CN115043756B - Organic near infrared thermal material, preparation method and application - Google Patents

Organic near infrared thermal material, preparation method and application Download PDF

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CN115043756B
CN115043756B CN202210544291.5A CN202210544291A CN115043756B CN 115043756 B CN115043756 B CN 115043756B CN 202210544291 A CN202210544291 A CN 202210544291A CN 115043756 B CN115043756 B CN 115043756B
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唐本忠
秦安军
韩鹏博
张贵泉
徐赫
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South China University of Technology SCUT
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Abstract

The invention discloses an organic near infrared thermal material, which is prepared by Sonogashira coupling and [2+2] click cycloaddition reaction, wherein tetraphenyl ethylene is used as a framework, different donor units and click receptor units are connected, the donor units are arylamine groups, heteroaromatic amine groups and alkylamino groups, and the receptor units are click reagents. The synthesis method of the organic near infrared thermal material is simple, raw materials are easy to obtain, the yield is close to 100%, the effect of a metal catalyst is not needed in the [2+2] cycloaddition process, the condition is mild, the structure is stable, and the storage is easy. The organic near infrared thermal material has high near infrared absorption efficiency and high photo-thermal conversion efficiency; the nano particles prepared by the organic near infrared photothermal material can be used as phototherapy reagents for biological photothermal treatment, have excellent treatment effect, and can be widely applied in the fields of biological treatment, sea water desalination, energy storage and the like.

Description

Organic near infrared thermal material, preparation method and application
Technical Field
The invention relates to the technical field of photo-thermal materials, in particular to an organic near-infrared photo-thermal material, a preparation method and application thereof.
Background
The organic near infrared thermal material has great advantages in the fields of biological treatment, sea water desalination, energy storage and the like because of the adjustable structure, reliable biodegradation and safety. The synthesis methods of the organic photo-thermal materials are numerous, and the general methods include Suzuki coupling reaction, stille coupling reaction and some polymerization reactions, but the reaction conditions are often harsh, the catalysis of noble metals is needed, and potential biological safety hazards exist. In addition, the synthesis of organic near infrared photothermal materials often requires complex steps to construct large pi conjugated planes. Therefore, the preparation of the organic near-infrared photo-thermal material by using a simple, efficient and metal-free synthesis method has a special significance.
In the context of green chemistry, the [2+2] cycloaddition click reaction has been receiving extensive attention because of its features of simplicity, high efficiency, no by-products, no use of metal catalysts, mild conditions, etc. The reaction is a click reaction of electron donating alkyne and electron withdrawing acceptor, and can be used for constructing a narrow band gap acceptor compound, and the constructed compound has proved to have excellent nonlinear optical characteristics. However, the preparation of organic near infrared photothermal materials based on this reaction is still rare. Therefore, the preparation of the organic near infrared thermal material by utilizing the [2+2] cycloaddition click reaction has important significance.
The invention discloses a near infrared absorption water-soluble conjugated polymer phototherapy reagent, which takes fluorene derivatives as electron donor (D), pyrrolopyrrolidone derivatives as electron acceptor (A), adopts an olefinic bond as pi-conjugated bridge, adopts an organometallic catalyzed Heck reaction to carry out alternating copolymerization, and obtains a near infrared absorption neutral conjugated polymer with a conjugated main chain of D-pi-A, and then obtains a near infrared absorption cationic water-soluble conjugated polymer through quaternization reaction. Chinese patent publication No. CN113069557a discloses a water-soluble conjugated oligomer fluorescence imaging and phototherapy reagent; according to the invention, fluorene derivatives are used as electron donor (D), pyrrolopyrrole dione derivatives are used as electron acceptor (A), thiophene is pi conjugated bridge, suzuki coupling reaction catalyzed by organic metal palladium is adopted, two hydrophobic conjugated oligomers with the structures of D-pi-A, D-pi-A-pi-D are obtained, and then cationic water-soluble conjugated oligomers with near infrared absorption and emission are obtained through side chain quaternization reaction. The conjugated polymers or conjugated oligomers in the above patent documents can be used as phototherapy preparations or fluorescent imaging agents, but the preparation process requires the action of a metal palladium catalyst.
Disclosure of Invention
The invention provides an organic near infrared thermal material, which takes tetraphenyl ethylene as a framework, is connected with different donor units and click receptor units, and has high near infrared absorption efficiency and high photo-thermal conversion efficiency; the nano particles prepared by the organic near infrared photothermal material can be used as phototherapy reagent for biological photothermal treatment, and has excellent treatment effect.
