CN117414423A - RuTiO (RuTiO) material 2-x @ TiCN heterojunction, preparation method and application - Google Patents
RuTiO (RuTiO) material 2-x @ TiCN heterojunction, preparation method and application Download PDFInfo
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Abstract
The invention relates to the technical field of biomedical application, in particular to RuTiO 2‑x The @ TiCN heterojunction, the preparation method and the application thereof comprise TiCN nano-sheets and Ru which is deposited on the surfaces of the TiCN nano-sheets in a reduction manner 3+ The TiCN nano-sheet is oxidized and converted into TiO with rich oxygen vacancies through hydrothermal reaction 2‑x And reducing and depositing Ru on the surface of TiCN nano-sheet 3+ To Ru nanoparticles to form Ru/TiO 2‑x @ TiCN heterojunction. The nano-enzyme is used as an acoustic sensitizer and a nano-enzyme for acoustic power combined nano-catalytic tumor treatment. The heterojunction prepared by the method has the advantages of enhanced acoustic dynamic performance and tumor catalytic treatment performance, high biocompatibility and no obvious long-term toxicityLow cost, high activity and good thermal stability, and is suitable for mass production.
Description
Technical Field
The invention relates to the technical field of biomedical application, in particular to RuTiO 2-x A @ TiCN heterojunction, a preparation method and application.
Background
Current clinical treatment modalities for cancer, including surgery, chemotherapy, and radiation therapy, are inadequate for eradication of malignant tumors due to their significant systemic toxicity. A variety of emerging tumor therapeutic modalities based on exogenous stimulation or endogenous chemical reactions to generate Reactive Oxygen Species (ROS) to kill cancer cells have been widely explored to replace traditional therapeutic approaches. Among them, nano-enzyme-based tumor catalytic treatment (NCT) relies on enzymatic reaction (TME) in tumor microenvironment, and can combine the advantages of nano-materials and natural enzymes to catalyze generation of ROS with high cytotoxicity, so as to achieve satisfactory therapeutic effect. Unlike inefficient and unstable natural enzymes, nanoenzymes have low cost, high stability, adjustable activity, mass production, high reproducibility, and the like, and have enhanced catalytic activity even in severe environments. Previously reported nanoenzymes, including noble metals, metal oxides or sulfides, metal organic frameworks, carbon-based nanomaterials, have been observed to mimic the functions of natural Peroxidases (POD), catalases (CAT) and glutathione peroxidases (GSH-px), exhibiting the ability of TME to regulate amplified ROS production. However, the biocompatibility of metal-based nanoenzymes is suspected, and their tumor therapeutic effect is often inhibited. Furthermore, these reported nanoezymes still have low catalytic activity due to their single enzyme mimic activity. Therefore, it is necessary to develop nanoezymes with various enzyme-like catalytic activities that can mimic not only POD-catalyzed H 2 O 2 Generates hydroxyl radical (. OH), and has GSH-px-like activity to avoidNo generated. OH was consumed.
In addition to exploring nanoenzymes with multiple enzyme-like catalytic activities, the combination of NCT with other tumor treatment modalities, such as photothermal or photodynamic therapy (PTT or PDT), sonodynamic therapy (SDT), is a promising strategy to achieve efficient tumor treatment. PTT or PDT has been considered a non-invasive therapeutic modality by irradiation of photothermal or photosensitizing agents with Near Infrared (NIR) laser light to generate high temperature or ROS, and is approved by the united states food and drug administration for clinical trials in the treatment of tumors. However, near Infrared (NIR) lasers have limited penetration depth even in the second near infrared region (1-2 cm), which makes PTT or PDT suitable only for surface tumor treatment. In contrast, ultrasound (US) triggered SDT has a greater penetration depth [ ]>10 cm), higher therapeutic efficiency and lower side effects, which makes SDT a surrogate for phototherapy for treating deep tumors. Unfortunately, traditional organic acoustic sensitizers have poor water stability, potential phototoxicity, chemical instability, and broad band gap and rapid electron-hole pair recombination of inorganic nanomaterials will result in low ROS yields. Therefore, searching for a semiconductor acoustic sensitizer with a narrow band gap, and further constructing a heterostructure to inhibit electron-hole recombination, it is possible to significantly improve the ROS production efficiency of the inorganic acoustic sensitizer. Furthermore, the efficiency of oxygen-dependent SDT-induced ROS production is severely limited by TME hypoxia. Various researches have reported that nano-enzyme with CAT-like catalytic activity can improve O in tumor 2 Is added to the (c). Thus, conferring trisaccharide-like catalytic activity can achieve a cascade of ROS production and break therapeutic resistance by alleviating tumor hypoxia and depleting overexpressed GSH.
