CN110128844A - A kind of Benzpyrole squaric acid cyanine dye and its preparation method and application - Google Patents
A kind of Benzpyrole squaric acid cyanine dye and its preparation method and application Download PDFInfo
- Publication number
- CN110128844A CN110128844A CN201910532107.3A CN201910532107A CN110128844A CN 110128844 A CN110128844 A CN 110128844A CN 201910532107 A CN201910532107 A CN 201910532107A CN 110128844 A CN110128844 A CN 110128844A
- Authority
- CN
- China
- Prior art keywords
- formula
- cyanine dye
- preparation
- squaric acid
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention belongs to squarylium cyanine dyes technical fields more particularly to a kind of Benzpyrole squaric acid cyanine dye and its preparation method and application.The present invention provides a kind of Benzpyrole squaric acid cyanine dye, shown in the structural formula of the Benzpyrole squaric acid cyanine dye such as formula (I)；Wherein, R is phenyl, anthryl or pyrenyl.Benzpyrole squaric acid cyanine dye of the present invention has high molar extinction coefficient near infrared region, it is strong in the near infrared region to absorb, it has a significant effect in sensitization singlet oxygen, it can be used as triplet photosensitizer, it is had a good application prospect in field of photodynamic, being able to solve existing squarylium cyanine dyes for optical dynamic therapy has that singlet oxygen quantum yield is low.
Description
Technical field
The invention belongs to squarylium cyanine dyes technical field more particularly to a kind of Benzpyrole squaric acid cyanine dye and preparation method thereof and
Using.
Background technique
Currently, the application and its research of all kinds of squarylium cyanine dyes are reported in many periodicals and The Chemicals.People
The CD used just has made of squarylium cyanine dyes film, and squarylium cyanine dyes can be applied in liquid crystal display, organic sun
The fields such as the research of energy battery, nonlinear optical material.Research also found that squarylium cyanine dyes have fluorescent emission near infrared region, and
This fluorescent emission is very strong, can be used to do fluorescence probe and apply in life science.Also, squarylium cyanine dyes also have use
In the prospect on optical dynamic therapy.
Optical dynamic therapy (Photodynamictherapy, PDT) is to carry out medical diagnosis on disease and treatment using photodynamic effect
A kind of new technology, to the therapeutic effects of certain cancers no less than operation, chemotherapy or radiotherapy, with the excellent of the following aspects
Point: 1) treatment time is short；2) it can be applied simultaneously with operation, radiation and chemotherapy；3) chief destructive cancer cell does not damage normal thin
Born of the same parents；4) more courses for the treatment of can be done, drug resistance will not be generated.The basic principle of optical dynamic therapy is by injecting to patient's body to tumour
The bioactivity group such as cell is woven with the photosensitizer of affinity interaction, is made using tumour cell to the selectivity intake and retention of photosensitizer
With, within a certain period of time, photosensitizer can selectively be enriched in focal zone, then with the laser irradiation focal zone of specific wavelength,
By ground state transition to excitation state after sensitiser absorption luminous energy, and the photosensitizer of excitation state energy transmission to the oxygen of surrounding, produce
Other reactive oxygen species (reactive such as the very strong singlet oxygen of liveliness proof or ultra-oxygen anion free radical, hydroxyl, hydrogen peroxide
Oxygen species, ROS), and then oxidation reaction occurs with adjacent large biological molecule, cytotoxic effect is generated, is destroyed
The activity of the biomolecule such as lipid, albumen, nucleic acid causes the serious damage and dysfunction of organelle, thin so as to cause tumour
The death of born of the same parents, reaches therapeutic purposes.
But existing squarylium cyanine dyes have that singlet oxygen quantum yield is low for optical dynamic therapy.
Summary of the invention
The present invention provides a kind of Benzpyrole squaric acid cyanine dyes and its preparation method and application, for solving existing side's acid cyanines dye
Material has that singlet oxygen quantum yield is low for optical dynamic therapy.
The specific technical solution of the present invention is as follows:
A kind of Benzpyrole squaric acid cyanine dye, shown in the structural formula of the Benzpyrole squaric acid cyanine dye such as formula (I)；
Wherein, R is phenyl, anthryl or pyrenyl.