The technical scheme adopted is as follows:
an organic near infrared thermal material has a structural formula shown as a formula (I) or a formula (II):
Figure BDA0003649254260000021
wherein the donor unit R 1 Is an arylamine group, a heteroaromatic amine group or an alkylamino group, R in the acceptor unit 2 Is hydrogen or fluorine.
The organic near infrared thermal material provided by the invention takes tetraphenyl ethylene as a framework, and connects different donor units and click receptor units, the structure has strong intramolecular charge transfer, the introduction of a strong electron withdrawing group can lead the wavelength to be red shifted to a near infrared region, the narrow band gap is favorable for the non-radiative transition, and the obtained material can release energy in a thermal form, and has excellent photo-thermal performance.
Preferably, the arylamine group includes any one of structural formulas shown in formula (III):
Figure BDA0003649254260000031
in the formula (III), R' is hydrogen, methoxy, cyano, fluorine or C1-C20 alkyl, and represents a substitution position.
Preferably, the heteroaromatic amine group comprises any one of the structural formulas shown in the formula (IV):
Figure BDA0003649254260000032
in formula (iv), R' is defined as in formula (iii) and represents the substitution position.
Preferably, the structural formula of the alkylamino group is shown as a formula (V):
Figure BDA0003649254260000033
in formula (v), n is a natural number of 1 to 10, and represents a substitution position.
The invention also provides a preparation method of the organic near infrared thermal material, which comprises the following steps:
when the structural formula of the organic near infrared thermal material is shown as the formula (I),
(1) Alkynyl monosubstituted tetraphenyl ethylene and R 1 The substituted p-halogenated benzene compound is used as a raw material in a molar ratio of 1:1.2 to 1.5, and carrying out a Sonogashira coupling reaction to obtain an intermediate 1;
(2) Taking the intermediate 1 prepared in the step (1) and the clicking reagent as raw materials in a molar ratio of 1:1-1.2 is subjected to [2+2] cycloaddition click reaction to obtain an organic near infrared thermal material with a structural formula shown as a formula (I);
when the structural formula of the organic near infrared thermal material is shown as a formula (II),
1) Alkynyl disubstituted tetraphenyl ethylene and R 1 The substituted p-halogenated benzene compound is used as a raw material in a molar ratio of 1:2.2-3 to obtain an intermediate 2 through a Sonogashira coupling reaction;
2) Taking the intermediate 2 and the clicking reagent prepared in the step 1) as raw materials in a molar ratio of 1:2-2.2 is subjected to [2+2] cycloaddition click reaction to obtain an organic near infrared thermal material with a structural formula shown as a formula (II);
wherein R is 1 Is defined as in formula (I) or formula (II).
The organic near infrared thermal material is prepared by utilizing the Sonogashira coupling reaction and the [2+2] cycloaddition reaction, and has the advantages of simple synthesis method, easily obtained raw materials, high yield, no need of the metal catalyst for the [2+2] cycloaddition reaction and mild conditions.
Preferably, the alkynyl monosubstituted tetraphenyl ethylene is 1- (4-ethynylphenyl) -1, 2-triphenylethylene, and the alkynyl disubstituted tetraphenyl ethylene is 1, 2-bis (4-ethynylphenyl) -1, 2-diphenylethylene.
Said R is 1 The structural formula of the substituted p-halogenated benzene compound is
Figure BDA0003649254260000041
Wherein X is Cl, br or I, R 1 Is defined as in formula (I) or formula (II). />
Preferably, the click reagent is any one of structural formulas shown in a formula (VI):
Figure BDA0003649254260000042
the invention also provides application of the organic photo-thermal material in biological treatment, the organic near infrared photo-thermal material has high near infrared absorption efficiency and high photo-thermal conversion efficiency, and nano particles with good photo-thermal performance can be further prepared for biological treatment, and the organic photo-thermal material has excellent treatment effect and wide application prospect in the field of biological treatment.
The organic near infrared thermal material has excellent photo-thermal performance, can convert light energy into heat energy, has a wide absorption spectrum, and can cover solar light wave bands, so that the sunlight irradiation material can be used for converting light into heat energy for desalination by evaporation of seawater or can be used for storing heat energy released by the material to realize energy storage, and has wide application prospects in the organic photo-thermal fields such as seawater desalination or energy storage.
Compared with the prior art, the invention has the beneficial effects that:
(1) The organic near infrared thermal material is prepared by adopting the [2+2] cycloaddition reaction, and has the advantages of simple synthesis method, easily available raw materials, nearly 100% of yield, no metal catalyst, mild condition, stable structure and easy storage.
