CN113648414A - Metal ion coordinated carbon dot/titanium dioxide heterojunction and preparation method and application thereof - Google Patents
Metal ion coordinated carbon dot/titanium dioxide heterojunction and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910003081 TiO2−x Inorganic materials 0.000 claims abstract description 35
- 239000002135 nanosheet Substances 0.000 claims abstract description 25
- 206010028980 Neoplasm Diseases 0.000 claims abstract description 22
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 210000004881 tumor cell Anatomy 0.000 claims abstract description 11
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 52
- 229960003180 glutathione Drugs 0.000 claims description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
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- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a metal ion coordinated carbon dot/titanium dioxide heterojunction and a preparation method and application thereof. The invention firstly prepares TiO doped with surface oxygen vacancy2‑xThe nano sheet achieves the purpose of reducing the forbidden bandwidth thereof, so that electrons are easier to be excited under the action of US; followed by the preparation of a metal ion (Cu) by complexation2+、Co3+、Fe3+、Pt4+、Mn4+) Coordinated carbon sites for the purpose of GSH depletion by carbon sites, and metal ion coordinated carbon sites for GSH detectionFor differentiating between normal cells and tumor cells; finally, by constructing metal ion coordinated carbon dots/TiO2‑xThe nano-sheet heterojunction greatly accelerates the carrier transmission rate and inhibits the recombination of electron hole pairs, and simultaneously realizes the regulation and control of a tumor microenvironment and enhanced acoustic dynamic tumor treatment by virtue of the GSH consumption capability of metal ions.
Description
Technical Field
The invention relates to the technical field of biomedicine, in particular to a metal ion coordinated carbon dot/titanium dioxide heterojunction and a preparation method and application thereof.
Background
Cancer, one of the most serious diseases worldwide, has caused millions of deaths, becoming the greatest threat to human health. In recent years, therapeutic strategies that produce highly biologically toxic Reactive Oxygen Species (ROS) from exogenously stimulated sensitizers have been considered as effective approaches to improve the current state of cancer therapy. For example, photodynamic therapy (PDT), which uses near infrared light (NIR) to activate ROS produced by photosensitizers, causes damage to DNA and thus induces apoptosis or necrosis of cancer cells. However, the penetration depth of near infrared light is limited (1cm), and deep tumors cannot be treated, which greatly limits the clinical application of PDT. Therefore, it is of great interest to develop a promising alternative approach to the treatment of deep tumors based on the mechanism of PDT. Sonodynamic therapy (SDT) primarily kills cancer cells by Ultrasound (US) triggering sonosensitizers to generate Reactive Oxygen Species (ROS). Compared to near-infrared lasers, US has a deeper tissue penetration depth (greater than 10cm) and has found widespread use in clinical diagnostics. Therefore, the US is used as an excitation source to develop the US mediated SDT, and is expected to essentially break through the limitation of the penetration depth of the traditional PDT treatment light and improve the treatment effect of deep tumors.
The acoustic sensitizers widely reported at present mainly comprise organic acoustic sensitizers and inorganic acoustic sensitizers. The organic sonosensitizer represented by porphyrin derivatives has the limitations of poor water solubility, fast in vitro clearance, short blood circulation time and the like while achieving a certain sonodynamic treatment effect. Inorganic semiconductor nanomaterials such as titanium dioxide (TiO) in contrast to organic sonosensitizers2) Has the advantages of chemical inertness to biological tissues, low cost, easy manufacture and the like, and is widely applied to SDT in recent years. But TiO 22The wide band gap structure (3.2eV) and the rapid recombination of electron-hole pairs (50 ± 30ns) reduce the quantum yield of ROS, resulting in poor SDT therapeutic effect. Therefore, the development of the high-efficiency and safe sound-sensitive agent has important significance for treating the tumor by the sound power.