In the present invention, Benzpyrole squaric acid cyanine dye is one of SQ-1~SQ-3；
Benzpyrole squaric acid cyanine dye of the present invention has high molar extinction coefficient near infrared region, strong in the near infrared region to absorb,
It has a significant effect in sensitization singlet oxygen, can be used as triplet photosensitizer, have in field of photodynamic good
Application prospect, being able to solve existing squarylium cyanine dyes for optical dynamic therapy has that singlet oxygen quantum yield is low.
The present invention also provides a kind of preparation methods of Benzpyrole squaric acid cyanine dye, comprising the following steps:
The compound of structure shown in formula (II) and aryl boric acid are subjected to Suzuki-Miyaura coupling reaction, obtain structure
Formula Benzpyrole squaric acid cyanine dye as shown in formula (I)；
Wherein, R is phenyl, anthryl or pyrenyl.
In the present invention, Benzpyrole squaric acid cyanine dye shown in formula (I) is one of SQ1~SQ3；
Preferably, the temperature of the Suzuki-Miyaura coupling reaction is 85 DEG C~95 DEG C；
The time of the Suzuki-Miyaura coupling reaction is 2~10h.
Preferably, the molar ratio of the compound Yu the aryl boric acid of structure shown in the formula (II) is 1:2~1:4.
In the present invention, the preparation method of Benzpyrole squaric acid cyanine dye preferably includes following steps:
Under protective atmosphere, the compound of structure shown in formula (II) and aryl boric acid are dissolved in solvent, in catalyst
Effect is lower to carry out Suzuki-Miyaura coupling reaction, obtains structural formula Benzpyrole squaric acid cyanine dye as shown in formula (I).
The protective atmosphere of Suzuki-Miyaura coupling reaction is preferably nitrogen, and catalyst is preferably four (triphenylphosphines)
Palladium, palladium acetate, palladium chloride and/or bis- (triphenylphosphine) palladium chlorides, more preferably tetrakis triphenylphosphine palladium, solvent are preferably second
Glycol dimethyl ether, toluene, tetrahydrofuran and/or ethyl alcohol, more preferably glycol dimethyl ether.
In the present invention, it is preferably added to saturated solution of sodium bicarbonate and carries out Suzuki-Miyaura coupling reaction.
When Benzpyrole squaric acid cyanine dye is SQ-1, the time of Suzuki-Miyaura coupling reaction is preferably 2h~8h；Indoles
When squarylium cyanine dyes are SQ-2, the time of Suzuki-Miyaura coupling reaction is preferably 2h~5h；Benzpyrole squaric acid cyanine dye is
When SQ-3, the time of Suzuki-Miyaura coupling reaction is preferably 2h~10h.
In the present invention, after carrying out Suzuki-Miyaura coupling reaction, structural formula indoles side as shown in formula (I) is obtained
Before sour cyanine dyes, further includes: purifying；
Purifying specifically includes: after Suzuki-Miyaura coupling reaction product is washed with ammonium chloride saturated aqueous solution, rotation
Turn evaporation of solvent, then after being extracted with methylene chloride and water, be dried using anhydrous sodium sulfate, rotary evaporation removes
Solvent, then carry out column Chromatographic purification.Wherein, when Benzpyrole squaric acid cyanine dye is SQ-1, it is preferred to use volume ratio is the petroleum ether of 2:1
Column chromatography is carried out with the mixed solution of methylene chloride；When Benzpyrole squaric acid cyanine dye is SQ-2, it is preferred to use volume ratio is the two of 3:1
The mixed solution of chloromethanes and petroleum ether carries out column chromatography；When Benzpyrole squaric acid cyanine dye is SQ-3, it is preferred to use volume ratio 1:2
Methylene chloride and petroleum ether mixed solution carry out column chromatography.
Preferably, the compound of structure shown in formula (II) is prepared according to the following steps:
Under protective atmosphere, the compound of structure shown in formula (III) is carried out first with side's acid and is reacted, formula (II) institute is obtained
Show the compound of structure；
Preferably, the temperature of first reaction is 115 DEG C~120 DEG C；
The time of first reaction is 1h~5h；
The molar ratio of the compound of structure shown in the formula (III) and side's acid is 2:1~3:1.