In recent years, transition metal carbonitrides have received a great deal of attention in the fields of electrocatalysis and energy storage due to their excellent thermal stability and high electron conductivity. Wherein, because of the vacancy in the lattice structure of TiCN, tiCN nano material has narrow band gap, and shows potential as enhanced inorganic sound sensitizer. In addition, due to the presence of Ti 3+ And Ti is 4+ TiCN is expected to exhibit catalytic activity of a variety of similar enzymes. However, to our knowledge, tiCN-based nanomaterials have not been reported to be used as acoustic sensitizers or nanoezymes for SDT or NCT. Besides exploring the semiconductor acoustic sensitizer, constructing the heterojunction based on TiCN nanomaterial can further improve its SDT performance because it can inhibit electron-hole pair recombination. In recent years, many heterostructure acoustic sensitizers have been prepared by depositing metal nanoparticles or inorganic nanomaterials on the surface of another semiconductor acoustic sensitizer. However, these post-load strategies for heterojunction formation typically require multiple steps of reactions, which can result in low yields of the heterojunction and significant waste of raw materials. Furthermore, the resulting heterojunction may not have a matched bandgap, resulting in low efficiency SDT characteristics.
In view of the above, the invention provides a RuTiO2-x@TiCN heterojunction, a preparation method and application thereof.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and providing a RuTiO 2-x A @ TiCN heterojunction, a preparation method and application.
In order to solve the technical problems, the following technical scheme is adopted:
Ru/TiO 2-x The @ TiCN heterojunction comprises a TiCN nano-sheet and Ru which is deposited on the surface of the TiCN nano-sheet in a reduction way 3 + The TiCN nano-sheet is oxidized and converted into TiO with rich oxygen vacancies through hydrothermal reaction 2-x And reducing and depositing Ru on the surface of TiCN nano-sheet 3+ To Ru nanoparticles to form Ru/TiO 2-x @ TiCN heterojunction.
As another technical scheme of the invention, the Ru/TiO is as follows 2-x The preparation method of the @ TiCN heterojunction comprises the following steps:
(1) Firstly adding TiCN nano-sheets into deionized water, wherein the ratio of the TiCN nano-sheets to the deionized water is (4.5-5.5): 1, then sequentially adding RuCl 3 And NaBF 4 The deionized water and RuCl 3 And NaBF 4 The ratio of (2) is 1: (2.5-3.5): (2-3), then carrying out ultrasonic treatment, and finally carrying out hydrothermal reaction for 10-14h;
(2) The above reaction is carried outCentrifuging the product, collecting precipitate, washing with deionized water and ethanol for 3-6 times, and oven drying to obtain Ru/TiO 2-x @ TiCN heterojunction.
Further, in step (1), the time of the ultrasonic treatment is 25 to 50 minutes.
Further, in step (1), the temperature of the hydrothermal reaction is 180 to 250 ℃.
Further, in the step (2), the temperature of the drying treatment is 75-90 ℃.
Further, the preparation method of the TiCN nanosheets comprises the following steps: firstly, mixing TiCN ceramic with HF, and stirring the mixed solution for 70-80 hours; the mixed solution was then added to the TPAOH solution and stirred for 20-30 hours to obtain TiCN nanoplatelets.
Further, the concentration of HF is 40%.
