CN114276313A - Preparation method and application of near-infrared fluorescent compound with photo-thermal conversion capability - Google Patents
Preparation method and application of near-infrared fluorescent compound with photo-thermal conversion capability Download PDFInfo
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- CN114276313A CN114276313A CN202011038117.0A CN202011038117A CN114276313A CN 114276313 A CN114276313 A CN 114276313A CN 202011038117 A CN202011038117 A CN 202011038117A CN 114276313 A CN114276313 A CN 114276313A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 21
- 239000007850 fluorescent dye Substances 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 4
- 229940125904 compound 1 Drugs 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 claims 1
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000004220 aggregation Methods 0.000 abstract description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004061 bleaching Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- -1 4-tert-butylphenyl Chemical group 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 238000007626 photothermal therapy Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
The invention discloses a compound integrating solid-state fluorescence emission and photo-thermal capability, a preparation method and application thereof, wherein the molecular formula of the compound is as follows:
Description
Technical Field
The invention belongs to the technical field of near-infrared fluorescence emission and photothermal conversion, and particularly relates to a compound integrating near-infrared solid-state fluorescence emission and photothermal conversion capabilities, and a preparation method and application thereof.
Background
Currently, the study of near-infrared fluorescent molecules is a challenging task. Meanwhile, near infrared (NIR, 700-900nm) fluorescent molecules have potential application values in the fields of biology and the like, so that the interest of a plurality of researchers is aroused. Photothermal materials can be used in the fields of photothermal therapy of cancer, etc., but materials having photothermal conversion ability are few. Therefore, the synthesis of materials with near-infrared light emission and photothermal conversion capabilities is urgently needed.
In 2001, the team of Thanksonics proposed the concept of aggregation-induced emission (AIE), i.e., a molecule that does not emit in solution but has a high fluorescence intensity in the aggregated state. At present, the mechanism of AIE is widely recognized as a limitation of intramolecular motion and energy dissipation. In biomedical applications, molecules are mostly used in the aggregate state. Therefore, the luminescence of the aggregate state of the molecule is of great research significance. Meanwhile, the molecular encapsulation of AIE characteristics in the nano-particles with biocompatibility is an effective method, and has the advantages of good biocompatibility, good light stability, low dark toxicity and the like. These factors make nanoparticles based on the properties of AIE a promising candidate for application. Therefore, a novel compound with aggregation-induced emission characteristics is developed, and the compound has photothermal conversion capability and near-infrared emission and has a wide application prospect.
Disclosure of Invention
The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method for preparing a near-infrared fluorescence emission and photothermal conversion compound having aggregation-induced emission characteristics. In the invention, a cross molecular structure is designed, wherein diphenylamine is used as an electron donor, and rhodanic-CN is used as an electron acceptor, the combination can obviously reduce the electron energy gap difference, and meanwhile, due to the introduction of diphenylamine and rhodanic-CN, the molecule has a proper twisting phenomenon, and the AIE characteristic is ensured.
The molecular chemical formula of the fluorescent compound 1 provided by the invention is shown as the formula (I):
the invention also provides a preparation method of the compound, which comprises the following steps:
a novel near-infrared fluorescent compound 1 with photothermal conversion ability and molecular formula C72H66N8O2S2
1)2, 5-bis (4-tert-butylphenyl) amine-1, 4-dicarbaldehyde and rhodanic-CN in 1, 4-dioxane;
2) adding 0.5ml triethylamine, reacting for 6h at 110 ℃;
3) after the reaction was cooled, the final product was obtained by recrystallization from dichloromethane/petroleum ether.
The molar ratio of the 2, 5-di (4-tert-butylphenyl) amine-1, 4-dicarboxaldehyde to rhodanic-CN is 0.2 mmol: 0.4 mmol.
