CN112375089A - Photosensitizer with high singlet oxygen yield and preparation method thereof - Google Patents

Photosensitizer with high singlet oxygen yield and preparation method thereof Download PDF

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CN112375089A
CN112375089A CN202011122256.1A CN202011122256A CN112375089A CN 112375089 A CN112375089 A CN 112375089A CN 202011122256 A CN202011122256 A CN 202011122256A CN 112375089 A CN112375089 A CN 112375089A
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photosensitizer
singlet oxygen
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吕世博
苗钰阳
刘大鹏
宋锋玲
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Abstract

The invention discloses a photosensitizer with high singlet oxygen yield and a preparation method thereof, and the photosensitizer is obtained by adopting Suzuki coupling reaction, reacting 4, 8-dibromo-6- (2-ethylhexyl) - [1,2,5] thiadiazole [3,4-F ] benzotriazole with 4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) pyridine under the catalysis of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and eliminating through oxidation addition and reduction. The photosensitizer disclosed by the invention has stronger absorption capacity in visible light, has a stable structure under the conditions of weak acid to weak base, has very high quantum yield and high singlet oxygen generation capacity, and can be used as a novel photosensitizer for fluorescent imaging or photodynamic therapy of tumors.

Description

Photosensitizer with high singlet oxygen yield and preparation method thereof
Technical Field
The invention relates to a photosensitizer, in particular to a photosensitizer with high singlet oxygen yield and a preparation method thereof.
Background
Traditional cancer treatments such as chemotherapy, surgery and radiotherapy have strong side effects such as damage to normal cells and the nervous system, and are often associated with high recurrence rates. Therefore, the development of a safe and effective cancer treatment is a research topic that is needed at present. In recent years, photodynamic therapy has received much attention due to its low toxic side effects, broad antitumor selectivity and minimal invasion. The main component in photodynamic therapy is the photosensitizer molecule. In this case, the photosensitizer absorbs light (visible light or near infrared light) from a specific wave source, and then is excited from a ground state to a singlet excited state, and then undergoes an intersystem crossing process to be converted to a triplet excited state. The triplet excited state energy can excite triplet oxygen molecules to form singlet oxygen molecules with strong oxidizing property, and the singlet oxygen molecules can directly kill cancer cells so as to achieve the effect of cancer treatment.
The photosensitizer materials reported at present are mainly divided into three main categories: porphyrins and modified molecules thereof, BODIPY fluoroboron fluorescent dye and modified molecules thereof and ruthenium-based metal organic compounds. The photosensitizer molecules reported at present are influenced by factors such as easy agglomeration, poor stability, relatively low singlet oxygen yield and the like. Wherein photosensitizer molecules that achieve high singlet oxygen yields are a major bottleneck in current PDT. Photosensitizer molecules that achieve high singlet oxygen yields are essential to drive the clinical application of photodynamic therapy.
At present, the strategy for improving the yield of singlet oxygen of photosensitizer molecules is mainly to modify or functionalize the three photosensitizer molecules. First, based on the phenomenon that the photosensitizer is easy to aggregate to cause fluorescence quenching, thereby causing low singlet oxygen yield, the surface of the photosensitizer molecule is functionalized, for example, a water-soluble branch is introduced, so that the aggregation of the photosensitizer molecule in an aqueous solution or a polar solvent is reduced. And the specific photosensitizer molecules are coordinated with metal, and the coordinated metal effectively blocks the agglomeration of the photosensitizer molecules, so that the formed metal organic nano-drug has higher yield of triplet oxygen. Second, the rate of intersystem crossing is increased to enhance the singlet oxygen generating capacity. In order to effectively improve the intersystem crossing capability, heavy atoms such as iodine, bromine atoms and the like can be introduced to improve the intersystem crossing process, so that the yield of singlet oxygen is improved. Thirdly, the rotation of photosensitizer molecules is reduced, rigid groups are introduced, non-radiative transition is reduced, and the energy of a triplet excited state is improved, so that the yield of singlet oxygen is improved. However, although the current strategies improve the singlet oxygen yield of photosensitizer molecules to a certain extent, the singlet oxygen yield is relatively low, and the dose needs to be increased to achieve the purpose of treating tumors, which also greatly hinders the development of photodynamic therapy in the field of cancer treatment.
Therefore, the synthesis of a novel photosensitizer molecule with high singlet oxygen yield, high stability and low toxicity is of great significance for photodynamic therapy.
Disclosure of Invention
In order to solve the technical problems, the invention provides a photosensitizer with high singlet oxygen yield and a preparation method thereof, so as to achieve the purposes of stronger absorption capacity in visible light, very high quantum yield and stable structure under the conditions of weak acid to weak base.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a photosensitizer with high singlet oxygen yield has the following structural formula:
Figure BDA0002732392550000021
a preparation method of a photosensitizer with high singlet oxygen yield adopts Suzuki coupling reaction to react 4, 8-dibromo-6- (2-ethylhexyl) - [1,2,5] thiadiazole [3,4-F ] benzotriazole with 4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) pyridine under the catalysis of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, and the photosensitizer is obtained through oxidative addition and reduction elimination.