As another technical scheme of the invention, ru/TiO 2-x Application of @ TiCN heterojunction in acoustic power performance to prepare Ru/TiO 2-x TiCN heterojunction by using 1, 3-diphenylisobenzofuran as the material 1 O 2 The probe detects the change of the absorption peak intensity at different ultrasonic time at the position 412 and nm by using an ultraviolet spectrophotometer so as to detect Ru/TiO 2-x The @ TiCN heterojunction is under ultrasonic irradiation 1 O 2 Generating efficiency.
As another technical scheme of the invention, ru/TiO 2-x The application of the @ TiCN heterojunction in catalytic activity is characterized in that: the Ru/TiO prepared above 2-x TiCN heterojunction, ru/TiO is detected by using 3, 5-tetramethylbenzidine as a probe and using an ultraviolet spectrophotometer to detect the change in absorption peak intensity after different incubation times at 654 nm 2-x At H @ TiCN heterojunction 2 O 2 OH formation efficiency in the presence of a catalyst;
Ru/TiO was evaluated by using 5,5' -dithiobis as GSH probe 2-x The ability of the @ TiCN heterojunction to consume GSH.
As another technical scheme of the invention, ru/TiO 2-x Stress of @ TiCN heterojunction for reducing tumor cells in vivo with acoustic power performanceIs used.
Due to the adoption of the technical scheme, the method has the following beneficial effects:
the Ru/TiO2-x@TiCN heterojunction is prepared, and the Ru/TiO2-x@TiCN heterojunction serving as a sound sensitizer and nanoenzyme is used for sound power combined nano catalytic tumor treatment. The heterojunction prepared by the method has the advantages of enhanced acoustic dynamic performance and tumor catalytic treatment performance, high biocompatibility, no obvious long-term toxicity, low cost, high activity and good thermal stability, and is suitable for large-scale production.
The invention adopts a one-step in-situ synthesis strategy to prepare Ru/TiO 2-x A TiCN heterojunction with excellent US-activated ROS generating capability and triple enzyme-like catalytic activity. Ternary Ru/TiO by simple hydrothermal reaction 2-x TiCN is converted into TiO with rich oxygen vacancies by oxidizing TiCN nanoplatelets 2-x Reduction deposition of Ru on TiCN surface 3+ To Ru nanoparticles to form a heterojunction. Ru/TiO as an enhanced sound-sensitive agent 2-x TiCN shows enhanced ROS production efficiency through heterojunction improved electron-hole separation. With these advantages, ru/TiO 2-x The @ TiCN achieves complete tumor eradication.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is Ru/TiO 2-x TEM and HRTEM pictures of TiCN heterojunction nanoenzyme.
FIG. 2 is Ru/TiO 2-x Production of TiCN and TiCN under US irradiation 1 O 2 Velocity contrast plot.
FIG. 3 is Ru/TiO 2-x POD simulated enzyme activity evaluation graphs of TiCN and TiCN.
FIG. 4 is Ru/TiO 2-x GSH-px simulated enzyme activity evaluation chart of TiCN and TiCN.
FIG. 5 is Ru/TiO 2-x Test pattern of tumor volume and mouse survival rate during tumor treatment with TiCN heterojunction nanoenzyme in vivo.
Description of the embodiments
The present invention will be further described in detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
Referring to FIG. 1, a Ru/TiO 2-x The @ TiCN heterojunction comprises a TiCN nano-sheet and Ru which is deposited on the surface of the TiCN nano-sheet in a reduction way 3+ The TiCN nano-sheet is oxidized and converted into TiO with rich oxygen vacancies through hydrothermal reaction 2-x And reducing and depositing Ru on the surface of TiCN nano-sheet 3+ To Ru nanoparticles to form Ru/TiO 2-x @ TiCN heterojunction.
As another embodiment of the present invention, a Ru/TiO as described above 2-x The preparation method of the @ TiCN heterojunction comprises the following steps:
(1) Firstly adding TiCN nano-sheets into deionized water, wherein the ratio of the TiCN nano-sheets to the deionized water is (4.5-5.5): 1, then sequentially adding RuCl 3 And NaBF 4 The deionized water and RuCl 3 And NaBF 4 The ratio of (2) is 1: (2.5-3.5): (2-3), then carrying out ultrasonic treatment for 25-50min, and finally carrying out hydrothermal reaction for 10-14h; the temperature of the hydrothermal reaction is 180-250 ℃.