The invention has the following beneficial effects:
the fluorescent molecule has the advantages of aggregation-induced emission characteristic and high aggregation state emission, and the fluorescence emission range is between 700nm and 1200nm of long wavelength. The stokes shift is up to 240 nm. In a mixed solution of tetrahydrofuran and water of a fluorescent compound 1, when the volume concentration of the water is less than 40%, the solution has almost no fluorescence, and the solution is clear and no aggregate is generated; when the volume concentration of water in the mixed solution of tetrahydrofuran and water is more than 40%, the compound generates fluorescence; the fluorescence becomes stronger with increasing water content.
Laser at 650nm (600 mw/cm)2) Under irradiation, the nanoparticle solution of compound 1 can be raised from 28 ℃ to 75 ℃ at 4 min. The temperature rise is proportional to the concentration of nanoparticles. In addition, for a fixed concentration of nanoparticles, the stronger the laser, the more pronounced the temperature increase. The maximum temperature of the nanoparticles was hardly changed even in five photothermal conversion processes. Indicating excellent photobleaching resistance.
The invention also provides a synthetic method of the fluorescent compound 2, and the structural formula (2) of the compound 2 is shown as follows:
the preparation method of the compound 2 comprises the following steps
1)2, 5-diamine-1, 4-dicarboxaldehyde and rhodanic-CN in 1, 4-dioxane;
2) adding 0.5ml triethylamine, reacting for 6h at 110 ℃;
3) after the reaction was cooled, the final product was obtained by recrystallization from dichloromethane/petroleum ether. The molar ratio of the 2, 5-diamine-1, 4-diformaldehyde to the rhodanic-CN is 0.2 mmol: 0.4 mmol.
Drawings
FIG. 1 is a graph of the UV-VIS absorption spectra of solutions of fluorescent compounds 1 and 2;
FIG. 2 is a graph showing fluorescence spectra of solutions of fluorescent compounds 1 and 2;
FIG. 3 is a graph showing fluorescence spectra of fluorescent compound 1 in tetrahydrofuran-water mixed solutions of different ratios;
FIG. 4 is a solid state fluorescence spectrum of fluorescent compounds 1 and 2;
FIG. 5 shows the temperature of fluorescent Compound 1 with time under different lasers
FIG. 6 is a graph of the temperature of fluorescent Compound 1 at different concentrations over time
FIG. 7 shows five photothermal cycles of fluorescent Compound 1
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
Example 1
The synthesis method of the compound 1 comprises the following steps:
the preparation method comprises the following steps:
1)2, 5-bis (4-tert-butylphenyl) amine-1, 4-dicarbaldehyde and rhodanic-CN in 1, 4-dioxane;
2) adding 0.5ml triethylamine, reacting for 6h at 110 ℃;
3) after the reaction was cooled, the final product was obtained by recrystallization from dichloromethane/petroleum ether.
The molar ratio of the 2, 5-di (4-tert-butylphenyl) amine-1, 4-dicarboxaldehyde to rhodanic-CN is 0.2 mmol: 0.4 mmol.
Example 2
The synthesis method of the compound 2 comprises the following steps:
the synthesis method comprises the following steps:
1)2, 5-diamine-1, 4-dicarboxaldehyde and rhodanic-CN in 1, 4-dioxane;
2) adding 0.5ml triethylamine, reacting for 6h at 110 ℃;
3) after the reaction was cooled, the final product was obtained by recrystallization from dichloromethane/petroleum ether. The molar ratio of the 2, 5-diamine-1, 4-diformaldehyde to the rhodanic-CN is 0.2 mmol: 0.4 mmol.
the fluorescent compound was dissolved in tetrahydrofuran to a final concentration of 5.0X 10-5M, as shown in FIG. 1: the maximum absorption of the ultraviolet-visible absorption spectrum is measured to be about 580 nm.
the fluorescent compound 1 hardly fluoresces in the tetrahydrofuran solution, and the fluorescence intensity is remarkably increased when the water content in the solution is 40%, and the fluorescence intensity is gradually increased with the increase of the water content. As can be seen from fig. 2, when the water content of the mixed solution is less than 40%, the solution has almost no fluorescence, and the solution is clear without the generation of aggregates; when the water content reaches 40%, the fluorescent molecular compound 1 starts to aggregate, the fluorescence intensity is obviously enhanced, and the fluorescence becomes stronger along with the increase of the water content.