(2) The organic near infrared thermal material prepared by the invention takes tetraphenyl ethylene as a framework, connects different donor units and click receptor units, has high near infrared absorption efficiency, realizes high-efficiency aggregated state photo-thermal performance, and has high photo-thermal conversion efficiency.
(3) The organic near infrared photothermal material prepared by the invention has excellent solid state photothermal conversion efficiency, can be used for preparing nano particles with high photothermal conversion efficiency, can be used as phototherapy preparation for biological photothermal treatment, and animal experiments prove that the nano particles prepared by the organic near infrared photothermal material can gradually reduce the tumor part of a mouse to disappear within 14 days in the photothermal treatment, and have excellent treatment effect.
Drawings
FIG. 1 shows the organic near-infrared thermal material 2ATPE-2F prepared in example 1 4 Light-heat conversion curve of solid state powder at 808nm laser.
FIG. 2 shows the organic near-infrared thermal material 2ATPE-2F prepared in example 1 4 Graph of maximum photothermal temperature versus power density for solid state powder at 808nm laser.
FIG. 3 shows the organic near-infrared thermal material 2ATPE-2F prepared in example 1 4 Light-heat conversion curve of solid powder under simulated sunlight.
FIG. 4 is a photo-thermal conversion curve of the water-soluble nanoparticle prepared in application example 1 under 808nm laser.
FIG. 5 is a graph showing the change of tumor volume of mice with time when the water-soluble nanoparticle prepared in application example 1 is applied to photothermal treatment of tumor sites of mice.
Detailed Description
The invention is further elucidated below in connection with the drawings and the examples. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
Example 1
In this example, the organic near infrared thermal material (2 ATPE-2F) 4 ) The structural formula of (2) is as follows:
Figure BDA0003649254260000061
the synthetic route is as follows:
Figure BDA0003649254260000062
(1) 1, 2-bis (4-ethynylphenyl) -1, 2-diphenylethylene (0.76 g,2.0 mmol), N- (4-iodophenyl) -N-phenylaniline (1.86 g,5.0 mmol), cuprous iodide (15 mg,0.08 mmol) and Pd (PPh) 3 ) 4 (46 mg,0.04 mmol) was added to a 50mL reaction flask, under nitrogen protection, 10mL ultra-dry Tetrahydrofuran (THF) and 10mL ultra-dry Triethylamine (TEA) were added, the mixture was refluxed overnight, the reaction was cooled, extracted with dichloromethane, and the organic phase was concentrated to give the crude product, which was then purified and separated by silica gel chromatography to give intermediate 2 as indicated in the above synthetic route in 86% yield;
(2) Adding the intermediate 2 (87 mg,0.1 mmol) obtained in the step (1) and 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone (56 mg,0.2 mmol) into a 5mL reaction bottle, adding 2mL Dichloromethane (DCM), reacting at room temperature, concentrating after the reaction, and passing through a column to obtain black solid 2ATPE-2F 4 The yield was 98%.
Product identification data were as follows:
1 H NMR(500MHz,CD 2 Cl 2 )δ(TMS,ppm):7.50-7.47(m,8H),7.40-7.22(m,20H),7.20-7.08(m,10H),7.03-6.91(m,8H).
13 C NMR(125MHz,CDCl 3 )δ(TMS,ppm):178.91,177.90,145.95145.10,141.08,139.25,135.40,129.06,128.32,125.70,124.90,123.04,115.93,112.58,71.15,613.39.
example 2
In this example, an organic near infrared thermal material (ATPE-F) was obtained 4 ) The structural formula of (2) is as follows:
Figure BDA0003649254260000071
the synthetic route is as follows:
Figure BDA0003649254260000072
(1) 1- (4-Acetylylphenyl) -1, 2-triphenylethylene (0.71 g,2.0 mmol), N- (4-iodophenyl) -N-phenylaniline (1.11 g,3.0 mmol), cuprous iodide (15 mg,0.08 mmol) and Pd (PPh) 3 ) 4 (46 mg,0.04 mmol) was added to a 50mL reaction flask, under nitrogen protection, 10mL ultra-dry Tetrahydrofuran (THF) and 10mL ultra-dry Triethylamine (TEA) were added, the reaction was refluxed overnight, cooled, extracted with dichloromethane, and the organic phase was concentrated to give the crude product, which was then purified and separated by silica gel chromatography to give intermediate 1 as indicated in the above synthetic route in 87% yield;
(2) Adding intermediate 1 (60 mg,0.1 mmol) obtained in step (1) and 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone (28 mg,0.1 mmol) into a 5mL reaction bottle, adding 2mL Dichloromethane (DCM), reacting at room temperature, concentrating after the reaction, and passing through a column to obtain black solid ATPE-F 4 The yield was 99%.