(2) Centrifuging the reaction product, collecting precipitate, washing with deionized water and ethanol for 3-6 times, and oven drying at 75-90deg.C to obtain Ru/TiO 2-x @ TiCN heterojunction.
As a further explanation of this example, the preparation method of the TiCN nanosheets is as follows: tiCN ceramic was first mixed with HF at a concentration of 40%. Stirring the mixed solution for 70-80h; the mixed solution was then added to the TPAOH solution and stirred for 20-30 hours to obtain TiCN nanoplatelets. In general terms, the process of the present invention,
the preparation thereof is further illustrated by the following specific examples.
Example 1
Ru/TiO 2-x The preparation method of the @ TiCN heterojunction comprises the following steps:
(1) 200 mg TiCN nanosheets are added into 40 mL deionized water, and then 120 mg RuCl is added in sequence 3 And 100 mg NaBF 4 Then carrying out ultrasonic treatment, wherein the ultrasonic treatment time is 30min, and finally carrying out hydrothermal reaction for 12h; the temperature of the hydrothermal reaction was 200 ℃.
(2) Centrifuging the reaction product, collecting precipitate, washing with deionized water and ethanol for 3 times, and oven drying to obtain Ru/TiO 2-x And the temperature of the drying treatment is 75-90 ℃ at the @ TiCN heterojunction.
Example 2
Ru/TiO 2-x The preparation method of the @ TiCN heterojunction comprises the following steps:
(1) 200 mg TiCN nanosheets are added into 40 mL deionized water, and then 120 mg RuCl is added in sequence 3 And 100 mg NaBF 4 Then carrying out ultrasonic treatment, wherein the ultrasonic treatment time is 30min, and finally carrying out hydrothermal reaction for 12h; the temperature of the hydrothermal reaction was 200 ℃.
(2) Centrifuging the reaction product, collecting precipitate, washing with deionized water and ethanol for 3 times, and oven drying to obtain Ru/TiO 2-x And the temperature of the drying treatment is 80 ℃ at the @ TiCN heterojunction.
Example 3
Ru/TiO 2-x The preparation method of the @ TiCN heterojunction comprises the following steps:
(1) 180 mg TiCN nanosheets are added into 35 mL deionized water, and then 110 mg RuCl is added in sequence 3 And 90 mg NaBF 4 Then carrying out ultrasonic treatment, wherein the ultrasonic treatment time is 30min, and finally carrying out hydrothermal reaction for 10h; the temperature of the hydrothermal reaction was 190 ℃.
(2) Centrifuging the reaction product, collecting precipitate, washing with deionized water and ethanol for 4 times, and oven drying to obtain Ru/TiO 2-x @ TiCN heterojunction, saidThe temperature of the drying treatment was 80 ℃.
Example 4
Ru/TiO 2-x The preparation method of the @ TiCN heterojunction comprises the following steps:
(1) 220 mg TiCN nanosheets are added into 45 mL deionized water, and then 130 mg RuCl is added in sequence 3 And 110 mg NaBF 4 Then carrying out ultrasonic treatment, wherein the ultrasonic treatment time is 25min, and finally carrying out hydrothermal reaction for 14h; the temperature of the hydrothermal reaction was 250 ℃.
(2) Centrifuging the reaction product, collecting precipitate, washing with deionized water and ethanol for 6 times, and oven drying to obtain Ru/TiO 2-x And the temperature of the drying treatment is 75 ℃ at the @ TiCN heterojunction.
Example 5
Ru/TiO 2-x The preparation method of the @ TiCN heterojunction comprises the following steps:
(1) 240 mg TiCN nanosheets are added into 50mL deionized water, and then 135mg RuCl is added in sequence 3 And 120 mg NaBF 4 Then carrying out ultrasonic treatment for 30min, and finally carrying out hydrothermal reaction for 13h; the temperature of the hydrothermal reaction was 230 ℃.
