocompatibility test chart of Rh-FePc-Ti3C2Tx provided by the present invention; the biocompatibility of the material is evaluated through a CCK-8 experiment after the nano-enzyme Rh-FePc-Ti3C2Tx and HUVECs cells and 143B cells are co-cultured for 24 hours, and the survival rate of the HUVECs cells is close to 98 percent when the nano-enzyme Rh-FePc-Ti3C2Tx is in the experiment range of 0-20ug, so that the nano-enzyme Rh-FePc-Ti3C2 cell is proved to have no toxicity to normal cells. While 143B cells were slightly toxic, and 143B cells survived approximately 75% at 20 ug.
FIG. 6 shows Rh-FePc-Ti provided by the present invention3C2TxKilling 143B tumor cells by photodynamic therapy and sonodynamic therapy; the capability of the nano material for killing osteosarcoma cells through photodynamic and sonodynamic is detected through a CCK-8 experiment after the nano material and 143B cells are co-cultured and near infrared illumination and ultrasonic conditions are applied, and the result shows that under the combined action of near infrared light and ultrasonic, the killing capability of the nano material on the osteosarcoma cells can reach about 40 percent, and the photodynamic therapy and the sonodynamic therapy can effectively kill the osteosarcoma cellsA bone-injured sarcoma cell.
Rh-FePc-Ti3C2TxFIG. 7 shows the ability of generating ROS in cells, and FIG. 7 shows Rh-FePc-Ti according to the present invention3C2TxThe ROS generating capability in cells is directly embodied, and the nano enzyme Rh-FePc-Ti is determined by a DCFH-DA fluorescent probe experiment3C2TxThe ability of generating ROS in cells can be seen, and the result shows that the nano enzyme Rh-FePc-Ti can generate the ROS in the cells under the condition of the synergy of the photoacoustic power3C2TxThe generated green fluorescence is strongest compared with other groups, and the result proves that the generated green fluorescence can well generate ROS and enhance the oxidative stress in cells.
The above description is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the present invention, and it is obvious to those skilled in the art that various modifications and variations can be made in the present invention. Variations, modifications, substitutions, integrations and parameter changes of the embodiments may be made by the conventional substitutes or the same functions may be performed within the spirit and principle of the invention without departing from the principle and spirit of the invention.
Claims (10)
1. FePc modified Ti3C2TxThe Rh-loaded nano enzyme is characterized in that the main component of the Rh-loaded nano enzyme is Rh-FePc-Ti3C2TxRh-FePc-Ti3C2TxThe preparation raw materials comprise FePc and Ti3C2TxNanosheets and RhCl3·3H2O; the FePc and Ti3C2TxThe mass ratio of the nanosheets is 2-8: 1-4.
2. The FePc-modified Ti of claim 13C2TxThe preparation method of the Rh-loaded nanoenzyme is characterized by comprising the following steps:
s1, FePc and Ti3C2TxContinuously performing ultrasonic treatment after mixing;
s2, washing and drying to obtain FePc-Ti3C2Tx；
S3 in FePc-Ti3C2TxAdding RhCl3·3H2O, and dissolving in polyethylene glycol together;
s4, ultrasonically dispersing and transferring to a reaction kettle;
s5, cooling, washing and centrifuging;
s6, drying and grinding to obtain Rh-FePc-Ti3C2TxAnd (3) compounding the nano enzyme.
3. The FePc-modified Ti of claim 23C2TxThe preparation method of the Rh-loaded nanoenzyme is characterized in that in the step S1, FePc and Ti are added3C2TxThe mixture ratio of the materials required by mixing is 10-40mg of FePc: 5-20mg of Ti3C2Tx: 6-10ml of ultrapure water.
4. The FePc-modified Ti of claim 23C2TxThe preparation method of the Rh-loaded nanoenzyme is characterized in that in the step S1, after mixing, continuous ultrasonic treatment is carried out for 4-8 hours at room temperature.
5. The FePc-modified Ti of claim 23C2TxThe preparation method of the Rh-loaded nano-enzyme is characterized in that in the step S2, washing and drying specifically comprise washing with absolute ethyl alcohol, centrifuging twice, placing in a vacuum drying oven for 12-24 hours, and then carrying out FePc-Ti3C2TxAnd (6) collecting.
6. The FePc-modified Ti of claim 23C2TxThe preparation method of the Rh-loaded nano-enzyme is characterized in that in the step S3, FePc-Ti3C2Tx、RhCl3·3H2The proportion of the O and the polyethylene glycol is 8-12mg of FePc-Ti3C2Tx: 3-6mL RhCl with a concentration of 2mg/mL3·3H2O：20-40ml of polyethylene glycol having a number average molecular weight of 200.
7. The FePc-modified Ti of claim 23C2TxThe preparation method of the Rh nano-enzyme is characterized in that in the step S4, ultrasonic dispersion is carried out for 1-2 hours until the solution is uniformly dispersed.
8. The FePc-modified Ti of claim 23C2TxThe preparation method of the Rh-loaded nano enzyme is characterized in that the reaction time in the reaction kettle in the step S4 is 12-16h, and the reaction temperature is 160-200 ℃.
9. The FePc-modified Ti of claim 23C2TxThe preparation method of the Rh-loaded nano enzyme is characterized in that a washing material in the step S5 is absolute ethyl alcohol, and the centrifugation times are three times.
10. The FePc-modified Ti of claim 23C2TxThe preparation method of the Rh-loaded nanoenzyme is characterized in that in the step S6, the specific drying method is to place the Rh-loaded nanoenzyme in a vacuum drying oven for drying for 12-24 hours.
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