CN105193843B - Preparation method of graphene composite doped TiO2 nano material - Google Patents
Preparation method of graphene composite doped TiO2 nano material Download PDFInfo
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- CN105193843B CN105193843B CN201510664732.5A CN201510664732A CN105193843B CN 105193843 B CN105193843 B CN 105193843B CN 201510664732 A CN201510664732 A CN 201510664732A CN 105193843 B CN105193843 B CN 105193843B
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Abstract
In order to search for a new cancer treatment method, the invention establishes a method for killing cancer cells by using titanium dioxide-based nano materials, and the invention content comprises the following steps: develops the titanium dioxide-based nano material, establishes an experimental method for killing cancer cells and an evaluation method for the efficiency of killing the cancer cells. The invention has the following characteristics: the titanium dioxide-based nano material has good stability and strong dispersibility, and has the function of killing cancer cells at a lower temperature (4-39 ℃), particularly at a normal human body temperature (37 ℃); the experimental method for killing the cancer cells is simple, easy to operate and low in implementation condition requirement, other requirements (such as illumination and the like) are not needed, and the evaluation method for the efficiency of killing the cancer cells is accurate and feasible. The invention opens up a new direction for cancer treatment.
Description
[ technical field ] A method for producing a semiconductor device
The invention establishes a method for killing cancer cells by using a titanium dioxide-based nano material. The newly developed titanium dioxide-based nano material is used for carrying out an experiment of killing cancer cells at a low temperature (4-39 ℃), particularly at a normal human body temperature (37 ℃), and the efficiency of killing the cancer cells is tested and evaluated. The novel methods belong to the field of cancer therapy.
[ background of the invention ]
Cancer is one of the diseases that are directly life-threatening to human in the world today, and the incidence of cancer has been on the rise in recent years worldwide. At present, the clinical methods mainly comprise surgical treatment, chemical treatment, radiation treatment and the like; the operation therapy is limited to local treatment, and chemotherapy and radiotherapy are accompanied by large side effects, so that the research and the research of a new method which has small toxic and side effects on a human body and effectively kills cancer cells are the key research direction in the field of the current cancer treatment.
The invention discloses a method for killing cancer cells by using a titanium dioxide-based nano material. The method effectively kills cancer cells at a low temperature (4-39 ℃) by using the developed titanium dioxide-based nano material, particularly at a normal human body temperature (37 ℃), is simple and easy to operate, has low implementation condition requirement, and has accurate evaluation on the efficiency of killing the cancer cells. At present, no report is found on a method for killing cancer cells by utilizing nano materials at normal human body temperature (37 ℃), which means that the invention has potential application prospect in the field of cancer treatment.
[ summary of the invention ]
The invention establishes a method for killing cancer cells by using a titanium dioxide-based nano material, and the invention content comprises the following aspects: 1. doped ionic salt, titanate or titanate is used as a precursor, a carbon-based material (such as graphene and the like) is used as a composite material, and a sol-gel method and the like are adopted to prepare the titanium dioxide-based nano material; 2. an experimental method for effectively killing cancer cells at a low temperature (4-39 ℃) by using the nano material, particularly at a normal human body temperature (37 ℃) and an evaluation method of cancer cell killing efficiency are established. 3. The experiment of killing cancer cells is carried out by using the titanium dioxide-based nano material. The result shows that the titanium dioxide-based nano material has stronger capability of killing cancer cells at a lower temperature (4-39 ℃), particularly at a normal human body temperature (37 ℃), the experimental method is simple, the operation is easy, the requirement on implementation conditions is low, and the evaluation method of the cancer cell killing efficiency is accurate and feasible.