Therefore, the fluorescent molecule compound 1 has typical aggregation-induced emission performance.
Characterization 3-photothermal conversion Capacity of the fluorescent Compound
Laser at 650nm (600 mw/cm)2) Under irradiation, the nanoparticle solution of compound 1 can be raised from 28 ℃ to 75 ℃ at 4 min. The temperature rise is proportional to the concentration of nanoparticles. In addition, for a fixed concentration of nanoparticles, the stronger the laser, the more pronounced the temperature increase. The maximum temperature of the nanoparticles was hardly changed even in five photothermal conversion processes. Indicating excellent photobleaching resistance.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (5)
1. A compound integrating solid-state fluorescence emission and photothermal conversion capabilities, which is characterized in that: compound 1 of formula C72H66N8O2S2The structural formula of the molecule is:
2. the compound of claim one, wherein the solid compound emits fluorescence under optical excitation with a wavelength of 700nm to 1200nm and a maximum fluorescence peak position of 820 nm.
3. A method of synthesis of a compound according to claim 1 or 2, comprising the steps of: a round-bottomed flask was charged with 2, 5-diphenylamine-1, 4-dialdehyde (100mg, 0.2mmol) and rhodanic-CN (104mg, 0.4mmol) dissolved in 1.2ml of 1, 4-dioxane, and 0.5ml of triethylamine was added thereto, and the mixture was refluxed at 110 ℃ for 6 hours. After the reaction was cooled, the final product was obtained by recrystallization from dichloromethane/petroleum ether.
4. The fluorescent compound is in a nanoparticle state and is excited by a laser beam (600 mw/cm) at 650nm2) Under irradiation, the nanoparticle solution of compound 1 can be raised from 28 ℃ to 75 ℃ at 4 min.
5. The maximum temperature of the nanoparticles was also hardly changed in the five photothermal conversion processes.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104830318A (en) * | 2015-05-15 | 2015-08-12 | 天津理工大学 | Fluorescence labeling molecule capable of emitting fluorescence in high aggregation state and preparation method of fluorescence labeling molecule |
| CN107722055A (en) * | 2017-10-09 | 2018-02-23 | 天津理工大学 | A kind of Mitochondrially targeted fluorescence probe sensitising agent of low-power white light driving and its synthetic method and application |
| CN109294557A (en) * | 2018-10-12 | 2019-02-01 | 北京化工大学 | A kind of preparation method and application of the composite nano materials with aggregation-induced emission property and photothermal conversion property |
| CN111004624A (en) * | 2019-12-24 | 2020-04-14 | 南开大学 | Preparation of near-infrared fluorescent probe with PTT effect and aggregation-induced emission enhancement effect |
-
2020
- 2020-09-28 CN CN202011038117.0A patent/CN114276313A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104830318A (en) * | 2015-05-15 | 2015-08-12 | 天津理工大学 | Fluorescence labeling molecule capable of emitting fluorescence in high aggregation state and preparation method of fluorescence labeling molecule |
| CN107722055A (en) * | 2017-10-09 | 2018-02-23 | 天津理工大学 | A kind of Mitochondrially targeted fluorescence probe sensitising agent of low-power white light driving and its synthetic method and application |
| CN109294557A (en) * | 2018-10-12 | 2019-02-01 | 北京化工大学 | A kind of preparation method and application of the composite nano materials with aggregation-induced emission property and photothermal conversion property |
| CN111004624A (en) * | 2019-12-24 | 2020-04-14 | 南开大学 | Preparation of near-infrared fluorescent probe with PTT effect and aggregation-induced emission enhancement effect |
Non-Patent Citations (1)
| Title |
|---|
| LUQI LIU等: ""One-for-All Phototheranostic Agent Based on Aggregation-Induced Emission Characteristics for Multimodal Imaging-Guided Synergistic Photodynamic/Photothermal Cancer Therapy"", ACS APPLIED MATERIALS & INTERFACES, vol. 13, no. 17, 25 April 2021 (2021-04-25), pages 19668 - 19678 * |
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