CN117106450A - Photosensitizer with high singlet oxygen yield, preparation method, using method and application thereof - Google Patents
Photosensitizer with high singlet oxygen yield, preparation method, using method and application thereof Download PDFInfo
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- 238000002428 photodynamic therapy Methods 0.000 claims abstract description 8
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
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- KADXVMUKRHQBGS-UHFFFAOYSA-L cadmium(2+);tetradecanoate Chemical compound [Cd+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O KADXVMUKRHQBGS-UHFFFAOYSA-L 0.000 description 2
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- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 230000002062 proliferating effect Effects 0.000 description 1
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- UMJICYDOGPFMOB-UHFFFAOYSA-N zinc;cadmium(2+);oxygen(2-) Chemical compound [O-2].[O-2].[Zn+2].[Cd+2] UMJICYDOGPFMOB-UHFFFAOYSA-N 0.000 description 1
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- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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Abstract
The invention belongs to the technical field of chemical catalysis, and discloses a photosensitizer with high singlet oxygen yield, which is an inorganic-organic hybrid system formed by cadmium selenide quantum dots and triplet acceptor molecules anchored on the surfaces of the cadmium selenide quantum dots. The invention uses cadmium selenide quantum dots as sensitizer and constructs an inorganic-organic hybrid system with triplet acceptor molecules, the singlet oxygen generation rate is nearly 4 times of that of single CdSe QDs, and the invention has great application prospect in photocatalysis and photodynamic therapy.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and relates to a photosensitizer with high singlet oxygen yield, and a preparation method, a use method and application thereof.
Background
Singlet oxygen, the excited state of oxygen molecules, is an important active oxygen species and has very strong oxidizing ability. The singlet oxygen has extremely important application value in the aspects of photodynamic therapy, organic synthesis, environmental catalysis and the like. Singlet oxygen is generated mainly by exciting an organic or metal organic compound photosensitizer from a ground state to a singlet excited state by means of light, converting the singlet state of the excited photosensitizer molecule into a triplet excited state through interstitial crossing, and transferring energy to an oxygen molecule by the photosensitizer in the triplet excited state, thereby generating singlet oxygen.
Photodynamic therapy is an emerging method of treating tumors, precancerous lesions, vascular diseases and proliferative skin disorders. The photodynamic therapy specifically comprises activating photosensitizer in tumor tissue by specific wavelength of light, and the activated photosensitizer further transmits energy to surrounding oxygen to generate singlet oxygen and other active oxygen substances, so as to induce chemical injury to cause death of tumor cells. Thus, the activity of the photosensitizer is a key factor affecting the efficiency of singlet oxygen production. Compared with the traditional three methods of treating tumor by surgery, radiotherapy and chemotherapy, the photodynamic therapy has the advantages of small side effect, high selectivity, good applicability, repeated treatment and the like, and has become a means for effectively treating tumor. However, there are still some problems to be solved, such as difficulty in obtaining photosensitizer with high efficiency of singlet oxygen generation.
Triplet energy transfer from semiconductor quantum dots to organic molecules has proven to be an effective method of molecular triplet sensitization. Compared with the conventional singlet-to-triplet interstitial crossing of the organic or metal-organic compound photosensitizer, the energy loss caused by the interstitial crossing of the semiconductor quantum dot is very small and can be ignored. In addition, the band gap size of the semiconductor quantum dot can be precisely adjusted by regulating the components and the sizes of the semiconductor quantum dot, so that the difficulty in combining the quantum dot with acceptor molecules with different triplet energy states is greatly reduced. More importantly, the large specific surface area enables the semiconductor quantum dots to be easily modified by triplet acceptor molecules, so that efficient triplet energy transfer is realized. Based on the method, the semiconductor quantum dot-organic intermolecular triplet energy transfer system has potential application prospect in the aspect of singlet oxygen generation.
Disclosure of Invention
Aiming at the technical problem of low singlet oxygen generation efficiency of photosensitizers in the prior art, the invention provides a photosensitizer with high singlet oxygen yield, cadmium selenide quantum dots are used as sensitizers, and an inorganic-organic hybrid system is constructed by the cadmium selenide quantum dots and triplet acceptor molecules, wherein the singlet oxygen generation rate is approximately 4 times that of single CdSe QDs, and the photosensitizer has great application prospects in photocatalysis and photodynamic therapy.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a photosensitizer with high singlet oxygen yield, which is an inorganic-organic hybrid system formed by cadmium selenide quantum dots and triplet acceptor molecules anchored on the surfaces of the cadmium selenide quantum dots, wherein the triplet acceptor molecules are polycyclic aromatic hydrocarbon molecules with carboxyl groups.
In one embodiment, the triplet acceptor molecule is selected from one of 1-pyrenecarboxylic acid or 9-anthranilic acid.
In one technical scheme, the concentration ratio of the triplet acceptor molecule to the cadmium selenide quantum dot is 20-30: 1.
in one technical scheme, the exciton absorption peak and the fluorescence emission peak of the cadmium selenide quantum dot are respectively positioned at 529nm and 542nm, and the average diameter of the cadmium selenide quantum dot is 2.4nm.
The invention also provides a preparation method of the photosensitizer with high singlet oxygen yield, which comprises the following steps: the cadmium selenide quantum dot is used as a sensitizer, and a ligand exchange method is adopted to anchor triplet state acceptor molecules to the surface of the cadmium selenide quantum dot to construct an inorganic-organic hybridization system. The preparation method of the cadmium selenide quantum dot comprises the following steps: cadmium myristate and tin dioxide are placed in a three-necked flask, octadecene is added, stirring and degassing are carried out at 55 ℃, and after the solution becomes transparent, the reaction solution is heated to 230 ℃ in a nitrogen environment; and adding oleic acid after reaching the target temperature, stopping heating after reacting for 10min, washing with ethanol after cooling to remove unreacted substances, and obtaining cadmium selenide quantum dots which are dispersed in n-hexane for standby.
The invention also provides a use method of the photosensitizer with high singlet oxygen yield, which comprises the following steps: the method comprises the steps of taking cadmium selenide quantum dots as sensitizers, adopting a ligand exchange method to anchor triplet receptor molecules to the surfaces of the cadmium selenide quantum dots to construct an inorganic-organic hybrid system, and generating singlet oxygen by illuminating the inorganic-organic hybrid system.
The invention also provides application of the photosensitizer with high singlet oxygen yield in preparing a medicine for photodynamic tumor treatment.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes cadmium selenide quantum dots as sensitizer, has large extinction coefficient, simple preparation and adjustable size, and can be well matched with molecules with different triplet energy; the specific surface area is large, so that the molecular structure is easily modified by a triplet acceptor molecule, thereby realizing efficient triplet energy transfer.
According to the invention, cadmium selenide quantum dots are used as sensitizers, and form covalent bond with two oxygen atoms on a triplet receptor molecule carboxylic acid group, so that the inorganic-organic hybrid system can effectively realize the generation of singlet oxygen under illumination, and the generation rate of the singlet oxygen is approximately 4 times that of single CdSe QDs, so that the inorganic-organic hybrid system has great application value in photocatalysis and photodynamic therapy.
Drawings
FIG. 1 is a transmission electron micrograph of CdSe QDs prepared in example 1.
FIG. 2 is a graph of ultraviolet-visible absorption and fluorescence spectra of CdSe QDs prepared in example 1.
FIG. 3 is a transmission electron microscope image of the CdSe QDs-PCA hybrid system prepared in example 2.
FIG. 4 is a graph of the ultraviolet-visible absorption and fluorescence spectra of the CdSe QDs-PCA hybrid system prepared in example 2.
FIG. 5 is a graph showing the fluorescence up-conversion of the mixed solution of Diphenylanthracene (DPA) and CdSe QDs-PCA under 532nm continuous laser irradiation in example 2.
FIG. 6 is a graph of fluorescence lifetime of CdSe QDs and CdSe QDs-PCA hybrid systems in example 2.
FIG. 7 is a graph showing the transient absorption spectra of CdSe QDs and CdSe QDs-PCA hybrid systems of example 2.
FIG. 8 is a graph of the absorption spectrum of DPBF at different illumination times.
FIG. 9 is a graph showing absorption spectra of a CdSeQDs+DPBF mixture and a CdSeQDs-PCA+DPBF mixture under 532nm continuous laser irradiation in example 4.
FIG. 10 is a graph showing the primary degradation kinetics of DBPF in a CdSe QDs system and a CdSe QDs-PCA hybrid system under the same light conditions as in example 4.
Detailed Description
The following examples are illustrative of the present invention and are not intended to limit the scope of the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. The test methods in the following examples are conventional methods unless otherwise specified.
Example 1 Synthesis of CdSe QDs sensitizer by high temperature thermal injection
0.057 g (0.1 mmol) of cadmium myristate and 0.011 g (0.1 mmol) of tin dioxide were taken in a 25ml three-necked flask, 6.3 mL octadecene was added and stirred with a magnet at 55℃and degassed for 10min, after the solution became transparent, the reaction solution was heated to 230℃under nitrogen. And (3) rapidly adding 0.1 mL oleic acid when the reaction solution reaches 230 ℃, further reacting for 10min, stopping heating, cooling the reaction solution to room temperature, washing with ethanol to remove unreacted substances, thereby obtaining the CdSeQDs sensitizer protected by oleic acid ligand, and dispersing the CdSeQDs sensitizer in n-hexane for later use.