In the present invention, the first reaction carries out preferably in dual solvent system, and dual solvent system is selected from n-butanol/first
The volume ratio of benzene, n-butanol/pyridine, ethanol/toluene or ethyl alcohol/pyridine, preferably n-butanol/toluene, n-butanol and toluene is
1:1.The protective atmosphere of first reaction is preferably nitrogen, the compound of structure shown in formula (III), side's acid and dual solvent system
Molar ratio is preferably 1:0.5:5~1:0.5:10.
In the present invention, after the first reaction, it is also preferable to include: the cooling of the first reaction product is precipitated, n-hexane is used
Filtration washing precipitating, then precipitating is purified.Purifying preferably includes: methylene chloride is added and water carries out dissolution extraction to precipitating
Take, then with anhydrous sodium sulfate it is dry after, rotary evaporation, then be 1:1 with volume ratio methylene chloride and petroleum ether mixed solution
It is purified, obtains the compound of structure shown in greenish solid product i.e. formula (II).
Preferably, the compound of structure shown in formula (III) is prepared according to the following steps:
Second will be carried out with 3- methyl -2- butanone to iodobenzene hydrazine to react, obtain the compound of structure shown in formula (III).
It is furthermore preferred that the compound of structure shown in formula (III) is prepared according to the following steps:
Iodobenzene hydrazine and 3- methyl -2- butanone will be dissolved in glacial acetic acid, and be heated to reflux the second reaction of progress, obtain formula
(III) compound of structure shown in.
In the present invention, after the second reaction, it is also preferable to include: the second reaction product is purified, more specifically: by the
Two reaction products revolving removes solvent, is extracted with ethyl acetate and water, and after the anhydrous sodium sulfate drying of extraction product, revolving is removed
Solvent, then the petroleum ether and ethyl acetate mixture that are 2:1 with volume ratio are purified, and orange oily liquids i.e. formula is obtained
(III) compound of structure shown in.
Preferably, the temperature of second reaction is 100 DEG C~120 DEG C；
The time of second reaction is 1h~3h；
The molar ratio to iodobenzene hydrazine and the 3- methyl -2- butanone is 1:2~1:3.
The sour cyanines in Benzpyrole squaric acid cyanine dye use side of the present invention are condensed with indole ring compounds, preparation method tool of the present invention
Have that reaction step is simple, reaction condition is mild, economic and environment-friendly, yield is high, there is general applicability.The present invention is with the sour cyanines system in side
For parent, triplet photosensitizer is constructed, promotes to alter jump efficiency between system, improves singlet oxygen production capacity, led in optical dynamic therapy
Domain has a good application prospect, and being able to solve existing squarylium cyanine dyes, there are singlet oxygen quantum yields for optical dynamic therapy
Low problem.
The present invention also provides prepare described in Benzpyrole squaric acid cyanine dye described in above-mentioned technical proposal and/or above-mentioned technical proposal
Application of the Benzpyrole squaric acid cyanine dye that method is prepared as photosensitizer.
Benzpyrole squaric acid cyanine dye of the present invention can be used for being sensitized singlet oxygen as photosensitizer.By the way that indoles side's acid cyanines are contaminated
Material and agent for capturing are scattered in organic solvent, carry out the detection of Benzpyrole squaric acid cyanine dye sensitization singlet oxygen, the results showed that, this hair
Bright Benzpyrole squaric acid cyanine dye has a significant effect in sensitization singlet oxygen.Wherein, organic solvent is preferably methylene chloride, first
Benzene, n-hexane and/or ethyl alcohol, more preferably methylene chloride；Agent for capturing is preferably 1,3 diphenyl isobenzofurans, 2,2,6,6-
Tetramethyl piperidine, methacrylic acid diisopropylaminoethyl ethyl ester and/or dimethyl acetamide, more preferably 1, the different benzene of 3 diphenyl
And furans；Benzpyrole squaric acid cyanine dye and the molar ratio of agent for capturing are preferably (0.2~0.5): 1, more preferably (0.2~0.4): 1,
Further preferably (0.2~0.3): 1；Benzpyrole squaric acid cyanine dye is (1~10) × 10 in the concentration of organic solvent-6M, agent for capturing
It is (1~10) × 10 in the concentration of organic solvent-5M, agent for capturing are preferably (0.5~1) × 10 in the concentration of organic solvent-5M。
Preferably, the photosensitizer is used to prepare optical dynamic therapy medicine.