1 H NMR(500MHz,CDCl 3 )δ(TMS,ppm):7.47(m,4H),7.35(m,2H),7.31(d,2H),7.28(m,4H),7.19(d,2H),7.14(m,9H),7.05(m,2H),7.00(m,4H)6.95(d,2H),6.91(d,2H).
13 C NMR(125MHz,CDCl 3 )δ(TMS,ppm):172.36,154.78,150.27144.27,143.73,142.71,142.58,142.29,139.11,136.39,132.54,131.68,131.29,131.25,131.17,130.32,129.46,128.12,127.88,127.86,127.78,127.32,127.16,127.13,127.04,87.23.
Example 3
In this example, the organic near infrared thermal material (NTPE-F) 4 ) The structural formula of (2) is as follows:
Figure BDA0003649254260000081
the synthetic route is as follows:
Figure BDA0003649254260000082
(1) 1- (4-Acetylylphenyl) -1, 2-triphenylethylene (0.71 g,2.0 mmol), 4-iodo-N, N-dimethylaniline (0.74 mg,3.0 mmol), cuprous iodide (15 mg,0.08 mmol), and Pd (PPh) 3 ) 4 (46 mg,0.04 mmol) in a 50mL reaction flask, under nitrogen protection, 10mL ultra-dry Tetrahydrofuran (THF) and 10mL ultra-dry Triethylamine (TEA) were added, refluxed overnight, cooled, extracted with dichloromethane, and the organic phase concentrated to give the crude product, which was then purified and separated by silica gel chromatography to give intermediate 1 as indicated in the above scheme in 85% yield;
(2) Intermediate 1 (48 mg,0.1 mmol) obtained in step (1) and 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone (28 mg,0.1 mmol) are added into a 5mL reaction bottle, 2mL Dichloromethane (DCM) is added for reaction at room temperature, and after the reaction, concentrated, the mixture is subjected to powder column chromatography to obtain black solid NTPE-F 4 The yield was 99%.
Example 4
In this example, the structural formula of the organic near infrared photothermal material (2 ATPE-2T) is shown as follows:
Figure BDA0003649254260000091
the synthetic route is as follows:
Figure BDA0003649254260000092
intermediate 2 (87 mg,0.1 mmol) obtained in step (1) of example 1 and 7,7', 8' -tetracyanodimethyl-p-benzoquinone (41 mg,0.2 mmol) were added to a 5mL reaction flask, 2mL Dichloromethane (DCM) was added, the reaction was carried out at room temperature, and the organic phase was concentrated to give a crude product which was then isolated by column purification on silica gel to give 2ATPE-2T as a black solid in 99% yield.
Application example 1
The organic near-infrared thermal material (2 ATPE-2F) prepared in example 1 4 ) The nano particles are prepared from raw materials and used for treating mouse tumors, and the preparation method comprises the following steps:
DSPE-PEG2000 and 2ATPE-2F4 were completely dissolved in THF. The mixture was quickly poured into deionized water and stirred in a fume hood for 24 hours, after which the sample was further filtered through a membrane filter to give nanoparticles.
Application example 2
The organic near-infrared thermal material (ATPE-2F) prepared in example 2 4 ) The nano particles are prepared from raw materials and used for treating mouse tumors, and the preparation method comprises the following steps:
DSPE-PEG2000 and ATPE-2F4 were completely dissolved in THF. The mixture was quickly poured into deionized water and stirred in a fume hood for 24 hours, after which the sample was further filtered through a membrane filter to give nanoparticles.
Sample analysis
Test example 1 organic near-infrared thermal Material 2ATPE-2F 4 (solid powder) photo-thermal properties at 808nm laser, the results are shown in fig. 1 and 2:
FIG. 1 is a diagram of 2ATPE-2F 4 At 808nm (power density: 1W cm) -2 ) Graph of photo-thermal conversion under laser. As can be seen from the figure, 2ATPE-2F 4 The solid powder has a power density of 1W cm -2 Under 808nm laser, the maximum photo-thermal temperature can reach 247 ℃, the temperature rising speed is high, and the maximum temperature can be reached in 20 s.
FIG. 2 is a schematic view of2ATPE-2F 4 Graph of power versus maximum photothermal temperature at lasers of different power densities at 808nm wavelength. As can be seen from the figure, the maximum photothermal temperature of the solid powder of material is in positive correlation with the laser power density.