FIG. 1 is a transmission electron microscope image of CdSe QDs prepared in example 1, from which it can be seen that the prepared quantum dots are uniform in size and have an average diameter of 2.4nm.
FIG. 2 is an ultraviolet-visible absorption spectrum and a fluorescence spectrum of CdSe QDs prepared in example 1, wherein exciton absorption and fluorescence emission peak positions are located at 529nm and 542nm, respectively.
Example 2
5ml of the CdSe QDs prepared in example 1 are taken and divided into two parts averagely, wherein 0.5mg of 1-Pyrene Carboxylic Acid (PCA) powder is added into one part and stirred vigorously for 40-60min, then a 0.22 mu m polytetrafluoroethylene needle filter is adopted to filter the solution to remove redundant PCA, and the CdSe QDs protected by PCA ligand, namely a CdSe QDs-PCA hybrid system, is obtained, and the other part is used as a control.
FIG. 3 is a transmission electron microscope image of the CdSe QDs-PCA hybrid system prepared in example 2. From the figure, it can be seen that PCA-modified CdSe QDs have good dispersibility and no aggregation occurs.
FIG. 4 is a graph of the ultraviolet-visible absorption and fluorescence spectra of the CdSe QDs-PCA hybrid system prepared in example 2. It can be seen from the figure that the exciton absorption peak of CdSe QDs did not change after ligand exchange with PCA, but that absorption of PCA molecules occurred in the uv region, indicating successful ligand exchange. In addition, the fluorescence of the quantum dots after PCA ligand exchange is obviously quenched, the quenching rate reaches 84%, and the energy of CdSe QDs under light excitation is effectively transferred to PCA molecules.
To demonstrate that quenching of CdSe QDs fluorescence in the presence of PCA in fig. 4 is caused by quantum dot to PCA triplet energy transfer, fluorescence up-conversion experiments were also performed, as shown in fig. 5, by excitation of diphenylanthracene (DPA, triplet energy 1.8 eV) and CdSe QDs-PCA mixed solution with 532nm continuous laser, significant blue light emission from DPA was observed, indicating that the energy of CdSe QDs is effectively transferred to the triplet state of PCA molecules under light excitation, the triplet state of PCA molecules further transferred energy to the triplet state of DPA molecules, and the two DPA triplet molecules emitted singlet fluorescence by annihilation by collision, i.e., the observed blue light. The inset is a physical picture of the mixed solution under light excitation, and the sample is preceded by a 500nm short-wave pass filter from which blue light emission under light excitation can be seen obviously. Specifically, since DPA and PCA molecules are not absorbed at 532nm, 532nm can only excite CdSe QDs.
FIG. 6 is a graph of fluorescence lifetime of CdSe QDs and CdSe QDs-PCA hybrid systems in example 2. The fluorescence lifetime of the sample is obtained under 440nm light excitation, and the PCA molecules are not absorbed at 440nm, so that only CdSe QDs can be excited at 440 nm. As can be seen from the graph, the fluorescence lifetime decay rate is significantly faster under the same test conditions compared to the CdSe QDs alone, cdSe QDs-PCA hybrid system, which also demonstrates the energy transfer of CdSe QDs to the acceptor PCA molecule under photoexcitation.
FIG. 7 is a graph showing the transient absorption spectra of CdSe QDs and CdSe QDs-PCA hybrid systems of example 2. Transient spectra were obtained at 470nm excitation, again 470nm excitation only for CdSe QDs. It can be seen from FIGS. 7a and 7b that under the same test conditions, recovery of the CdSe QDs exciton bleach peak was significantly faster when PCA molecules were present. From 7c, it can be seen more intuitively that the dynamic decay rate of the CdSe QDs excitons is faster after the PCA functionalization, further proving that the energy of the photoexcited CdSe QDs is effectively transferred to the triplet state of the PCA molecule.
Example 3 detection of stability of DPBF alone under light irradiation by UV-visible absorbance photometry
The generation of singlet oxygen was detected using 1, 3-Diphenylisobenzofuran (DPBF) as a probe, and the absorption peak at 410nm of DPBF was decreased by reacting with singlet oxygen. 4.5mM/L and 100 μl of 1, 3-diphenyl isobenzofuran (DPBF) are added into 1.8mL of normal hexane solution and irradiated under 532nm continuous laser, an ultraviolet-visible spectrophotometer is adopted to test the absorption spectrum of the DPBF solution under different illumination time, and the stability condition is judged by observing the change of the absorption spectrum with time.
As a blank, fig. 8 is a graph of the absorption spectrum of DPBF at different illumination times, and it can be seen that the absorption spectrum of DPBF does not change with increasing illumination time, which indicates that no degradation of DPBF occurs under illumination.
Example 4: ultraviolet-visible absorbance photometry for detecting generation capacity of singlet oxygen in CdSe QDs and CdSe QDs-PCA hybrid system
1.8mL of n-hexane solution of the CdSe QDs and the CdSe QDs-PCA hybrid system is taken, the equal exciton absorption degree (0.22) of the CdSe QDs and the CdSe QDs-PCA hybrid solution is ensured to be equal in experiment, and equal amount of DPBF100 [ mu ] L is added into the solution. And respectively irradiating the mixed solution containing DPBF (cadmium zinc oxide) CdSe QDs and CdSe QDs-PCA by adopting 532nm continuous laser under the same condition, and testing the change of the absorption spectrum of the mixed solution with time by adopting an ultraviolet-visible spectrophotometer. The effect of singlet oxygen production was judged by the change in the absorption peak of DPBF at 410 nm.
FIGS. 9a and 9b are graphs showing the absorption spectra of the CdSeQDs+DPBF mixture and the CdSeQDs-PCA+DPBF mixture, respectively, under 532nm continuous laser irradiation. From the graph, the absorbance of the characteristic peak of DPBF at 410nm gradually decreases with the increase of illumination time, which indicates that singlet oxygen is generated in the system under illumination. In addition, compared with the single CdSe QDs system, the absorption of the DPBF characteristic peak in the CdSe QDs-PCA hybrid system under the same illumination condition is rapidly reduced, which indicates that the generation rate of singlet oxygen in the CdSe QDs-PCA hybrid system under illumination is faster. This is because triplet energy transferred from CdSe QDs to PCA molecules under photoexcitation can be further transferred to ground state oxygen molecules, thereby effectively improving the efficiency of singlet oxygen generation. More importantly, we can observe that the exciton absorption peak of CdSe QDs is almost unchanged under the light condition, which suggests that CdSe QDs have excellent photostability.
FIG. 10 is a graph of the first order degradation kinetics (410 nm) of DBPF in CdSe QDs and CdSe QDs-PCA hybrid systems under the same illumination conditions, with slopes of the straight lines extracted by linear fitting of the kinetics being-0.104 and-0.403, respectively. Since the degradation rate of DBPF is proportional to the generation rate of singlet oxygen in the system, it is possible to obtain a CdSe QDs-PCA hybrid system with nearly 4 times the generation rate of singlet oxygen than CdSe QDs alone.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and other embodiments can be easily made by those skilled in the art through substitution or modification according to the technical disclosure in the present specification, so that all changes and modifications made in the principle of the present invention shall be included in the scope of the present invention.
Claims (7)
1. The photosensitizer with high singlet oxygen yield is characterized by being an inorganic-organic hybrid system formed by cadmium selenide quantum dots and triplet acceptor molecules anchored on the surfaces of the cadmium selenide quantum dots, wherein the triplet acceptor molecules are polycyclic aromatic hydrocarbon molecules with carboxyl groups.
2. The photosensitizer according to claim 1, characterized in that the triplet acceptor molecule is selected from one of 1-pyrenecarboxylic acid or 9-anthramic acid.
3. The photosensitizer according to claim 1, wherein the concentration ratio of triplet acceptor molecules to cadmium selenide quantum dots is 20-30: 1.
4. the photosensitizer according to claim 1, wherein the exciton absorption peak and the fluorescence emission peak of the cadmium selenide quantum dot are located at 529nm and 542nm, respectively, and the average diameter of the cadmium selenide quantum dot is 2.4nm.
5. The method for preparing the photosensitizer with high singlet oxygen yield according to any one of claims 1 to 4, comprising the following steps: the cadmium selenide quantum dot is used as a sensitizer, and a ligand exchange method is adopted to anchor triplet state acceptor molecules to the surface of the cadmium selenide quantum dot to construct an inorganic-organic hybridization system.
6. The method of using a photosensitizer with high singlet oxygen yield according to any one of claims 1-4, comprising the steps of: the method comprises the steps of taking cadmium selenide quantum dots as sensitizers, adopting a ligand exchange method to anchor triplet receptor molecules to the surfaces of the cadmium selenide quantum dots to construct an inorganic-organic hybrid system, and generating singlet oxygen by illuminating the inorganic-organic hybrid system.
7. The use of a photosensitizer with high singlet oxygen yield according to any one of claims 1-4 for the preparation of a photodynamic therapy tumor drug.
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