In conclusion the structural formula of the Benzpyrole squaric acid cyanine dye is such as the present invention provides a kind of Benzpyrole squaric acid cyanine dye
Shown in formula (I)；Wherein, R is phenyl, anthryl or pyrenyl.Benzpyrole squaric acid cyanine dye of the present invention near infrared region there is high mole to disappear
Backscatter extinction logarithmic ratio, it is strong in the near infrared region to absorb, it has a significant effect in sensitization singlet oxygen, can be used as triplet photosensitizer,
It is had a good application prospect in field of photodynamic, is able to solve existing squarylium cyanine dyes for optical dynamic therapy and there is list
The problem of line state oxygen amount sub- low yield.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the ultraviolet-visible absorption spectroscopy of SQ-1, SQ-2 and SQ-3 in the embodiment of the present invention；
Fig. 2 is the fluorescence emission spectrum of SQ-1, SQ-2 and SQ-3 in the embodiment of the present invention；
Fig. 3 is SQ-1 as photosensitizer, and 1,3- diphenyl isobenzofuran (DPBF) is used as agent for capturing in methylene chloride
Sensitization singlet oxygen spectrogram；
Fig. 4 is SQ-2 as photosensitizer, sensitization singlet oxygen spectrogram of the DPBF as agent for capturing in methylene chloride；
Fig. 5 is SQ-3 as photosensitizer, sensitization singlet oxygen spectrogram of the DPBF as agent for capturing in methylene chloride；
Fig. 6 is the singlet oxygen quantum yield comparison diagram of SQ, SQ-1, SQ-2 and SQ-3 in the embodiment of the present invention.
Specific embodiment
The present invention provides a kind of Benzpyrole squaric acid cyanine dyes and its preparation method and application, for solving existing side's acid cyanines dye
Material has that singlet oxygen quantum yield is low for optical dynamic therapy.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
The present embodiment passes through the compound to structure shown in iodobenzene hydrazine and 3- methyl -2- butanone preparation formula (III).
Iodobenzene hydrazine (1.17g, 5mmol) and 3- methyl -2- butanone (0.52g, 6mmol) will be dissolved in 30ml glacial acetic acid,
It is heated to reflux 3h and carries out the second reaction, after being cooled to room temperature, revolving removes solvent, is extracted with ethyl acetate and water, extracts product
After anhydrous sodium sulfate drying, revolving removes solvent, then is purified with petroleum ether and ethyl acetate (volume ratio 2:1), obtains
To the compound 1.09g of structure shown in orange oily liquids, that is, formula (III), purity 98%, yield 76.5%.
The nuclear magnetic data of the compound of structure shown in formula (III):1H NMR(400MHz,CDCl3)δ7.56–7.49(m,
2H), 7.20 (d, J=7.9Hz, 1H), 2.16 (s, 3H), 1.18 (s, 6H).
Embodiment 2
The compound of structure shown in compound and side's acid preparation formula (II) of the present embodiment by structure shown in formula (III)
(SQ)。
Under nitrogen protection, in Dean-Stark device, general side's acid (0.11g, 1mmol) is placed in 10ml n-butanol and 10ml
In toluene, after being heated to reflux 1h, square acid is dissolved in dual solvent system, obtains reaction solution.By the chemical combination of structure shown in formula (III)
Object (0.57g, 2mmol) is dissolved in 5ml n-butanol and 5ml toluene, is added dropwise to reaction solution, stop after 3h first reacts anti-
It answers.The cooling solid that is precipitated of first reaction product is precipitated, n-hexane filtration washing precipitating is added, adds methylene chloride and water pair
Precipitating carries out dissolution extraction, then with anhydrous sodium sulfate it is dry after, rotary evaporation, then the methylene chloride and stone that are 1:1 with volume ratio
The mixed solution of oily ether is purified, and the compound 446.1mg of structure shown in greenish solid product i.e. formula (II) is obtained, and purity is
99%, yield 68.1%.