In the above scheme, the reaction is carried out under an inert gas atmosphere.
In the above scheme, the reaction temperature is 80 ℃ and the reaction time is 24 hours.
In the scheme, the reaction solution is extracted and separated by dichloromethane and purified by a column.
Through the technical scheme, the photosensitizer with high singlet oxygen yield has stronger absorption capacity in visible light and has very high quantum yield. And the compound has stable structure under the conditions of weak acid to weak base and stable fluorescence property in common polar solvents such as methanol, ethanol and dimethyl sulfoxide. Most importantly, it has a long lifetime of triplet excited state and a high quantum yield (95%) of singlet oxygen. The photosensitizer molecule has wide application prospect in the field of photodynamic therapy.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a photosensitizer molecule;
FIG. 2 is an absorption and emission spectrum of a photosensitizer molecule in ethanol;
fig. 3a is a graph of the uv absorption of a photosensitizer molecule in a slightly acidic (pH 6.5) solution;
fig. 3b is a graph of the uv absorption of a photosensitizer molecule in a weak base (pH 8.5) ethanol solution;
FIG. 4 is a triplet excited state lifetime fit curve for a photosensitizer molecule at a wavelength of 550 nm;
FIG. 5 is an EPR spectrum of a photosensitizer molecule;
FIG. 6 is a graph comparing the rate of singlet oxygen production in ethanol for photosensitizer molecules and the commercial dye TPPS.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The invention provides a photosensitizer with high singlet oxygen yield, which has the following structural formula:
Figure BDA0002732392550000031
the preparation method of the photosensitizer comprises the following steps:
introducing into a vacuum reaction bottle for about 15 minutesN of (A)2To ensure the oxygen-free environment in the vacuum reaction bottle and to ensure the reaction bottle to contain N2The vacuum reaction bottle is added with a mixed solution of 20mL of toluene solution and 5mL of water as a reaction solvent, and N is introduced into the vacuum reaction bottle for about 20 minutes through a long needle tube2To remove oxygen from the solvent.
Adding K first2CO3(129.7mg,0.868mmol) of a solid powder was provided with a basic environment, and then under these conditions 4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) pyridine (97.79mg,0.477mmol) and 4, 8-dibromo-6- (2-ethylhexyl) - [1,2,5] were added]Thiadiazole [3,4-F ]]Benzotriazole (100mg,0.217mmol) was added to a vacuum reaction flask and reacted with [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (12.53mg,0.01mmol) was heated to 80 ℃ over a catalyst. After reacting for 24 hours, the reaction solution is extracted and separated by dichloromethane and purified by a column.
And detecting the obtained product BTZPy, wherein a synthesized photosensitizer molecule nuclear magnetic resonance hydrogen spectrogram is shown in a figure 1.
The absorption and emission spectra of the photosensitizer molecules in ethanol are shown in figure 2. Through ultraviolet and fluorescence spectrum tests, the maximum absorption wavelength and the maximum emission wavelength of photosensitizer molecules are 508nm and 570nm respectively, and the Stokes shift reaches 62 nm.
The uv absorption curves of the photosensitizer molecules in slightly acidic (pH 6.5) and weak base (pH 8.5) ethanol solutions are shown in fig. 3a and 3 b. This experiment shows that photosensitizer molecules can exist stably under the conditions of weak acid and weak base.
The LP920K laser flash photolysis/transient absorption spectrometer is adopted to detect the triplet excited state life of the substance, the photophysical property is researched, the excitation wavelength is 532nm, the monitoring range is 600-900nm, and the concentration of photosensitizer molecules in argon deoxygenation ethanol is 2.4 multiplied by 10-4And M. A triplet excited state lifetime fit curve for the photosensitizer molecule at wavelength 550nm is shown in FIG. 4.
Firstly, the ROS type generated during light irradiation is confirmed through Electron Spin Resonance (ESR), a bruker EMXnano electron paramagnetic resonance spectrometer instrument is adopted, the light irradiation wavelength is 530nm, the light irradiation time is 60s, and TEMP is adopted as a singlet oxygen trapping agent. An EPR spectrum of the photosensitizer molecule is obtained, as shown in fig. 5, which indicates that the photosensitizer molecule can generate singlet oxygen molecules under visible light irradiation.
1, 3-diphenyl isobenzofuran (DPBF) is selected as1O2Catching agent, DPBF quilt1O2The photosensitizer molecule and the commercial dye TPPS are evaluated for the generation capacity of singlet oxygen by monitoring the change of the absorption intensity of DPBF at 410nm through oxidation and consumption, which leads to the weakening of the strong absorption of the DPBF at 410 nm. An LED light source with the power of 20mW and the excitation wavelength of 530nm is adopted in the experiment. The ratio of the rates of singlet oxygen production in ethanol for the photosensitizer molecule and the commercial dye TPPS is shown in figure 6. The results show that: the photosensitizer molecule being produced in 4s1O2This resulted in a significant bleaching consumption of DPBF at 410nm, in contrast to the commercial dye TPPS which only appeared after 8 s.
Calculated by the formula:
ΦΔ＝Φ(TPPS)×k(BTZPy)×F(TPPS)/k(TPPS)×F(BTZPy)
F＝1–10OD(OD: optical density at irradiation wavelength)
Wherein phi: (TPPS) Represents the singlet oxygen yield of tetraphenylporphyrin tetrasulfonic acid hydrate, k: (BTZPy) Showing the slope of decrease in singlet oxygen of the BTZPy substance, F: (TPPS) 1-10 of tetraphenylporphyrin tetrasulfonic acid hydrate-ODThe value (OD value indicates absorbance value), k (TPPS) indicates the slope of decrease in singlet oxygen of tetraphenylporphyrin tetrasulfonic acid hydrate, F (BTZPy) Represents BTZPy substances 1 to 10-ODThe value is obtained.
The relative singlet oxygen quantum yield Φ Δ of the photosensitizer molecule was 95% (referred to as TPPS).
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (5)

1. A photosensitizer with high singlet oxygen yield, characterized by the following structural formula:
Figure FDA0002732392540000011
2. a preparation method of a photosensitizer with high singlet oxygen yield is characterized in that Suzuki coupling reaction is adopted, 4, 8-dibromo-6- (2-ethylhexyl) - [1,2,5] thiadiazole [3,4-F ] benzotriazole and 4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) pyridine react under the catalysis of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, and the photosensitizer is obtained through oxidative addition and reductive elimination.
3. The method of claim 2, wherein the reaction is carried out under an inert gas atmosphere.
4. The method for preparing a photosensitizer with high singlet oxygen yield according to claim 2, wherein the reaction temperature is 80 ℃ and the reaction time is 24 hours.
5. The method according to claim 2, wherein the reaction solution is extracted and separated with dichloromethane and purified by column chromatography.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115508298A (en) * 2022-09-20 2022-12-23 常州大学 High-sensitivity aqueous singlet oxygen nano probe based on DPBF, preparation method and application
CN115636780A (en) * 2022-08-26 2023-01-24 湖南师范大学 Organic photosensitizer and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030203322A1 (en) * 1994-11-16 2003-10-30 Eastman Kodak Company Photothermographic element with reduced woodgrain interference patterns
CN101074236A (en) * 2007-06-22 2007-11-21 山东大学 N,N-bi-substituted-methylpyrazole (4,5,e) (2,1,3)-thiadiazine-2,2,4-triketone derivative, its production and use
CN101648962A (en) * 2009-08-28 2010-02-17 河南大学 C3/C3 fluoroquinolone dipolymer derivative taking s-triazolo-[3,4-b][1,3,4] thiadiazole as connecting chain and preparation method and application thereof
CN103073553A (en) * 2013-01-25 2013-05-01 山东大学 Water-soluble naphthalocyanine base compound, preparation method and application of compound as photosensitizer
CN106883389A (en) * 2017-03-17 2017-06-23 杭州电子科技大学 The synthetic method of the N type conjugated polyelectrolytes based on electron deficient heterocycle main chain
CN111388448A (en) * 2020-03-16 2020-07-10 华南理工大学 Nano particles for photothermal treatment of tumors and preparation and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030203322A1 (en) * 1994-11-16 2003-10-30 Eastman Kodak Company Photothermographic element with reduced woodgrain interference patterns
CN101074236A (en) * 2007-06-22 2007-11-21 山东大学 N,N-bi-substituted-methylpyrazole (4,5,e) (2,1,3)-thiadiazine-2,2,4-triketone derivative, its production and use
CN101648962A (en) * 2009-08-28 2010-02-17 河南大学 C3/C3 fluoroquinolone dipolymer derivative taking s-triazolo-[3,4-b][1,3,4] thiadiazole as connecting chain and preparation method and application thereof
CN103073553A (en) * 2013-01-25 2013-05-01 山东大学 Water-soluble naphthalocyanine base compound, preparation method and application of compound as photosensitizer
CN106883389A (en) * 2017-03-17 2017-06-23 杭州电子科技大学 The synthetic method of the N type conjugated polyelectrolytes based on electron deficient heterocycle main chain
CN111388448A (en) * 2020-03-16 2020-07-10 华南理工大学 Nano particles for photothermal treatment of tumors and preparation and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ECK LIP DEXTER TAM等，: ""Can time-dependent density functional theory predict intersystem crossing in organic chromophores? A case study on benzo(bis)-X-diazole based donor–acceptor–donor type molecules"", 《PHYS. CHEM. CHEM. PHYS.》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115636780A (en) * 2022-08-26 2023-01-24 湖南师范大学 Organic photosensitizer and preparation method thereof
CN115508298A (en) * 2022-09-20 2022-12-23 常州大学 High-sensitivity aqueous singlet oxygen nano probe based on DPBF, preparation method and application

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