CN113101366B - Molybdenum disulfide-based material with photo-thermal and photodynamic properties and preparation method thereof - Google Patents
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Abstract
The invention discloses a molybdenum disulfide-based material with both photothermal and photodynamic properties, which takes a molybdenum disulfide nanosheet as a carrier, wherein TCPP is coupled on the surface of the molybdenum disulfide nanosheet through cysteamine, and NH is coupled on the surface of the molybdenum disulfide nanosheet through lipoic acid 2 -PEG-TPP. The molybdenum disulfide in the molybdenum disulfide-based material has good biocompatibility, and the permeability of the molybdenum disulfide in organisms can be improved when the molybdenum disulfide-based material is prepared into a sheet shape for application; in addition, it has high retention effect in organisms as a nano-scale material; finally, adopting flaky molybdenum disulfide as a carrier to couple TCPP and NH 2 After PEG-TPP, on the one hand, the pharmacokinetics of TCPP in vivo can be changed, on the other hand, TCPP can be separated from each other so as not to be aggregated, thus improving the photostability of the TCPP, and the introduction of the targeting group can lead the photothermal and photodynamic material to target mitochondria of tumor cells, thus further enhancing the killing effect of the photothermal and photodynamic material on cancer cells.
Description
Technical Field
The invention relates to a molybdenum disulfide-based material with both photo-thermal and photodynamic properties, and also relates to a preparation method of the molybdenum disulfide-based material with both photo-thermal and photodynamic properties.
Background
Photothermal therapy of cancer is a new non-invasive anti-cancer means that has emerged in recent years. The tumor is locally high Wen Shashang malignant tumor cells by light induction, has almost no side effect on normal tissues of human bodies, and is called as green therapy in the international medical community. In recent years, a great deal of research has shown that: the molybdenum disulfide has good optical characteristics, and the photo-thermal conversion efficiency (35%) of the molybdenum disulfide is obviously higher than that of the gold nanorod (20%). Therefore, compared with other photothermal conversion materials, molybdenum disulfide has stronger photothermal conversion advantage in the aspect of photothermal treatment of tumors, so that molybdenum disulfide is often used as a thermal material for photothermal treatment of tumors.
Photodynamic therapy is a laser medical technique for the treatment of localized lesions, particularly malignant tumors, in the human body, based on the interaction of light, photosensitizers and oxygen. When the photosensitizer is irradiated by light with specific wavelength, it can absorb photon to be excited, and can quickly transfer the absorbed light energy to surrounding oxygen molecules by intersystem crossing to be converted into triplet state, and the oxygen molecules can produce a series of photochemical reactions to form singlet oxygen so as to kill tumor or other pathological tissues and achieve the therapeutic purpose. The meso-tetra (4-carboxyphenyl) porphin (TCPP) has higher quantum yield and can be used as a photodynamic material. However, because of its small molecular weight, aggregation is easy to occur (small molecules with particularly strong conjugation effect, intermolecular pi-pi stacking is easy to occur, that is, intermolecular attraction is strong, aggregation is easy to occur in any case, and in water, because TCPP has poor solubility, aggregation effect is more obvious in order to reduce surface tension), resulting in a decrease in fluorescence yield and quantum yield, and poor light stability.
Disclosure of Invention
The invention aims to: aiming at the problems of poor light stability, poor water solubility and low bioavailability of the photodynamic material TCPP on the other hand, the invention provides a molybdenum disulfide base material with both the photothermal and photodynamic performances.
The invention also provides a preparation method of the molybdenum disulfide-based material with both photothermal and photodynamic properties.
The technical scheme is as follows: the molybdenum disulfide-based material with both photothermal and photodynamic properties takes a molybdenum disulfide nanosheet as a carrier, TCPP is coupled on the surface of the molybdenum disulfide nanosheet through cysteamine, and meanwhileCoupling NH on the surface of molybdenum disulfide nanosheets through lipoic acid 2 -PEG-TPP。
Wherein, the molybdenum disulfide nano-sheet with S lattice defect adsorbs cysteamine and lipoic acid on the surface thereof by chemical adsorption. N-butyllithium is intercalated into molybdenum disulfide (molybdenum disulfide is similar to a graphene structure and is a layered structure of a multi-layer stack), water is added to form a large amount of hydrogen, a large amount of heat is generated in the process, the layered structure is flushed away by the hydrogen to form a layer-by-layer two-dimensional sheet structure, in the flushing-away process, as molybdenum disulfide is crystal, a part of chemical bonds are broken through energy input, then sulfur lattice defects are formed, a part of sulfur atoms of the molybdenum disulfide can be deleted, namely a part of S atoms can run away after flushing away, a plurality of S vacancies are reserved in situ, then S-containing compounds can occupy the vacancies, and the chemical adsorption force between the S-containing compounds and the molybdenum disulfide is strong.
Wherein the length of the molybdenum disulfide nanosheets is 200-400 nm, the width is 200-400 nm, and the thickness is 2-10 nm.
Wherein the load capacity of TCPP on the surface of the molybdenum disulfide nanosheets is 10-20% of the mass of the molybdenum disulfide nanosheets; surface NH of molybdenum disulfide nanosheets 2 The loading amount of the PEG-TPP is 5-6% of the mass of the molybdenum disulfide nanosheets.
The preparation method of the molybdenum disulfide-based material with the photo-thermal and photodynamic properties comprises the following steps:
(1) Dispersing blocky molybdenum disulfide in hexane solution containing n-butyllithium, continuously stirring for at least 2 days under the protection of nitrogen, filtering and collecting molybdenum disulfide solid, dispersing the collected molybdenum disulfide solid in water, performing ultrasonic treatment (the purpose of ultrasonic treatment is to further break Van der Waals force, because n-butyllithium intercalation is possibly not completely washed away after being washed away by hydrogen, then assisting ultrasonic treatment to become monodisperse molybdenum disulfide nanosheets, the Van der Waals force between layers is weak at this time), performing centrifugal solid-liquid separation after ultrasonic treatment, dispersing the collected flaky molybdenum disulfide in water again after separation, and removing small molecular impurities adsorbed on the molybdenum disulfide nanosheets by dialysis(the salt formed after the reaction of the n-butyllithium is also a small amount of the salt is adsorbed on the molybdenum disulfide nanosheets at the moment) so as to obtain a molybdenum disulfide aqueous solution; the two-dimensional flaky molybdenum disulfide has the following advantages: on the one hand improve MoS 2 Is used for the utilization rate of the (a); on the other hand, the specific surface area is increased, the specific surface area of the two-dimensional flaky molybdenum disulfide is larger than that of the massive molybdenum disulfide, the active sites are more than that of the massive molybdenum disulfide, and in addition, the high-activity singlet oxygen generated in the PDT (photodynamic) process is generated 1 O2) extremely short lifetime in water (2. Mu.s), two-dimensional sheet MoS 2 Can improve% 1 O2) diffusion distance and effect;
(2) Adding cysteamine and lipoic acid into molybdenum disulfide water solution, reacting, and sequentially adding TCPP and NH under the action of an activating agent 2 -PEG-TPP, continuing the reaction to obtain solution B;
(3) After the solution B is subjected to centrifugal solid-liquid separation, TCPP and NH loaded on the surface are obtained 2 -molybdenum disulfide nanosheets of PEG-TPP. On one hand, the carrier function of molybdenum disulfide changes the pharmacokinetics of TCPP in vivo (small molecular substances have low bioavailability and are easy to metabolize), and on the other hand, the TCPP is separated and not aggregated, so that the photostability of the TCPP is improved.
In photothermal therapy, moS is generally used 2 Putting into PBS or physiological saline, and simply MoS 2 The nanoplatelets aggregate when placed in PBS or physiological saline for a short period of time, and MoS if PEG is absent 2 The nano-sheets can be directly aggregated in PBS or physiological saline; thus modifying MoS with PEG 2 The nano-sheet can improve the dispersibility of the nano-sheet in PBS and physiological saline; in addition, the human body has no immune recovery effect on PEG, namely the human body can treat the PEG as endogenous substances and does not reject the PEG, if MoS is directly added 2 The nanometer sheet can be metabolized by human body quickly, and the PEG has the functions of improving the dispersivity and the solubility of the nanometer sheet in PBS and physiological saline on one hand and improving MoS on the other hand 2 The bioavailability of the nano-sheet is not easy to be metabolized.
In the step (1), the mixing mass ratio of molybdenum disulfide, n-butyllithium and hexane is as follows: (0.8-1.2): (0.8-1.2): (5-7).
Wherein in the step (2), the activator (the reaction of activated carboxyl and amino) is a compound of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide with equal molar concentration.
Wherein, in the step (2), the adding mole ratio of the cysteamine and the lipoic acid is (0.8-1.2): (1-1.5).
Cysteamine and lipoic acid modified molybdenum disulfide and TCPP and NH 2 Reaction mechanism of PEG-TPP:
the beneficial effects are that: molybdenum disulfide has good biocompatibility, and can improve the permeability of the molybdenum disulfide in organisms when the molybdenum disulfide is prepared into a sheet shape for application; in addition, it has high retention effect in organisms as a nano-scale material; finally, adopting flaky molybdenum disulfide as a carrier to couple TCPP and NH 2 After PEG-TPP, on the one hand, the pharmacokinetics of TCPP in vivo can be improved, and due to the fact that the vascular permeability near the tumor is better and the vascular gap is larger, the tumor tissue has better absorption and uptake capacity on the nano particles, so that the nano particles have natural targeting capacity on the tumor tissue; since TCPP is originally a small molecule, it is stably supported on MoS 2 On the nanoplatelets, they are protected so that in vivo metabolism is MoS compliant 2 Metabolic conditions of nanoplatelets in vivo; on the other hand, the intermolecular acting force of TCPP can be weakened, and the accumulation and aggregation phenomenon does not occur, so that the light stability of the TCPP is improved; finally, the introduction of the targeting group can lead the photothermal and photodynamic materials to target mitochondria of tumor cells on one hand, and further enhance the killing effect of the photothermal and photodynamic materials on cancer cells; on the other hand, after PEG modification, moS can be improved 2 Bioavailability of the nanoplatelets.
Drawings
FIG. 1 is MoS 2 Transmission electron microscopy of nanoplatelets;
FIG. 2 is a schematic diagram of a molybdenum disulfide-based two-dimensional nano-meter according to the present inventionRice flake (TCPP@MoS) 2 -TPP accumulated TCPP release amount over 48h of incubation in PBS (ph=7.0);
FIG. 3 is a graph of free TCPP and TCPP@MoS 2 -comparison of photostability of TPP nanoplatelets under 660nm laser irradiation;
FIG. 4 is MoS 2 PEG-TPP, TCPP and TCPP@MoS 2 TPP on breast cancer cells MCF-7 under darkness and laser light (660 nm, 5 mW/cm) 2 30 min).
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1
Weighing 1g of blocky molybdenum disulfide, dispersing in 10mL of hexane solution containing 1.025g of n-butyllithium, continuously stirring for 2 days under the protection of nitrogen, filtering and collecting molybdenum disulfide solids, dispersing the collected molybdenum disulfide solids in water, carrying out ultrasonic treatment for 1h, carrying out centrifugal solid-liquid separation after ultrasonic treatment, dispersing the collected flaky molybdenum disulfide in water again, and removing small molecular impurities adsorbed on molybdenum disulfide nano-sheets in a dialysis mode to obtain molybdenum disulfide aqueous solution; adding 2mol of lipoic acid and 2mol of cysteamine into the molybdenum disulfide aqueous solution, and reacting for 12 hours; after the reaction, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added in equal amounts to the mixture, and 2mol of TCPP and 1mol of NH were added 2 -PEG-TPP, continuing the reaction for 30min; after the reaction, the reaction solution is centrifugally separated at the rotating speed of 15000rpm, and the molybdenum disulfide-based material with both photothermal and photodynamic performances is obtained.
Example 2
Weighing 1g of massive molybdenum disulfide, dispersing in 10mL of hexane solution containing 1.025g of n-butyllithium, continuously stirring for 2 days under the protection of nitrogen, filtering to collect molybdenum disulfide solid, dispersing the collected molybdenum disulfide solid in water, carrying out ultrasonic treatment for 1h, carrying out centrifugal solid-liquid separation after ultrasonic treatment, dispersing the collected flaky molybdenum disulfide in water again after centrifugation, removing small molecular impurities adsorbed on molybdenum disulfide nano-sheets in a dialysis mode, and obtaining the molybdenum disulfide water-soluble productA liquid; adding 2mol of lipoic acid and 2mol of cysteamine into the molybdenum disulfide aqueous solution, and reacting for 13h; after the reaction, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added in equal amounts to the mixture, and 2mol of TCPP and 1mol of NH were added 2 -PEG-TPP, continuing the reaction for 35min; after the reaction, the reaction solution is centrifugally separated at the rotating speed of 15000rpm, and the molybdenum disulfide-based material with both photothermal and photodynamic performances is obtained.
Example 3
Weighing 1g of blocky molybdenum disulfide, dispersing in 10mL of hexane solution containing 0.925g of n-butyllithium, continuously stirring for 2 days under the protection of nitrogen, filtering to collect molybdenum disulfide solids, dispersing the collected molybdenum disulfide solids in water, carrying out ultrasonic treatment for 1h, carrying out centrifugal solid-liquid separation after ultrasonic treatment, dispersing the collected flaky molybdenum disulfide in water again, and removing small molecular impurities adsorbed on molybdenum disulfide nano-sheets in a dialysis mode to obtain molybdenum disulfide aqueous solution; adding 2mol of lipoic acid and 2mol of cysteamine into the molybdenum disulfide aqueous solution, and reacting for 12 hours; after the reaction, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added in equal amounts to the mixture, and 2mol of TCPP and 1mol of NH were added 2 -PEG-TPP, continuing the reaction for 35min; after the reaction, the reaction solution is centrifugally separated at the rotating speed of 15000rpm, and the molybdenum disulfide-based material with both photothermal and photodynamic performances is obtained.
Example 4
Weighing 1.3g of blocky molybdenum disulfide, dispersing in 10mL of hexane solution containing 0.925g of n-butyllithium, continuously stirring for 2 days under the protection of nitrogen, filtering to collect molybdenum disulfide solids, dispersing the collected molybdenum disulfide solids in water, carrying out ultrasonic treatment for 1h, carrying out centrifugal solid-liquid separation after ultrasonic treatment, dispersing the collected flaky molybdenum disulfide in water again, and removing small molecular impurities adsorbed on molybdenum disulfide nano-flakes in a dialysis mode to obtain a molybdenum disulfide aqueous solution; adding 2mol of lipoic acid and 2mol of cysteamine into the molybdenum disulfide aqueous solution, and reacting for 13h; after the reaction, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide are added in equal amounts to the mixtureImine, add 2mol TCPP and 1mol NH 2 -PEG-TPP, continuing the reaction for 35min; after the reaction, the reaction solution is centrifugally separated at the rotating speed of 15000rpm, and the molybdenum disulfide-based material with both photothermal and photodynamic performances is obtained.
Example 5: in vitro Release test
Stability of the molybdenum disulfide-based two-dimensional nanosheets under physiological conditions: the molybdenum disulfide-based two-dimensional nanosheets prepared in example 1 were dispersed in a certain amount of PBS solution having pH of 7.0, and supernatants were centrifuged at specific time intervals (1, 2, 4, 8, 16, 24, 48 hours) and tested for ultraviolet absorption peaks, respectively. As shown in FIG. 2, TCPP was stably adsorbed to MoS during 48h of incubation 2 Less than 5% of TCPP on the nanoplatelets is leaking.
Example 6: light stability test
The molybdenum disulfide-based two-dimensional nanosheets are applied to a photostability test in photodynamic therapy: the molybdenum disulfide-based two-dimensional nano sheet prepared in the embodiment 1 is irradiated by using a 660nm infrared laser for 10min, free TCPP is used as a reference, and the light stability of the free TCPP and the molybdenum disulfide-based two-dimensional nano sheet is quantitatively evaluated by comparing the absorption intensity change of the free TCPP and the molybdenum disulfide-based two-dimensional nano sheet under a 420nm characteristic absorption peak, as shown in figure 3, after the laser irradiation for 10min, the degradation rate of the free TCPP reaches 40%, but the light degradation rate of the molybdenum disulfide-based two-dimensional nano sheet does not exceed 8%, so that the aggregation and accumulation effect of TCPP molecules can be effectively prevented when the TCPP is loaded on the molybdenum disulfide nano sheet, and the light stability of the TCPP on the molybdenum disulfide nano sheet is improved.
Example 7
Dispersing the molybdenum disulfide-based two-dimensional nano-sheet prepared in the example 1 in a neutral PBS (phosphate buffer solution) solution with the concentration of 8mg/mL (pH of 7.0), selecting MCF-7 as a cell model for anti-tumor effect, and examining cytotoxicity of the molybdenum disulfide-based two-dimensional nano-sheet under 660nm illumination with the illumination intensity of 5mW/cm 2 The illumination time is 30min.
Using breast cancer MCF-7 as cell model, different concentrations of MoS were explored 2 PEG-TPP, TCPP and TCPP@MoS 2 -survival of TPP to MCF-7 cellsIs a function of (a) and (b). As shown in FIG. 4, in the absence of illumination, moS 2 PEG-TPP, TCPP and TCPP@MoS 2 TPP has no significant effect on the survival rate of MCF-7, meaning that they are all well biocompatible. After applying the light for 30min, moS 2 PEG-TPP and TCPP produced moderate cytotoxicity on MCF-7 cell viability, indicating insufficient photothermal and photodynamic alone to kill all cancer cells, but when the two were combined we incubated MCF-7 cells with TCPP@MoS2-TPP and illuminated for 30min, we found less than 5% cell viability, meaning TCPP@MoS 2 TPP implements MoS 2 Organic combination of photothermal and TCPP photodynamic therapy.
Claims (3)
1. A molybdenum disulfide-based material with both photothermal and photodynamic properties is characterized in that: the material takes a molybdenum disulfide nanosheet as a carrier, TCPP is coupled on the surface of the molybdenum disulfide nanosheet through cysteamine, and NH is coupled on the surface of the molybdenum disulfide nanosheet through lipoic acid 2 -PEG-TPP；
The molybdenum disulfide-based material is prepared by the following method, and specifically comprises the following steps: weighing 1g of blocky molybdenum disulfide, dispersing in 10mL of hexane solution containing 1.025g of n-butyllithium, continuously stirring for 2 days under the protection of nitrogen, filtering and collecting molybdenum disulfide solids, dispersing the collected molybdenum disulfide solids in water, carrying out ultrasonic treatment for 1h, carrying out centrifugal solid-liquid separation after ultrasonic treatment, dispersing the collected flaky molybdenum disulfide in water again, and removing small molecular impurities adsorbed on molybdenum disulfide nano-sheets in a dialysis mode to obtain molybdenum disulfide aqueous solution; adding 2mol of lipoic acid and 2mol of cysteamine into the molybdenum disulfide aqueous solution, and reacting for 12 hours; after the reaction, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added in equal amounts to the mixture, and 2mol of TCPP and 1mol of NH were added 2 -PEG-TPP, continuing the reaction for 30min; after the reaction, centrifugally separating the reaction solution at the rotating speed of 15000rpm to obtain molybdenum disulfide-based material TCPP@MoS2-TPP with both photo-thermal and photodynamic properties; the TCPP load capacity on the surface of the molybdenum disulfide nanosheet is the mass of the molybdenum disulfide nanosheet10-20%; surface NH of molybdenum disulfide nanosheets 2 The loading amount of the PEG-TPP is 5-6% of the mass of the molybdenum disulfide nanosheets;
MCF-7 cells were incubated with TCPP@MoS2-TPP and less than 5% of the cells survived 30min after illumination.
2. The molybdenum disulfide-based material having both photothermal and photodynamic properties according to claim 1, wherein: the molybdenum disulfide nanosheets having S lattice defects adsorb cysteamine and lipoic acid on the surfaces thereof by chemical adsorption.
3. The molybdenum disulfide-based material having both photothermal and photodynamic properties according to claim 1, wherein: the length of the molybdenum disulfide nanosheets is 200-400 nm, the width of the molybdenum disulfide nanosheets is 200-400 nm, and the thickness of the molybdenum disulfide nanosheets is 2-10 nm.
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