On the other hand, with the occurrence and development of tumors, the tumor microenvironment can be obviously changed, and the rational utilization or regulation of the tumor microenvironment is an important way for enhancing the tumor treatment effect. Research shows that the reduction level (glutathione, GSH) in tumor cells is higher than that of normal cells, and excessive GSH can greatly consume ROS generated by a sound-sensitive agent under the action of US, so that the treatment efficiency of the SDT is greatly reduced, and the clinical application of the SDT is limited. In addition, GSH is an important antioxidant, and has the functions of resisting oxidation, scavenging free radicals and regulating important physiological and biochemical processes in cells. At present, methods for measuring the content of GSH mainly comprise an electrochemical method, a high performance liquid chromatography method, a fluorescence photometry method and the like, and the conventional colorimetric method for measuring the GSH such as a DTNB method, a new copper reagent method and the like has the problems of low sensitivity, easy interference, low detection limit and the like. Therefore, the design and synthesis of the novel nano acoustic sensitizer not only has enhanced acoustic dynamic performance, but also has GSH consumption capability, and simultaneously has GSH detection capability with high sensitivity, good selectivity and simplicity, thereby being the key and difficult point of the current SDT research.
Disclosure of Invention
The invention provides a metal ion coordinated carbon dot/titanium dioxide heterojunction and a preparation method and application thereof in order to solve the technical problems.
The invention adopts the following technical scheme.
A preparation method of a metal ion coordinated carbon dot/titanium dioxide heterojunction comprises the following steps:
a. preparation of pyridine N-doped carbon dots
S1, adding pyrene into concentrated nitric acid according to the mass volume ratio of 1 (50-100), and carrying out condensation reflux at the temperature of 80-85 ℃ for 24-96 h; cooling, washing to neutrality, and drying to obtain trinitropyrene;
s2, adding the trinitropyrene prepared in the step S1 into water, and then adding hydrazine hydrate into the solution, wherein the mass-volume ratio of the trinitropyrene to the hydrazine hydrate is (1.25-5): 100; stirring the obtained mixed solution for 10-12min, and then reacting for 1-60min at the temperature of 180-;
s3, cooling, taking out the carbon dots prepared in the step S2, filtering, dialyzing for 2-3 days, and drying to obtain pyridine N-doped carbon dot powder;
b. preparation of metal ion coordinated carbon dots
Dissolving pyridine N-doped carbon dots and metal ion precursor powder in water, stirring for 1-2 hours, collecting precipitates, washing and drying to obtain metal ion coordinated carbon dots;
c. oxygen vacancy doped TiO2-xPreparation of
S1, mixing tetra-n-butyl titanate with hydrofluoric acid, carrying out ultrasonic treatment for 10-12min, and reacting at 185 ℃ for 22-26 h; the volume ratio of the tetra-n-butyl titanate to the hydrofluoric acid is 25 (2-10); after cooling, collecting the precipitate, washing and drying to obtain TiO2Nanosheets;
s2, preparing the TiO prepared in the step S12Mixing the powder with sodium borohydride, and keeping the mixture at 380 ℃ and 400 ℃ for 2.5 to 3 hours under the nitrogen atmosphere, wherein the TiO is2The mass ratio of the powder to the sodium borohydride is 1 (0.5-2); cooling, adding the obtained product into 1M hydrochloric acid solution, stirring for 1-2h, collecting precipitate, washing and drying to obtain oxygen vacancy doped TiO2-xNanosheets;
d. preparation of metal ion coordinated carbon dot/titanium dioxide heterojunction
C, doping the oxygen vacancy-doped TiO prepared in the step c2-xThe nanosheets being dispersed in water towards the TiO2-xAdding the TiO doped with the carbon points and oxygen vacancies coordinated by the metal ions prepared in the step b into the solution2-xThe mass ratio of the carbon points coordinated by the nanosheets and the metal ions is 1: (0.5-2), mixing and stirring for 22-26 h; and washing and drying to obtain the metal ion coordinated carbon dot/titanium dioxide heterojunction.
Further, in the step b, CuCl is selected as the metal ion precursor2、Co(NH3)6Cl3、FeCl3·6H2O、K2PtCl4Or K2MnF6。
Further, in the step b, the mass ratio of the pyridine N-doped carbon dots to the metal ion precursor powder is 1: (0.5-5).
A metal ion coordinated carbon dot/titanium dioxide heterojunction prepared by the preparation method.
An application of the carbon dot/titanium dioxide heterojunction coordinated by the metal ions in preparing a sonosensitizer for sonodynamic tumor treatment.
An application of the metal ion coordinated carbon dot/titanium dioxide heterojunction in preparing a product for detecting tumor cells.
Further, the carbon dot/titanium dioxide heterojunction coordinated by the metal ions distinguishes tumor cells from normal cells by detecting the content of glutathione in the cells.