The nuclear magnetic data of the compound of structure shown in formula (II):1H NMR(400MHz,CDCl3) δ 12.72 (d, J=
128.9Hz, 2H), 7.63-7.49 (m, 4H), 6.92 (dd, J=19.9,8.1Hz, 2H), 5.48 (d, J=33.3Hz, 2H),
1.43(s,12H).
Embodiment 3
The present embodiment prepares SQ-1 by the compound and aryl boric acid of structure shown in formula (II).
By the compound (324.2mg, 0.5mmol) and tetrakis triphenylphosphine palladium of structure shown in formula (II) (57.7mg,
It 0.05mmol) is dissolved in the glycol dimethyl ether of 15ml, under nitrogen protection, after vacuumizing, addition phenyl boric acid (134.2mg,
1.1mmol) with saturated solution of sodium bicarbonate (168.1mg, 2mmol), temperature is heated to 95 DEG C, carries out 4h Suzuki-
Miyaura coupling reaction cleans Suzuki-Miyaura coupling reaction product three times with ammonium chloride saturated aqueous solution, and revolving is removed
Solvent is removed, then with after methylene chloride and water extraction, is dried using anhydrous sodium sulfate, rotary evaporation removes solvent, finally uses
The mixed solution of petroleum ether and methylene chloride that volume ratio is 2:1 carries out column Chromatographic purification, obtains greenish solid product i.e. SQ-1
56.4mg, purity 99%, yield 20.6%.
The nuclear magnetic data of SQ-1:1H NMR(400MHz,CDCl3) δ 12.79 (d, J=115.2Hz, 2H), 7.58 (dd, J=
7.7,4.5Hz, 4H), 7.55-7.43 (m, 8H), 7.43 (s, 1H), 7.34 (t, J=7.3Hz, 2H), 7.19 (d, J=8.1Hz,
1H), 5.53 (d, J=28.1Hz, 2H), 1.51 (s, 12H).
Embodiment 4
The present embodiment prepares SQ-2 by the compound and aryl boric acid of structure shown in formula (II).
By the compound (324.2mg, 0.5mmol) and tetrakis triphenylphosphine palladium of structure shown in formula (II) (57.7mg,
It 0.05mmol) is dissolved in the glycol dimethyl ether of 15ml, under nitrogen protection, after vacuumizing, addition anthracene boric acid (333.1mg,
1.5mmol) with saturated solution of sodium bicarbonate (168.1mg, 2mmol), temperature is heated to 95 DEG C, carries out 5h Suzuki-
Miyaura coupling reaction cleans Suzuki-Miyaura coupling reaction product three times with ammonium chloride saturated aqueous solution, and revolving is removed
It after removing solvent, then methylene chloride and water extraction, is dried using anhydrous sodium sulfate, rotary evaporation removes solvent, finally uses body
Product carries out column Chromatographic purification than the mixed solution of the petroleum ether and methylene chloride that are 1:3, obtains brown-red solid product i.e. SQ-2
20.1mg, purity 99%, yield 5.4%.
The nuclear magnetic data of SQ-2:1H NMR(400MHz,CDCl3)δ13.08(s,2H),7.68–7.65(m,4H),7.63–
7.59 (m, 4H), 7.55 (dd, J=4.7,1.5Hz, 4H), 7.49-7.44 (m, 8H), 6.96 (d, J=8.2Hz, 2H), 6.78
(d, J=8.2Hz, 2H), 5.65 (s, 2H), 1.45 (s, 12H).
Embodiment 5
The present embodiment prepares SQ-3 by the compound and aryl boric acid of structure shown in formula (II).