In order to achieve the object of the present invention, the present invention provides a method for killing cancer cells using a titanium dioxide-based nanomaterial, comprising: developing titanium dioxide-based nano materials, and establishing an experimental method for killing cancer cells and an evaluation method for the efficiency of killing the cancer cells; the titanium dioxide-based nano material is characterized in that metal or nonmetal doped TiO is prepared by taking doped ionic salt, titanate or titanate as a precursor by adopting a sol-gel method2Nano material or carbon-based material composite metal or non-metal doped TiO2A nanomaterial; the nano material has good dispersibility and strong stability, and has high efficiency of killing cancer cells at a lower temperature of 4-39 ℃; an experimental method for killing cancer cells and an evaluation method of efficiency of killing cancer cells are characterized in that cancer cells are cultured in 1640 medium containing 10% fetal calf serum, 100U/mL streptomycin and 100. mu.g/mL penicillin, and the cultured cells are placed at 37 ℃ and contain 5% CO2The incubator with saturated humidity; cancer cells in logarithmic growth phase were first trypsinized to a concentration of 1X 10 per ml5Injecting the cancer cell suspension of each cell into a 96-well plate with 200 μ L per well to ensure that each well has 2X 104(ii) individual cells; then culturing for 24 hours in an incubator, removing the original culture medium, injecting 1640 culture medium containing titanium dioxide base nano materials with different concentrations, continuously culturing for 16 hours in the incubator with saturated humidity to ensure the interaction of the nano materials and cancer cells, finally detecting the survival rate of the cancer cells by adopting a standard MTT method, and evaluating the survival rate of the cancer cellsEfficiency of the cells.
The further technical proposal is that the lower temperature is 37 ℃ of the normal human body temperature.
The further technical proposal is that the method for preparing the titanium dioxide-based nano material comprises the following steps: (1) doped TiO22Preparing nano particles: preparing a doped ion salt solution with a certain concentration at normal temperature, adding a diluent, adding an acidifier and titanate or titanate under the condition of continuous stirring to prepare a mixed sol, aging for 24 hours at normal temperature to obtain a mixed gel, drying at 90-150 ℃, and calcining for 2.5-6 hours at 450-800 ℃ in air to prepare the doped TiO2Nanoparticles; (2) graphene composite doped TiO2The preparation method of the nano material comprises the following steps: adding a proper amount of concentrated sulfuric acid into a beaker under the ice-water bath condition; adding crystalline flake graphite and sodium nitrate under continuous stirring; controlling the reaction temperature to be below 20 ℃, and adding potassium permanganate to prepare dark green liquid; raising the reaction temperature to 35 ℃, continuing stirring for 1h, slowly adding a certain amount of deionized water, violently boiling the liquid, keeping the temperature at 98 ℃ for 15-30 min, continuing adding a proper amount of distilled water and hydrogen peroxide, standing for 24h to obtain a reddish brown precipitate, and finally washing with a 5% HCl solution and deionized water until no sulfate radical is detected in the filtrate; drying the obtained solid at 60 ℃ to obtain graphene oxide; TiO is mixed according to a certain proportion of 9: 1-3: 72Placing the base nanoparticles and graphene oxide in a 250ml beaker, adding a diluent, and carrying out ultrasonic treatment for 80-120 min; drying the solid powder obtained after centrifugation at 40-80 ℃, calcining for 2-5 h at 300-450 ℃ under the protection of inert gas, and preparing the graphene composite doped TiO2And (3) nano materials.
According to a further technical scheme, the cancer cell is any one of human lung cancer cell A549, human colon cancer cell, human cervical cancer cell or synovial membrane cell.
The further technical proposal is that the titanium dioxide-based nano material is titanium dioxide doped with metal or nonmetal ions or titanium dioxide doped with metal or nonmetal ions compounded by graphene carbon-based materials.
Further technical scheme is that the doping ion is single doping or double doping of any two of palladium, indium, platinum, tin or nitrogen metal or nonmetal ions.
According to a further technical scheme, the acidifying agent is any one or a mixture of hydrochloric acid, nitric acid, phosphoric acid, glacial acetic acid and perchloric acid.
The titanate or titanate is selected from one or a mixture of the following: ti (OC)4H9)4、Ti(OC2H5)4、Ti(iso-OC3H7)4、Ti(SO4)2Or TiCl4。
The further technical proposal is that the diluent is any one or a mixture of more of high-purity water, absolute ethyl alcohol, absolute methyl alcohol, glacial acetic acid or formic acid.
In a further aspect, the inert gas is any one of nitrogen, argon or helium.
[ description of the drawings ]
FIG. 1 Raman spectra of the sample of the example (vs. pure TiO)2Comparison);
FIG. 2 is a graph of the efficiency of the example sample in killing lung cancer cells A549 (vs. pure TiO)2Comparison);
FIG. 3 is a graph of the efficiency of killing carcinoid synovial cells in the example (vs. pure TiO)2Comparison);
the present invention will be further described with reference to the following specific examples and accompanying drawings, which illustrate the preparation of the titanium dioxide-based nanomaterial of the present invention, the experimental method for killing cancer cells, and the evaluation method of the efficiency of killing cancer cells.
[ detailed description ] embodiments
The preparation method of the Pd-doped titanium dioxide nano material comprises the following steps: at room temperature, 5mL of PdCl was prepared first2The solution (0.1036mol/L) was added with 40mL of anhydrous ethanol. After stirring for half an hour, 1mL of concentrated hydrochloric acid and 12mL of tetrabutyltitanate are added and then aged for 24h, giving a mixed gel. Drying at 100 deg.C, grinding into powder, calcining at 450 deg.C for 2.5h to obtain Pd-TiO2Nanoparticles.
The preparation method of the graphene composite titanium dioxide-based nano material comprises the following steps: A1L beaker was assembled in an ice-water bath, and 115mL of concentrated sulfuric acid was added. A solid mixture of 5g of flake graphite and 2.5g of sodium nitrate was added with constant stirring, and then 15g of potassium permanganate was added in portions, the reaction temperature being controlled not to exceed 20 ℃. The liquid was then warmed to 35 ℃ and stirred for a further 60 min. 230mL of deionized water was then added slowly and the liquid was boiled vigorously and held at about 98 ℃ for 15 min. And 0.7L of distilled water and 12.5mL of hydrogen peroxide are added, and finally, the mixture is washed by 1L of 5% HCl solution and deionized water until no sulfate radical is detected in the filtrate. And finally, fully drying in a vacuum drying oven at 60 ℃ to obtain the graphene oxide.
Pd-TiO is mixed according to the mass ratio of 6: 42And placing the graphene oxide in a 250ml beaker, adding 150ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 100 min. After centrifugation, the mixture is dried in an oven at 50 ℃. Finally calcining for 2h at 300 ℃ under the protection of argon gas to obtain graphene/Pd-TiO2And (3) nano materials. Pure graphene adopts the same preparation method, except that no Pd-TiO is added in the preparation process2。
FIG. 1 is a graph relating to pure TiO2In comparison, the raman spectra of the samples of the above examples. As can be seen from the figure, at 144cm-1(Eg)， 194cm-1(Eg)，396cm-1(B1g)，516cm-1(A1g and B1g) And 638cm-1(Eg) A distinct diffraction peak appears indicating that the titanium dioxide produced is of a typical anatase structure. In addition, at 1314cm-1And 1588cm-1Intensity peaks also appear, corresponding to the D and G peaks of graphene, respectively. Thus indicating successful preparation of TiO2，Pd-TiO2Graphene and graphene/Pd-TiO2And (3) nano materials.
The results of FIGS. 2 and 3 show TiO2Almost has no cancer cell killing effect, and the cell survival rate is still kept about 85 percent; the activity of the sample in killing cancer cells A549 at normal human body temperature (see figure 2), and when the concentration of the nano material is 400 mug/mL, the graphene/Pd-TiO2The survival rate of A549 cancer cells of the sample is only 7.2%; and pure TiO2The survival rate of A549 cancer cells of the sample is 87.5 percent, and the survival rate of the Pd-TiO is2The survival rate of the a549 cancer cells of (a) is 45.8%; the synoviocyte activity of the sample is killed at normal human body temperature (see figure 3), and the graphene/Pd-TiO is reacted for 16h when the concentration of the nano material is 400 mug/mL2The A549 synovial cell survival rate of the sample was 21.4%, while that of pure TiO2The synovial cell survival rate of the sample is 81 percent, and the Pd-TiO is2The survival rate of synovial cancer cells was 46.5%.
As can be seen from the examples, graphene/Pd-TiO2Sample and pure TiO2Compared with the traditional Chinese medicine, the efficiency of killing the lung cancer cells is improved by about 7.4 times, and the efficiency of killing the synovial cells of the carcinoid cells is improved by about 4.1 times.
Claims (6)
1. Graphene composite doped TiO2The preparation method of the nano material is characterized by comprising the following steps: (1) doped TiO22Preparing nano particles: preparing a doped ion salt solution with a certain concentration at normal temperature, adding a diluent, adding an acidifier and titanate or titanate under the condition of continuous stirring to prepare a mixed sol, aging for 24 hours at normal temperature to obtain a mixed gel, drying at 90-150 ℃, and calcining for 2.5-6 hours at 450-800 ℃ in air to prepare the doped TiO2Nanoparticles; (2) graphene composite doped TiO2Preparing a nano material: adding a proper amount of concentrated sulfuric acid into a beaker under the ice-water bath condition; adding crystalline flake graphite and sodium nitrate under continuous stirring; controlling the reaction temperature to be below 20 ℃, and adding potassium permanganate to prepare dark green liquid; raising the reaction temperature to 35 ℃, continuing stirring for 1h, slowly adding a certain amount of deionized water, violently boiling the liquid, keeping the temperature at 98 ℃ for 15-30 min, continuing adding a proper amount of distilled water and hydrogen peroxide, standing for 24h to obtain a reddish brown precipitate, finally washing with a 5% HCl solution and deionized water until no sulfate radical is detected in the filtrate, and drying at 60 ℃ to obtain graphene oxide; doping TiO according to a certain proportion of 9: 1-3: 72Placing the nano particles and the graphene oxide in a 250ml beaker, adding a diluent, and carrying out ultrasonic treatment for 80-120 min; drying the solid powder obtained after centrifugation at 40-80 ℃, and carrying out 30% of drying under the protection of inert gasCalcining for 2-5 h at 0-450 ℃ to obtain graphene composite doped TiO2And (3) nano materials.
2. The graphene composite doped TiO of claim 12The preparation method of the nano material is characterized by comprising the following steps: the dopant ions are either single doped or double doped with any two of palladium, indium, platinum, tin, or nitrogen.
3. The graphene composite doped TiO of claim 12The preparation method of the nano material is characterized by comprising the following steps: the acidifying agent is any one or mixture of hydrochloric acid, nitric acid, phosphoric acid, glacial acetic acid and perchloric acid.
4. The graphene composite doped TiO of claim 12The preparation method of the nano material is characterized by comprising the following steps: the titanate or titanate is selected from one or a mixture of the following: ti (OC)4H9)4、Ti(OC2H5)4、Ti(iso-OC3H7)4、Ti(SO4)2Or TiCl4。
5. The graphene composite doped TiO of claim 12The preparation method of the nano material is characterized by comprising the following steps: the diluent is one or more of high purity water, anhydrous ethanol, anhydrous methanol, glacial acetic acid and formic acid.
6. The graphene composite doped TiO of claim 12The preparation method of the nano material is characterized by comprising the following steps: the inert gas is any of nitrogen, argon or helium.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101301619A (en) * | 2008-07-03 | 2008-11-12 | 南开大学 | Method for preparing high efficiency metallic, non-metallic ion co-doped nano-TiO2 visible-light responsive photocatalyst |
| CN101444724A (en) * | 2008-12-24 | 2009-06-03 | 南开大学 | Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst |
| CN101890344A (en) * | 2010-07-27 | 2010-11-24 | 华东理工大学 | Preparation method of graphene/titanium dioxide composite photocatalyst |
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| US20060210798A1 (en) * | 2005-03-16 | 2006-09-21 | Clemens Burda | Doped metal oxide nanoparticles and methods for making and using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101301619A (en) * | 2008-07-03 | 2008-11-12 | 南开大学 | Method for preparing high efficiency metallic, non-metallic ion co-doped nano-TiO2 visible-light responsive photocatalyst |
| CN101444724A (en) * | 2008-12-24 | 2009-06-03 | 南开大学 | Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst |
| CN101890344A (en) * | 2010-07-27 | 2010-11-24 | 华东理工大学 | Preparation method of graphene/titanium dioxide composite photocatalyst |
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| Study on the visible-light-induced photokilling effect of nitrogen-doped TiO2 nanoparticles on cancer cells;Li,et al;《Nanoscale research letters》;20111231;第1-7页 * |
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