The present invention obtains the following advantageous effects.
The method effectively solves the problems that the yield of Reactive Oxygen Species (ROS) is low, the ROS is easily consumed by endogenous GSH and the like in the existing nano sound-sensitive agent. The metal ion coordinated carbon dot/titanium dioxide heterojunction acoustic sensitivity agent prepared by the method not only has the synergistically enhanced acoustic dynamic performance, but also has the capability of detecting the content of Glutathione (GSH) in cells. In addition, the sound-sensitive agent also has the capacity of regulating and controlling the tumor microenvironment, and can consume excessive GSH in tumor cells so as to realize amplification of ROS quantum yield. The nano sound-sensitive agent has high biocompatibility, no obvious long-term toxicity, simple preparation process and lower cost, and is suitable for large-scale production.
Drawings
FIG. 1 is a representation of the products prepared in examples 1 to 4 of the present invention (wherein: a. TiO)2TEM and HRTEM images of the nanoplates; TiO 22-xTEM and HRTEM images of the nanoplates; TEM images of cds; TEM image of Pt (IV) -CDs; pt (IV) -CD @ TiO2-xTEM and HRTEM images of);
FIG. 2 is a schematic representation of the products prepared in examples 1-4 of the present invention1O2OH formation efficiency test results (wherein: a. Pt (IV) -CD @ TiO)2-xHeterojunction, TiO2-xNanosheet and TiO2Of nanosheets1O2Generating a rate map; pt (IV) -CD @ TiO2-xHeterojunction, TiO2-xNanosheet and TiO2OH generation rate map of nanoplates);
FIG. 3 shows Pt (IV) -CD @ TiO prepared in example 4 of the present invention2-xA graph of the results of the detection of heterojunction consumed GSH;
FIG. 4 is a drawing of the present inventionPt (IV) -CD @ TiO prepared in example 42-xA cell viability detection result graph of the heterojunction under the irradiation or the non-irradiation of the US;
FIG. 5 shows Pt (IV) -CD @ TiO prepared in example 4 of the present invention2-xGraph of the in vivo sonodynamic therapeutic effect of the heterojunction sonosensitizer (wherein: a. graph of the change of tumor volume during tumor therapy; b. graph of the change of body weight of nude mice during tumor therapy; c. graph of the life span of nude mice in different treatment groups);
FIG. 6 shows Pt (IV) -CD @ TiO prepared in example 4 of the present invention2-xAnd (3) applying the heterojunction sound-sensitive agent to a result graph of intracellular GSH content detection.
Detailed Description
The present invention will be further described with reference to examples.
Example 1
Preparation method of pyridine N-doped Carbon Dots (CDs)
a. Slowly adding 4g of pyrene into 320mL of concentrated nitric acid (mass fraction is 68%), carrying out condensation reflux at 80 ℃ for reacting for 48h, cooling to room temperature, diluting with deionized water to obtain a mixture solution, repeatedly carrying out suction filtration and washing until the mixture solution is neutral, and drying to obtain trinitropyrene;
b. weighing 0.025g of trinitropyrene obtained in the step a, and adding the trinitropyrene into 10mL of water; then adding 1mL of hydrazine hydrate into the solution, stirring the solution for 10min, transferring the solution into a 30mL microwave reaction tube, and reacting for 30min at the temperature of 200 ℃;
c. and (c) after natural cooling, taking out the carbon dots obtained in the step (b), filtering with a 220nm filter membrane, transferring the filtered solution into a dialysis bag for dialysis for 2 days, and performing rotary evaporation and drying on the solution to finally obtain pyridine N-doped carbon dot powder.
Example 2
Preparation method of metal ion coordinated carbon dots (Pt (IV) -CDs):
weighing CDs and K according to the mass ratio of 1:22PtCl4Dissolving the powder in water, stirring and reacting for 1.5 hours at room temperature, centrifugally collecting precipitates after the reaction is finished, centrifugally washing for 3 times by using deionized water, and drying to obtain the platinum coordination functionalized carbon dots.