By the compound (324.2mg, 0.5mmol) and tetrakis triphenylphosphine palladium of structure shown in formula (II) (57.7mg,
It 0.05mmol) is dissolved in the glycol dimethyl ether of 15ml, under nitrogen protection, after vacuumizing, addition pyrene boric acid (270.7mg,
1.1mmol) with saturated solution of sodium bicarbonate (168.1mg, 2mmol), temperature is heated to 95 DEG C, carries out 10h Suzuki-
Miyaura coupling reaction cleans Suzuki-Miyaura coupling reaction product three times with ammonium chloride saturated aqueous solution, and revolving is removed
Solvent is removed, then with after methylene chloride and water extraction, is dried using anhydrous sodium sulfate, rotary evaporation removes solvent, finally uses
The mixed solution of petroleum ether and methylene chloride that volume ratio is 1:2 carries out column Chromatographic purification, obtains brown-red solid product i.e. SQ-
3 56.4mg, purity 99%, yield 20.6%.
The nuclear magnetic data of SQ-3:1H NMR(400MHz,CDCl3) δ 12.90 (d, J=115.1Hz, 2H), 8.26-8.16
(m, 8H), 8.11 (s, 4H), 8.09-7.98 (m, 6H), 7.55 (ddd, J=8.9,4.7,2.0Hz, 4H), 7.37 (dd, J=
27.9,7.9Hz, 2H), 5.61 (d, J=26.6Hz, 2H), 1.26 (s, 12H).
Embodiment 6
The present embodiment carries out ultravioletvisible absorption to the SQ-3 of the SQ-1 of embodiment 3, the SQ-2 of embodiment 4 and embodiment 5
Spectrum test and fluorescence emission spectrum test, the result is shown in Figure 1 and Fig. 2, Fig. 1 are SQ-1, SQ-2 and SQ- in the embodiment of the present invention
3 ultraviolet-visible absorption spectroscopy, Fig. 2 are the fluorescence emission spectrum of SQ-1, SQ-2 and SQ-3 in the embodiment of the present invention.In Fig. 1,
SQ-1, SQ-2 and SQ-3 have strong absorb between 650nm~700nm；In Fig. 2, SQ-1, SQ-2 and SQ-3 are in 650nm
There is wide transmitting between~800nm；The result shows that the absorption spectrum and emission spectrum of SQ-1, SQ-2 and SQ-3 are all in near-infrared
Area.
Embodiment 7
The present embodiment is respectively by the SQ of the SQ-1 of embodiment 3, the SQ-2 of embodiment 4, the SQ-3 of embodiment 5 and embodiment 2
It is dissolved in methylene chloride, adjusting absorbance is 0.2, adds agent for capturing DPBF, and adjusting absorbance is 1.0.By above-mentioned solution
The 660nm laser excitation for being 0.5mw with power, every 2min test is primary, test sensitization singlet oxygen spectrogram such as Fig. 3 to Fig. 5 institute
Show.
The quantum yield of the singlet oxygen of sample to be tested is calculated by following formula:
Φsam=Φstd×(ksam/kstd)×(Fstd/Fsam)×(ηsam/ηstd)
F=1-10--A
Wherein: Φ represents singlet oxygen quantum yield；K represents absorbance change slope；A represents excitation wave strong point extinction
Degree；η represents solvent viscosity；Sam represents sample to be tested；Std represents standard sample.Standard sample is SQ, the singlet oxygen amount of SQ
Sub- yield is 6.29%.
Fig. 3 is SQ-1 as photosensitizer, sensitization singlet oxygen spectrogram of the DPBF as agent for capturing in methylene chloride.Fig. 3
Show that SQ-1 can carry out effectively being sensitized singlet oxygen under 660nm light, the quantum yield of singlet oxygen is 8.87%.
Fig. 4 is SQ-2 as photosensitizer, sensitization singlet oxygen spectrogram of the DPBF as agent for capturing in methylene chloride.Fig. 4
Show that SQ-2 can carry out effectively being sensitized singlet oxygen under 660nm light, the quantum yield of singlet oxygen is 12.44%.
Fig. 5 is SQ-3 as photosensitizer, sensitization singlet oxygen spectrogram of the DPBF as agent for capturing in methylene chloride.Fig. 5
Show that SQ-3 can carry out effectively being sensitized singlet oxygen under 660nm light, the quantum yield of singlet oxygen is 7.39%.