FIG. 3 is a diagram of 2ATPE-2F 4 Solid powder in simulated sunlight (power density: 100mW cm -2 ) The lower photothermal conversion curve, as can be seen from FIG. 3, is 2ATPE-2F 4 The maximum photothermal temperature of the solid powder under the simulated sunlight can reach 74 ℃.
FIG. 4 shows the water-soluble nanoparticle (concentration: 100. Mu.g/mL) of application example 1 at 808nm (1W cm) -2 ) Graph of photo-thermal conversion under laser. As can be seen from the figure, application example 1 was performed with 2ATPE-2F 4 The maximum photothermal temperature of the water-soluble nano particles prepared by the raw materials can reach 80 ℃.
FIG. 5 shows the tumor volume change of the water-soluble nanoparticle prepared in application example 1 after 15d photothermal treatment after being injected into the tumor site of mice. As can be seen from the figure, compared with the control group (injected PBS buffer plus laser irradiation, injected water-soluble nanoparticles without laser irradiation), the mice of the experimental group (injected water-soluble nanoparticles with laser irradiation) gradually reduced the tumor volume to disappear within 14 days after photo-thermal treatment, and the therapeutic effect was excellent.
In conclusion, the invention introduces a strong electron withdrawing group on the tetraphenyl ethylene derivative through click reaction, and the high-efficiency near-infrared photo-thermal molecule is obtained, and the photo-thermal material has high-efficiency solid state conversion temperature. The nano particles prepared by the organic near infrared photothermal material are injected into the tumor part of the mouse as a photothermal reagent for photothermal treatment, and the treatment effect is excellent, namely the organic near infrared photothermal material prepared by the invention has wide application prospect in the organic photothermal fields such as biological treatment and the like.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.

Claims (6)

1. An organic near infrared thermal material is characterized in that the structural formula is shown as a formula (I) or a formula (II):
Figure FDA0004092547510000011
wherein the donor unit R 1 Is an arylamine group, a heteroaromatic amine group or an alkylamino group, R in the acceptor unit 2 Hydrogen or fluorine;
the arylamine group is any one of structural formulas shown in a formula (III):
Figure FDA0004092547510000012
in the formula (III), R' is hydrogen, methoxy, cyano, fluorine or C1-C20 alkyl, and represents a substitution position;
the heteroaromatic amine group is any one of structural formulas shown in a formula (IV):
Figure FDA0004092547510000021
in formula (iv), R' is as defined for formula (iii), and represents the substitution position;
the structural formula of the alkylamino is shown as a formula (V):
Figure FDA0004092547510000022
in formula (v), n is a natural number of 1 to 10, and represents a substitution position.
2. The method for preparing an organic near infrared photothermal material according to claim 1, comprising the steps of:
(1) By alkynyl radicalsSubstituted tetraphenyl ethylene and R 1 The substituted p-halogenated benzene compound is used as a raw material in a molar ratio of 1:1.2 to 1.5, and carrying out a Sonogashira coupling reaction to obtain an intermediate 1;
(2) Taking the intermediate 1 prepared in the step (1) and the clicking reagent as raw materials in a molar ratio of 1:1-1.2 is subjected to [2+2] cycloaddition click reaction to obtain an organic near infrared thermal material with a structural formula shown as a formula (I);
or comprises the following steps:
1) Alkynyl disubstituted tetraphenyl ethylene and R 1 The substituted p-halogenated benzene compound is used as a raw material in a molar ratio of 1:2.2-3 to obtain an intermediate 2 through a Sonogashira coupling reaction;
2) Taking the intermediate 2 and the clicking reagent prepared in the step 1) as raw materials in a molar ratio of 1:2-2.2 is subjected to [2+2] cycloaddition click reaction to obtain an organic near infrared thermal material with a structural formula shown as a formula (II);
wherein R is 1 Is defined as in formula (I) or formula (II).
3. The method for preparing an organic near infrared thermal material according to claim 2, wherein the alkynyl monosubstituted tetraphenyl ethylene is 1- (4-ethynylphenyl) -1, 2-triphenylethylene, and the alkynyl disubstituted tetraphenyl ethylene is 1, 2-bis (4-ethynylphenyl) -1, 2-diphenylethylene.
4. The method for preparing organic near infrared photothermal material as defined in claim 2, wherein R is 1 The structural formula of the substituted p-halogenated benzene compound is
Figure FDA0004092547510000031
Wherein X is Cl, br or I, R 1 Is defined as in formula (I) or formula (II).
5. The method for preparing an organic near infrared photothermal material according to claim 2, wherein the click reagent is any one of structural formulas shown in formula (vi):
Figure FDA0004092547510000032
6. use of the organic near infrared thermal material according to claim 1 in the field of sea water desalination or energy storage.
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