Example 3
Oxygen vacancy doped TiO2-xThe preparation method comprises the following steps:
a. measuring 10mL of tetra-n-butyl titanate into a 50mL of reaction kettle with a polytetrafluoroethylene lining, slowly adding 1.2mL of hydrofluoric acid under the stirring condition, and carrying out ultrasonic treatment for 10min to react for 24 hours at 180 ℃;
b. after naturally cooling to room temperature, collecting white precipitate, washing with ethanol and deionized water for three times, and drying to obtain white TiO2Nanosheets;
c. weighing 0.6g of the white TiO prepared in step b2The powder and 0.6g of sodium borohydride are fully and uniformly mixed and then placed in a tube furnace to be kept for 3 hours at 400 ℃ under the nitrogen atmosphere, the mixture is naturally cooled to room temperature, the obtained black powder is slowly added into 1M hydrochloric acid solution to be stirred for 1.5 hours, black precipitate is centrifugally collected and washed by ethanol and deionized water for multiple times, and finally vacuum drying is carried out to obtain the oxygen vacancy doped TiO2-xNanosheets.
Example 4
Metal ion coordinated CD @ TiO2-xThe preparation method of the heterojunction acoustic sensitivity agent comprises the following steps:
take Pt (IV) coordinated carbon sites as an example, weigh 10mg of the oxygen vacancy doped TiO prepared in example 32-xThe nanoplatelets were dispersed in 10mL deionized water, after which the Pt (IV) coordinated carbon dots (Pt (IV) -CDs) (2mg/mL) prepared in example 2 were slowly added to the TiO2-xMixing the solution evenly, stirring the solution for 24 hours at room temperature, centrifugally washing the solution by deionized water to remove excessive Pt (IV) -CDs, and carrying out centrifugal washing on the prepared Pt (IV) -CD @ TiO2-xAnd freeze-drying the heterojunction sonosensitizer in a freeze dryer and then storing.
The products obtained in examples 1 to 4 were characterized by instrumental testing, and the experimental results are shown in FIG. 1. As can be seen from FIG. 1, the resulting TiO2The nano sheet is of a two-dimensional lamellar structure, the particle size distribution of the nano sheet is 30-60 nm, and the nano sheet has good dispersibility in a water phase; under the observation of a high power electron microscope, the crystal lattice has obvious crystal lattice stripes. Oxygen vacancy doped TiO2-xThe nano sheet also has a two-dimensional lamellar structure, the particle size distribution is 30-60 nm, and the nano sheet is compared with TiO2Nanosheets, TiO2-xThe lattice fringes of the nano-sheets are not obvious and the dispersibility is poorThis is due to the reduced water solubility of the high temperature treatment after the introduction of oxygen vacancies. The average particle diameter of CDs is 3.7 +/-0.7 nm, and the dispersity is good. The particle size distribution of Pt (IV) -CDs is 20-50 nm, and the dispersibility is good; pt (IV) -CD @ TiO2-xTEM and HRTEM of heterojunctions show that Pt (IV) -CDs can be distributed very uniformly on TiO2-xThe surface of the nanoplatelets.
Performance detection
1. Pt (IV) -CD @ TiO prepared in example 42-xAcoustic dynamic performance detection of heterojunction acoustic sensitizers
(1) Pt (IV) -CD @ TiO prepared in example 4 of the present invention2-xThe sonosensitizer can generate a large amount of singlet oxygen under low-intensity ultrasound (1O2) By using 1, 3-Diphenylisobenzofuran (DPBF) as1O2Probe for detecting Pt (IV) -CD @ TiO2-xUnder ultrasonic irradiation of sonosensitizer1O2Efficiency was generated to evaluate its acoustic dynamic performance.
(2) Pt (IV) -CD @ TiO prepared in example 4 of the present invention2-xThe sonosensitizer can generate a large amount of hydroxyl radicals (. OH) under low-intensity ultrasound, and Pt (IV) -CD @ TiO (TiO) is detected by using 3,3,5, 5-Tetramethylbenzidine (TMB)2-xOH generation efficiency of the sonosensitizer under ultrasonic irradiation.
Pt (IV) -CD @ TiO prepared in example 4 of this application2-xOf a heterojunction1O2FIG. 2 shows the results of measuring OH formation efficiency. As can be seen from FIG. 2, Pt (IV) -CD @ TiO2-xOf a heterojunction1O2The production rate of OH and OH is superior to that of TiO2-xNanosheet and TiO2Nanosheets.