The SQ of the SQ-1 of embodiment 3, the SQ-2 of embodiment 4, the SQ-3 of embodiment 5 and embodiment 2 is sensitized singlet oxygen
Test result compare, as a result referring to Fig. 6, for SQ, SQ-1, SQ-2 and SQ-3 in the embodiment of the present invention singlet oxygen
Quantum yield comparison diagram.The singlet oxygen quantum yield of SQ-1 is that the singlet oxygen quantum yield of 8.87%, SQ-2 is
The singlet oxygen quantum yield of 12.44%, SQ-3 are 7.39%, and the singlet oxygen quantum yield of SQ is 6.29%, as a result table
Bright Benzpyrole squaric acid cyanine dye of the present invention has excellent singlet oxygen production capacity.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of Benzpyrole squaric acid cyanine dye, which is characterized in that shown in the structural formula of the Benzpyrole squaric acid cyanine dye such as formula (I)；
Wherein, R is phenyl, anthryl or pyrenyl.
2. a kind of preparation method of Benzpyrole squaric acid cyanine dye, which comprises the following steps:
The compound of structure shown in formula (II) and aryl boric acid are subjected to Suzuki-Miyaura coupling reaction, obtain structural formula such as
Benzpyrole squaric acid cyanine dye shown in formula (I)；
Wherein, R is phenyl, anthryl or pyrenyl.
3. preparation method according to claim 2, which is characterized in that the temperature of the Suzuki-Miyaura coupling reaction
It is 85 DEG C~95 DEG C；
The time of the Suzuki-Miyaura coupling reaction is 2~10h.
4. preparation method according to claim 2, which is characterized in that the compound of structure shown in the formula (II) with it is described
The molar ratio of aryl boric acid is 1:2~1:4.
5. preparation method according to claim 2, which is characterized in that the compound of structure shown in formula (II) is according to following step
Rapid preparation:
Under protective atmosphere, the compound of structure shown in formula (III) is carried out first with side's acid and is reacted, obtains knot shown in formula (II)
The compound of structure；
6. preparation method according to claim 5, which is characterized in that the temperature of first reaction is 115 DEG C~120
℃；
The time of first reaction is 1h~5h；
The molar ratio of the compound of structure shown in the formula (III) and side's acid is 2:1~3:1.
7. preparation method according to claim 5, which is characterized in that the compound of structure shown in formula (III) is according to following
Step preparation:
Second will be carried out with 3- methyl -2- butanone to iodobenzene hydrazine to react, obtain the compound of structure shown in formula (III).
8. preparation method according to claim 7, which is characterized in that the temperature of second reaction is 100 DEG C~120
℃；
The time of second reaction is 1h~3h；
The molar ratio to iodobenzene hydrazine and the 3- methyl -2- butanone is 1:2~1:3.
9. preparation method described in Benzpyrole squaric acid cyanine dye described in claim 1 and/or claim 2 to 8 any one is prepared into
Application of the Benzpyrole squaric acid cyanine dye arrived as photosensitizer.