(2) Centrifuging the reaction product, collecting precipitate, washing with deionized water and ethanol for 5 times, and oven drying to obtain Ru/TiO 2-x And the temperature of the drying treatment is 90 ℃ at the @ TiCN heterojunction.
As another embodiment of the present invention, ru/TiO was verified 2-x Use of TiCN heterojunction in Acoustic dynamic Properties, referring to FIG. 2, ru/TiO prepared in examples 1-5 above 2-x TiCN heterojunction by using 1, 3-diphenylisobenzofuran as the material 1 O 2 The probe detects the change of the absorption peak intensity at different ultrasonic time at the position 412 and nm by using an ultraviolet spectrophotometer so as to detect Ru/TiO 2-x The @ TiCN heterojunction is under ultrasonic irradiation 1 O 2 Generating efficiency.
As another embodiment of the present invention, ru/TiO was verified 2-x Use of the @ TiCN heterojunction in catalytic Activity referring to FIG. 3, ru/TiO prepared in examples 1-5 above 2-x TiCN heterojunction, ru/TiO is detected by using 3, 5-tetramethylbenzidine as a probe and using an ultraviolet spectrophotometer to detect the change in absorption peak intensity after different incubation times at 654 nm 2-x At H @ TiCN heterojunction 2 O 2 OH formation efficiency in the presence of a catalyst;
referring to FIG. 4, ru/TiO was evaluated by using 5,5' -dithiobis as GSH probe 2-x The ability of the @ TiCN heterojunction to consume GSH.
As another embodiment of the present invention, ru/TiO was verified 2-x Application of @ TiCN heterojunction in reducing tumor cells in vivo with acoustic power performance. Referring to FIG. 5, 100. Mu.L (500 ten thousand) of human osteosarcoma cells (143B) were subcutaneously implanted in the armpit of 3-5 weeks female nude mice until the tumor volume became 100 mm 3 When nude mice were divided into 5 groups (5 per group): (1) Blank control group, (2) US irradiation alone (50 kHz, 1.0W cm -2 , 5 min）、（3）Ru/TiO 2-x The @ TiCN heterojunction nano-enzyme, (4) TiCN+US irradiation (50 kHz, 1.0W cm) -2 , 5 min）、（5）Ru/TiO 2-x TiCN+US irradiation (50 kHz, 1.0W cm) -2 5 min). The weight of nude mice was recorded daily and tumor volume was measured every other day to evaluate Ru/TiO 2-x In vivo tumor therapeutic efficiency of TiCN heterojunction nanoenzyme.
The heterojunction nano-enzyme prepared in the embodiment is subjected to relevant experiments such as characterization, acoustic dynamic performance detection, GSH consumption capability detection, hydrogen peroxide catalytic capability detection, tumor treatment in vivo by intravenous injection and the like through instrument detection, and the results are as follows:
as can be seen from FIG. 1, ru/TiO 2-x TEM of @ TiCN heterojunction nanoenzyme shows Ru nanoparticles and TiO 2-x The nano-sheets can be uniformly distributed on the surface of the TiCN nano-sheets.
As can be seen from FIG. 2, ru/TiO 2-x @ TiCN heterojunction nanoenzyme 1 O 2 The production rate is superior to that of TiCN nanosheets.
As can be seen from FIGS. 3 and 4, ru/TiO 2-x H of @ TiCN heterojunction nano-enzyme 2 O 2 Is superior to TiCN nano-sheets in catalytic capability and GSH consumption capability.
As can be seen from FIG. 5, ru/TiO under US irradiation 2-x The @ TiCN heterojunction nano-enzyme has the optimal tumor treatment effect, can completely inhibit the growth of tumors, and can survive for more than 50 days.
The invention discloses a Ru/TiO 2-x The preparation process of TiCN heterojunction and its use as sound sensitizer and nanometer enzyme in sound and power combined nanometer catalytic tumor treatment are disclosed. The heterojunction prepared by the method has the advantages of enhanced acoustic dynamic performance and tumor catalytic treatment performance, high biocompatibility, no obvious long-term toxicity, low cost, high activity and good thermal stability, and is suitable for large-scale production.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to solve the substantially same technical problems and achieve the substantially same technical effects are encompassed within the scope of the present invention.
Claims (10)
1. Ru/TiO 2-x The @ TiCN heterojunction is characterized in that: comprises TiCN nano-sheets and Ru which is deposited on the surface of the TiCN nano-sheets in a reduction way 3+ The TiCN nano-sheet is oxidized and converted into TiO with rich oxygen vacancies through hydrothermal reaction 2-x And reducing and depositing Ru on the surface of TiCN nano-sheet 3+ To Ru nanoparticles to form Ru/TiO 2-x @ TiCN heterojunction.
2. A Ru/TiO according to claim 1 2-x The preparation method of the @ TiCN heterojunction is characterized by comprising the following steps of:
(1) Firstly adding TiCN nano-sheets into deionized water, wherein the ratio of the TiCN nano-sheets to the deionized water is (4.5-5.5): 1, then sequentially adding RuCl 3 And NaBF 4 The deionized water and RuCl 3 And NaBF 4 The ratio of (2) is 1: (2.5-3.5):(2-3), then carrying out ultrasonic treatment, and finally carrying out hydrothermal reaction for 10-14h;
(2) Centrifuging the reaction product, collecting precipitate, washing with deionized water and ethanol for 3-6 times, and oven drying to obtain Ru/TiO 2-x @ TiCN heterojunction.
3. A Ru/TiO according to claim 2 2-x The preparation method of the @ TiCN heterojunction is characterized by comprising the following steps: in the step (1), the ultrasonic treatment time is 25-50min.
4. A Ru/TiO according to claim 2 2-x The preparation method of the @ TiCN heterojunction is characterized by comprising the following steps: in step (1), the temperature of the hydrothermal reaction is 180-250 ℃.
5. A Ru/TiO according to claim 2 2-x The preparation method of the @ TiCN heterojunction is characterized by comprising the following steps: in the step (2), the temperature of the drying treatment is 75-90 ℃.
6. A Ru/TiO according to claim 2 2-x The preparation method of the @ TiCN heterojunction is characterized by comprising the following steps: the preparation method of the TiCN nanosheets comprises the following steps: firstly, mixing TiCN ceramic with HF, and stirring the mixed solution for 70-80 hours; the mixed solution was then added to the TPAOH solution and stirred for 20-30 hours to obtain TiCN nanoplatelets.
7. A Ru/TiO according to claim 6 2-x The preparation method of the @ TiCN heterojunction is characterized by comprising the following steps: the concentration of HF was 40%.
8. Ru/TiO 2-x The application of the @ TiCN heterojunction in acoustic power performance is characterized in that: a Ru/TiO prepared according to any one of claims 2 to 7 2-x TiCN heterojunction by using 1, 3-diphenylisobenzofuran as the material 1 O 2 Probe for detecting different supers at 412 and nm by using ultraviolet spectrophotometerDetection of Ru/TiO by variation of absorption peak intensity at Acoustic time 2-x The @ TiCN heterojunction is under ultrasonic irradiation 1 O 2 Generating efficiency.
9.Ru/TiO 2-x The application of the @ TiCN heterojunction in catalytic activity is characterized in that: a Ru/TiO prepared according to any one of claims 2 to 7 2-x TiCN heterojunction, ru/TiO is detected by using 3, 5-tetramethylbenzidine as a probe and using an ultraviolet spectrophotometer to detect the change in absorption peak intensity after different incubation times at 654 nm 2-x At H @ TiCN heterojunction 2 O 2 OH formation efficiency in the presence of a catalyst;
Ru/TiO was evaluated by using 5,5' -dithiobis as GSH probe 2-x The ability of the @ TiCN heterojunction to consume GSH.
10. Ru/TiO 2-x Application of @ TiCN heterojunction in reducing tumor cells in vivo with acoustic power performance.
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