(3) Pt (IV) -CD @ TiO prepared in example 4 of the present invention2-xThe sonosensitizer may endogenously consume Glutathione (GSH), and Pt (IV) -CD @ TiO was assessed by using 5,5' -dithiobis (2-nitrobenzoic acid) (DTNB) as a GSH probe2-xThe ability of sonosensitizers to consume GSH.
Pt (IV) -CD @ TiO prepared in example 4 of this application2-xThe results of the detection of GSH consumption by the heterojunction are shown in fig. 3. As can be seen from FIG. 3, Pt (IV) -CD @ TiO2-xThe heterojunction can efficiently consume GSH.
2. Pt (IV) -CD @ TiO prepared in example 42-xIn vitro sonodynamic treatment of heterojunction sonosensitizers
The invention carries out the MTT method on Pt (IV) -CD @ TiO2-xThe cells after heterojunction and US irradiation treatment were examined for cell viability. Human osteosarcoma cells (143B) were seeded into 96-well plates at a density of 5000 per well, cultured for 24 hours, and then added at various concentrations (0, 25, 50, 100, 200, 300. mu.gmL)-1) Pt (IV) -CD @ TiO (2)2-xThe heterojunctions were incubated for 4 hours with US (50kHz,2.0W cm)-2) After 5 minutes of irradiation, the cells were further cultured for 24 or 48 hours, 20. mu.L of MTT was added, the incubation was further continued at 37 ℃ for 4 hours, and finally the culture medium in each well was aspirated, dissolved by adding 150. mu.L of dimethyl sulfoxide, and the absorbance at 490nm was measured with a microplate reader. In addition, Pt (IV) -CD @ TiO alone without US irradiation was simultaneously detected2-xCell viability after heterojunction treatment to assess biocompatibility of the heterojunction sonosensitizers.
Pt (IV) -CD @ TiO prepared in example 4 of the present application2-xThe results of the heterojunction cell viability assay are shown in figure 4. As can be seen from FIG. 4, Pt (IV) -CD @ TiO2-xThe heterojunction has excellent biocompatibility; pt (IV) -CD @ TiO under US irradiation2-xThe heterojunction can completely kill the tumor cells.
3. Pt (IV) -CD @ TiO prepared in example 42-xIn vivo sonodynamic treatment of heterojunction sonosensitizers
100 mu.L (500 ten thousand) of human osteosarcoma cells (143B) were subcutaneously implanted in axilla of a female nude mouse for 3-5 weeks until the tumor volume reached 100mm3At the time, nude mice were divided into 6 groups (5 per group): (1) physiological saline, (2) US irradiation alone (50kHz,2.0W cm)-2,5min)、(3)Pt(IV)-CD@TiO2-xHeterojunction, (4) TiO2-x+ US irradiation (50kHz,2.0W cm)-2,5min)、(5)CD@TiO2-x+ US irradiation (50kHz,2.0W cm)-2,5min)、(6)Pt(IV)-CD@TiO2-x+ US irradiation (50kHz,2.0W cm)-25 min). Tumor volume was measured every other day and nude mice were recorded daily for assessment of Pt (IV) -CD @ TiO2-xHeterojunction acoustic sensitizersThe efficiency of internal acoustic dynamic therapy.
Pt (IV) -CD @ TiO prepared in example 4 of the present invention2-xThe results of in vivo sonodynamic therapy with heterojunction sonosensitizers are shown in figure 5. As can be seen from FIG. 5, under US irradiation, in contrast to TiO2-xNanosheet and CD @ TiO2-xHeterojunction, Pt (IV) -CD @ TiO2-xThe heterojunction has optimal tumor treatment effect, can completely inhibit tumor growth, prolong the life of nude mice, and simultaneously Pt (IV) -CD @ TiO2-xThe heterojunctions do not exhibit significant long-term toxicity in vivo.
4. Pt (IV) -CD @ TiO prepared in example 42-xApplication of heterojunction acoustic sensitivity agent in detecting content of GSH (glutathione) in cells
Hela cells, 143B cells and LO2 cells were planted in a confocal dish overnight, and after 24h incubation, Pt (IV) -CD @ TiO was added2-xAnd incubating the heterojunction in fresh culture solution for 0h, 3h, 6h, 12h and 24h respectively. Fluorescence imaging capabilities were studied using Confocal Laser Scanning Microscopy (CLSM).
As shown in fig. 6, it is understood from fig. 6 that the CDs gave bright fluorescent signals to the tumor cells (Hela, 143B) and the normal cells (LO2) after 24 hours, indicating that the carbon spots alone could not detect the intracellular GSH concentration. The fluorescence signal of the tumor cells (Hela, 143B) after the metal ion coordinated carbon dots (Pt (IV) -CD) are endowed is obviously stronger than that of the normal cells (LO2), and the Pt (IV) -CD @ TiO (titanium dioxide) is proved to be2-xThe heterojunction can be used as GSH probe to distinguish tumor cells from normal cells.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (7)
1. A preparation method of a metal ion coordinated carbon dot/titanium dioxide heterojunction is characterized by comprising the following steps: the method comprises the following steps:
a. preparation of pyridine N-doped carbon dots
S1, adding pyrene into concentrated nitric acid according to the mass volume ratio of 1 (50-100), and carrying out condensation reflux at the temperature of 80-85 ℃ for 24-96 h; cooling, washing to neutrality, and drying to obtain trinitropyrene;
s2, adding the trinitropyrene prepared in the step S1 into water, and then adding hydrazine hydrate into the solution, wherein the mass-volume ratio of the trinitropyrene to the hydrazine hydrate is (1.25-5): 100; stirring the obtained mixed solution for 10-12min, and then reacting for 1-60min at the temperature of 180-;
s3, cooling, taking out the carbon dots prepared in the step S2, filtering, dialyzing for 2-3 days, and drying to obtain pyridine N-doped carbon dot powder;
b. preparation of metal ion coordinated carbon dots
Dissolving pyridine N-doped carbon dots and metal ion precursor powder in water, stirring for 1-2 hours, collecting precipitates, washing and drying to obtain metal ion coordinated carbon dots;
c. oxygen vacancy doped TiO2-xPreparation of
S1, mixing tetra-n-butyl titanate with hydrofluoric acid, carrying out ultrasonic treatment for 10-12min, and reacting at 185 ℃ for 22-26 h; the volume ratio of the tetra-n-butyl titanate to the hydrofluoric acid is 25 (2-10); after cooling, collecting the precipitate, washing and drying to obtain TiO2Nanosheets;
s2, preparing the TiO prepared in the step S12Mixing the powder with sodium borohydride, and keeping the mixture at 380 ℃ and 400 ℃ for 2.5 to 3 hours under the nitrogen atmosphere, wherein the TiO is2The mass ratio of the powder to the sodium borohydride is 1 (0.5-2); cooling, adding the obtained product into 1M hydrochloric acid solution, stirring for 1-2h, collecting precipitate, washing and drying to obtain oxygen vacancy doped TiO2-xNanosheets;
d. preparation of metal ion coordinated carbon dot/titanium dioxide heterojunction
C, doping the oxygen vacancy-doped TiO prepared in the step c2-xThe nanosheets being dispersed in water towards the TiO2-xAdding the TiO doped with the carbon points and oxygen vacancies coordinated by the metal ions prepared in the step b into the solution2-xThe mass ratio of the carbon points coordinated by the nanosheets and the metal ions is 1: (0.5-2), mixing and stirring for 22-26 h; and washing and drying to obtain the metal ion coordinated carbon dot/titanium dioxide heterojunction.
2. The method of claim 1, wherein the metal ion coordinated carbon dot/titanium dioxide heterojunction: in the step b, the metal ion precursor is CuCl2、Co(NH3)6Cl3、FeCl3·6H2O、K2PtCl4Or K2MnF6。
3. The method of claim 1, wherein the metal ion coordinated carbon dot/titanium dioxide heterojunction: in the step b, the mass ratio of the pyridine N-doped carbon dots to the metal ion precursor powder is 1: (0.5-5).
4. A metal ion coordinated carbon dot/titanium dioxide heterojunction prepared by the preparation method as claimed in any one of claims 1 to 3.
5. Use of a metal ion coordinated carbon dot/titanium dioxide heterojunction as claimed in claim 4 in the preparation of a sonosensitizer for sonodynamic tumour therapy.
6. Use of a metal ion-coordinated carbon dot/titanium dioxide heterojunction as defined in claim 4 in the preparation of a product for detecting tumor cells.
7. Use according to claim 4, characterized in that: the carbon dot/titanium dioxide heterojunction coordinated by the metal ions distinguishes tumor cells from normal cells by detecting the content of glutathione in the cells.
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