10. application according to claim 9, which is characterized in that the photosensitizer is used to prepare optical dynamic therapy medicine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910532107.3A CN110128844B (en) | 2019-06-19 | 2019-06-19 | Indole squarylium cyanine dye and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910532107.3A CN110128844B (en) | 2019-06-19 | 2019-06-19 | Indole squarylium cyanine dye and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110128844A true CN110128844A (en) | 2019-08-16 |
| CN110128844B CN110128844B (en) | 2021-01-26 |
Family
ID=67578131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910532107.3A Active CN110128844B (en) | 2019-06-19 | 2019-06-19 | Indole squarylium cyanine dye and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110128844B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117379A (en) * | 2020-01-13 | 2020-05-08 | 广州铭汇建设工程有限公司 | Pipeline antirust coating |
| CN114478393A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Organic light-emitting material with high exciton utilization rate and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109010826A (en) * | 2018-07-12 | 2018-12-18 | 北京化工大学 | A kind of targeting material based on Benzpyrole squaric acid cyanine dye and preparation method thereof and fluorescent nano particles and preparation method thereof |
-
2019
- 2019-06-19 CN CN201910532107.3A patent/CN110128844B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109010826A (en) * | 2018-07-12 | 2018-12-18 | 北京化工大学 | A kind of targeting material based on Benzpyrole squaric acid cyanine dye and preparation method thereof and fluorescent nano particles and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LOREDANA SERPE ET AL.: "Squaraines bearing halogenated moieties as anticancerphotosensitizers: Synthesis, characterization and biological evaluation", 《EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY》 * |
| PATRIZIO SALICE ET AL.: "Photophysics of Squaraine Dyes: Role of Charge-Transfer in Singlet Oxygen Production and Removal", 《J. PHYS. CHEM. A》 * |
| SIMON KUSTER ET AL.: "Strategies and investigations on bridging squaraine dye units", 《DYES AND PIGMENTS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117379A (en) * | 2020-01-13 | 2020-05-08 | 广州铭汇建设工程有限公司 | Pipeline antirust coating |
| CN114478393A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Organic light-emitting material with high exciton utilization rate and preparation method and application thereof |
| CN114478393B (en) * | 2020-10-26 | 2024-02-02 | 中国石油化工股份有限公司 | Organic luminescent material with high exciton utilization rate and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110128844B (en) | 2021-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108864106B (en) | The preparation and application of two area's small organic molecule fluorescence probe of near-infrared | |
| CN108727256B (en) | Photosensitizer based on triphenylamine polypyridine salt and preparation method and application thereof | |
| CN108714222B (en) | Preparation and application of novel multifunctional supermolecule vesicle | |
| CN108070275B (en) | Squaric acid dye compound, preparation method and application | |
| CN106008581B (en) | The azole derivatives of fluorine boron two and its preparation and application containing six trifluoromethyl groups | |
| CN108102408B (en) | A kind of preparation and application of the nir dye based on azepine fluorine borine | |
| CN114213419B (en) | Fluorescent probe with fluorescence imaging and I-type photodynamic/photothermal cancer cell killing activities as well as preparation method and application thereof | |
| CN107722024A (en) | Amido phenoxy group substituted phthalocyanine and its application in pharmaceutical field | |
| CN110128844A (en) | A kind of Benzpyrole squaric acid cyanine dye and its preparation method and application | |
| CN111662333A (en) | Bis-terpyridyl iridium (III) complex and synthetic method thereof | |
| CN112094263B (en) | Quinoxaline-based D-A-pi-A type organic photosensitizer and synthesis method and application thereof | |
| CN105585872B (en) | Asymmetric near-infrared cyanine dye and preparing method and application thereof | |
| CN113683602B (en) | Heptamethine cyanine micromolecule for multi-modal treatment of hypoxic tumors, and preparation method and application thereof | |
| Li et al. | Triphenylamine flanked boron difluoride formazanate for NIR-II fluorescence imaging-guided photothermal therapy | |
| CN112409365B (en) | 3-sulfopropane sulfydryl modified phthalocyanine, preparation method thereof and application thereof in pharmaceutical field | |
| CN113045455A (en) | Aggregation-induced emission photosensitizer with near-infrared emission and high singlet oxygen yield and preparation method and application thereof | |
| CN108503673B (en) | Near-infrared azapyrrolidine dye and preparation method and application thereof | |
| CN104650129B (en) | A kind of silicon phthalocyanine of axial ester bond connection piperidines or morpholine derivative | |
| CN108715591B (en) | Near infrared absorbing porphyrin compounds as photosensitizers and uses thereof | |
| CN110615755A (en) | Near-infrared fluorescent molecule for controlled release of singlet oxygen and preparation method thereof | |
| CN102249939B (en) | Lipid-water amphiphilic benzylidene cyclopentanone dye and preparation method and application in photodynamic therapy thereof | |
| CN105198934B (en) | The platinum-like compounds of Photodynamic activity near infrared absorption, preparation method and applications | |
| CN113387949A (en) | Perylene diimide derivative, hollow nanocapsule PDI-R-4b @ SNC, and preparation method and application thereof | |
| CN109651383B (en) | Compounds for photosensitizers and uses thereof | |
| CN111569069A (en) | Tumor double-targeting diagnosis and treatment photosensitizer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |