Chromone-based organic small molecules, methods, and dual-ratio temperature sensors based on the dual emission intensity and lifetime of organic small molecules

Abstract

The present invention discloses an organic small molecule based on chromone. The structural formula of the organic small molecule is shown in Formula I: The organic small molecule based on chromone of the present invention has long-lived room temperature phosphorescence under ultraviolet light irradiation, and has a large difference in fluorescence and phosphorescence wavelengths, with little interference with each other during inspection. It can be used as a small molecule probe in intensity- and lifetime-based dual-ratio luminescent temperature probes, and good results have been obtained.

Description

Technical Field

[0001] The present invention belongs to the technical field of temperature sensors, and in particular to an organic small molecule based on chromone, a method, and a dual-ratio type temperature sensor based on the dual emission intensity and lifetime of the organic small molecule. Background Art

[0002] Temperature is considered one of the fundamental indicators of energy in living or non-living systems. Various types of thermometers based on different temperature-related physical properties, such as mercury, thermocouples, and optics, have been developed for quantitative temperature measurement. Among various thermal probes, luminescent probes based on temperature-related radiative transition properties are widely used in microscopic resolution due to advantages such as visual observation, high sensitivity, and excellent spatio-temporal resolution. According to the changes in the intensity, single emission wavelength, lifetime, and dual emission intensity ratio of the luminescent probe, the luminescent probe is divided into four different types. Among them, the probe based on the dual emission intensity ratio is an excellent strategy for microscopic thermometry because it can provide self-calibrated readings to avoid the disadvantages of photobleaching and concentration-dependent luminescence.

[0003] In the past few decades, organic room temperature phosphorescence (ORTP) emitters have attracted great interest due to their advantages of low cost, biocompatibility, and easy molecular regulation. Compared with traditional fluorescent materials, ORTP emitters have longer wavelengths and lifetimes, which are beneficial for observation and measurement. In addition, ORTP emitters usually exhibit two temperature-related emission peaks (fluorescence and phosphorescence), which can be used for microscopic thermometers. To achieve accurate measurement, the wavelength difference (Δλ) between the two emission bands usually needs to be as large as possible. However, the energy gap between the singlet and triplet states in ORTP emitters usually needs to be very small to facilitate the intersystem crossing (ISC) process of efficient RTP, which inevitably results in a small Δλ between fluorescence and phosphorescence, and thus a large overlap between the two spectral bands in the photoluminescence spectrum, which is not conducive to the accuracy of the ratio-type thermometer. Therefore, it is still challenging to simultaneously achieve efficient room temperature phosphorescence and a large Δλ, which is crucial for realizing an accurate microscopic thermometer.

[0004] Conformation is a fundamental parameter of organic / polymer semiconductors, which significantly affects their physical and chemical properties. Many efforts have been made to adjust the conformation to achieve high-performance organic / polymer semiconductors for optoelectronic devices, such as organic solar cells (OSCs), organic thin film transistors (OTFTs), organic photodetectors (OPDs), and organic light-emitting diodes (OLEDs). Among them, intramolecular non-covalent interactions (NIIs), such as S···O, Se···O, S···F, etc., have become important methods for regulating the conformation and physicochemical properties of organic / polymer semiconductors, but are rarely used to regulate the properties of molecular triplets.

[0005] Through retrieval, the following patent publication documents related to this invention patent application were found:

[0006] 1. A preparation method and application of a dual-ratio aptamer sensor based on electrochemistry and photoelectrochemistry (CN110702757A), specifically, a novel dual-ratio aptamer sensor based on electrochemistry and photoelectrochemistry is first proposed for the specific detection of streptomycin (STR). The steps are as follows: Step 1: Preparation of gold nanoparticles (AuNPs) and design of the bases of each nucleotide chain in the hybridization chain reaction; Step 2: Construction of a dual-ratio aptamer sensor based on electrochemistry and photoelectrochemistry. The dual-ratio aptamer sensor based on electrochemistry and photoelectrochemistry constructed in the present invention provides an effective way to reduce the influence of the external environment and accurately and widely detect streptomycin.

[0007] 2. A preparation method and application of a dual-ratio biosensor for amplifying the linear range based on aptamers with different structures (CN112285172A), specifically related to a preparation method and application of a dual-ratio electrochemical aptamer sensor for amplifying the linear range based on a linear aptamer-hairpin aptamer; forming an AQ-rGO composite material through the non-covalent interaction between AQ and rGO; fixing the thiol-modified hairpin aptamer-linear aptamer on the sensing interface by AuNPs; a part of the hairpin aptamer includes an aptamer sequence carrying the electrochemical molecule methylene blue, and the linear aptamer carries the ferrocene electrochemical signal molecule, thereby constructing a novel dual-ratio electrochemical aptamer sensor; compared with the hairpin aptamer, the binding of the linear aptamer to its target AFB1 is more likely to occur. Therefore, the concentration of AFB1 that causes the change of the MB signal molecule carried by the hairpin aptamer can be used as the concentration point for the qualitative analysis of AFB1, realizing the qualitative analysis of AFB1 in food, with high detection sensitivity and good stability.

[0008] By comparison, this invention patent application is essentially different from the above patent publication documents. Summary of the Invention

[0009] The purpose of the present invention is to overcome the deficiencies in the prior art and provide an organic small molecule based on chromone, a method, and a dual-ratio temperature sensor based on the dual emission intensity and lifetime of the organic small molecule.

[0010] The technical solution adopted by the present invention to solve its technical problems is:

[0011] An organic small molecule based on chromone, and the structural formula of the organic small molecule is shown in Formula I:

[0012]

[0013] Furthermore, the organic small molecule has long-lived phosphorescence at room temperature.

[0014] Use of the chromone-based organic small molecule as described above in the preparation of a temperature detection device.

[0015] Further, the temperature detection device is a temperature sensor and / or a temperature probe for the intensity and lifetime ratio of dual emission of fluorescence and phosphorescence.

[0016] Further, the chromone-based organic small molecule is used as a temperature-sensing luminescent material for preparing a temperature detection device.

[0017] Preparation method of the chromone-based organic small molecule as described above, including the steps of formula II:

[0018]

[0019] Further, the method includes the following steps:

[0020] 3-bromochromone, phenylboronic acid, Pd(PPh3)4 and K2CO3 are added into a two-necked flask. The flask is evacuated and purged with dry nitrogen three times, then toluene and deionized water are added. Stir overnight at 120 °C under a nitrogen atmosphere; after cooling to room temperature, the mixture is poured into water and extracted with dichloromethane, dried, filtered, and the solvent is removed by rotary evaporation to obtain a dark solid, which is purified by silica gel column chromatography (=) to obtain a white solid, which is the chromone-based organic small molecule;

[0021] Wherein, the ratio of 3-bromochromone:phenylboronic acid:Pd(PPh3)4:K2CO3:toluene:deionized water is mmol:mmol:mmol:mmol:mL:mL = 1.0:1.0:0.05:8.0:10.0:1.0.

[0022] Further, ethyl acetate and petroleum ether with a volume ratio of 1:20 are used during chromatography;

[0023] Alternatively, the yield of the chromone-based organic small molecule is 54%.

[0024] A dual-ratio type temperature sensor based on the organic small molecule prepared by using the organic small molecule as described above, and the preparation method includes the following steps:

[0025] 3TC molecular single crystals are obtained by the method of slow evaporation in a n-hexane solution, which is the dual-ratio type temperature sensor.

[0026] A use method of the dual-ratio type temperature sensor as described above, including the following steps:

[0027] By testing the photoluminescence spectra and lifetimes of the dual-ratio type temperature sensor at different temperatures, performing ratio processing on the intensities and lifetimes of the dual emissions, for an unknown ambient temperature, specific temperature information can be obtained by simply measuring the intensities and lifetimes of the two emission peaks of the dual-ratio type temperature sensor at that temperature.

[0028] The advantages and positive effects achieved by the present invention are as follows:

[0029] 1. The organic small molecule of the present invention is based on chromone, and its crystal has long-lived room temperature phosphorescence under ultraviolet light irradiation, with a lifetime reaching 6 ms, and the wavelength difference between the fluorescence and phosphorescence peak dual emissions is as high as 188 nm, resulting in little interference with each other when detecting intensities. To date, the prior art has not utilized the lifetime ratio of dual emissions to prepare temperature probes, nor has it utilized the intensity ratio of fluorescence and phosphorescence dual emissions to prepare temperature probes. And currently, the position difference between the fluorescence and phosphorescence peaks of organic molecules is about 100 nm, which will inevitably interfere with each other during detection. The lifetimes of fluorescence and phosphorescence themselves span a large range, and the phosphorescence intensity and lifetime are extremely sensitive to temperature. Based on this, the first fluorescence-phosphorescence dual-ratio type luminescent temperature probe model was established, achieving good results.

[0030] 2. In the chromone molecule of the present invention, by introducing intramolecular non-covalent interactions (NIIs), the triplet energy levels of organic molecules are regulated, and organic molecules with small fluorescence-phosphorescence dual-emission overlaps are obtained. Based on the ratios of their intensities and lifetimes, a three-dimensional dual-ratio type temperature probe is constructed. The regulation of NIIs makes T1 far from S1 to generate phosphorescence with a longer wavelength, while the high triplet excited state is regulated to be close to S1 to obtain efficient intersystem crossing. Therefore, the compounds obtained by this mechanism have efficient room temperature phosphorescence and a large dual-emission wavelength difference, ensuring the minimum mutual interference during the detection of the dual-emission bands and achieving good results. It can be applied to large-area temperature detection and precise detection at positions where ordinary temperature detectors cannot penetrate, such as in cells / animal in vivo. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is the single crystal structure diagram of the organic small molecule in the present invention;

[0032] Figure 2 It is the photoluminescence spectrum diagram of the organic small molecule provided in Example 1 of the present invention;

[0033] Figure 3 It is the photoluminescence delayed spectrum diagram of the organic small molecule provided in Example 1 of the present invention;

[0034] Figure 4 It is the photoluminescence spectrum diagram of the organic small molecule provided in Example 1 of the present invention at different temperatures;

[0035] Figure 53D map of the dual-ratio probe for the fluorescence and phosphorescence intensities and lifetimes of the organic small molecule provided in Example 1 of the present invention;

[0036] Figure 6 CIE coordinate diagram of the luminescence color of the organic small molecule provided in Example 1 of the present invention at different temperatures. Detailed implementation manners

[0037] The embodiments of the present invention are described in detail below. It should be noted that the present embodiments are narrative and not restrictive, and the protection scope of the present invention cannot be limited thereby.

[0038] The raw materials used in the present invention are all conventional commercially available products without special instructions; the methods used in the present invention are all conventional methods in the art without special instructions.

[0039] An organic small molecule based on chromone, and the structural formula of the organic small molecule is shown in Formula I:

[0040]

[0041] Preferably, the organic small molecule has long-lived phosphorescence at room temperature.

[0042] Application of the above-mentioned organic small molecule based on chromone in the preparation of temperature detection devices.

[0043] Preferably, the temperature detection device is a temperature sensor and / or a temperature probe with the intensity and lifetime ratio of dual fluorescence and phosphorescence emission.

[0044] Preferably, the organic small molecule based on chromone is used as a temperature-sensing luminescent material for preparing a temperature detection device.

[0045] Preparation method of the above-mentioned organic small molecule based on chromone, including the steps as shown in Formula II:

[0046]

[0047] Preferably, the method includes the following steps:

[0048] 3-bromochromone, phenylboronic acid, Pd(PPh3)4 and K2CO3 are added to a two-necked flask. The flask is evacuated and purged with dry nitrogen three times, then toluene and deionized water are added, and the mixture is stirred at 120 °C overnight under a nitrogen atmosphere; after cooling to room temperature, the mixture is poured into water and extracted with dichloromethane, dried, filtered, and the solvent is removed by rotary evaporation to obtain a dark solid, which is purified by silica gel column chromatography (=) to obtain a white solid, which is the organic small molecule based on chromone;

[0049] Among them, the ratio of 3-bromochromone: phenylboronic acid: Pd(PPh3)4: K2CO3: toluene: deionized water in mmol: mmol: mmol: mmol: mL: mL is 1.0: 1.0: 0.05: 8.0: 10.0: 1.0.

[0050] Preferably, ethyl acetate and petroleum ether with a volume ratio of 1:20 are used during chromatography;

[0051] Alternatively, the yield of the chromone-based organic small molecule is 54%.

[0052] A dual-ratio type temperature sensor based on the dual emission intensity and lifetime of an organic small molecule prepared using the organic small molecule as described above, the preparation method comprising the following steps:

[0053] 3TC molecular single crystals are obtained by the method of slow evaporation in a n-hexane solution, which is the dual-ratio type temperature sensor.

[0054] A method for using the dual-ratio type temperature sensor as described above, comprising the following steps:

[0055] By testing the photoluminescence spectrum and lifetime of the dual-ratio type temperature sensor at different temperatures, ratio processing is performed on the intensity and lifetime of the dual emission. For an unknown ambient temperature, specific temperature information can be obtained by simply measuring the intensities and lifetimes of the two emission peaks of the dual-ratio type temperature sensor at this temperature. Measure the fluorescence phosphorescence emission intensity of the molecule and its lifetime, perform ratio calculation, and determine the temperature according to the relationship between the dual ratio and the temperature.

[0056] Specifically, the relevant preparation and detection examples are as follows:

[0057] Example 1

[0058] The preparation method of the chromone-based small molecule compound in this example is characterized in that: the method comprises the following steps:

[0059]

[0060]

[0061] 3-Bromochromone (0.23 g, 1.0 mmol), phenylboronic acid (0.12 g, 1.0 mmol), Pd(PPh3)4 (57.5 mg, 0.05 mmol) and K2CO3 (1.10 g, 8.0 mmol) were added to a two-necked flask. The flask was evacuated and purged with dry nitrogen three times, then toluene (10.0 mL) and deionized water (1.0 mL) were added, and the mixture was stirred at 120 °C overnight under a nitrogen atmosphere. After cooling to room temperature, the mixture was poured into water and extracted with dichloromethane, dried, filtered, and the solvent was removed by rotary evaporation to obtain a dark solid, which was purified by silica gel column chromatography (ethyl acetate: petroleum ether = 1:20) to obtain a white solid (54% yield).

[0062] The structural characterization data of the 3TC molecule are as follows:

[0063] 1 1H NMR (500 MHz, CDCl3) δ (ppm): 8.32 (d, J = 6.3 Hz, 1H), 8.24 (s, 1H), 8.00 (s, 1H), 7.68 (t, J = 6.9 Hz, 1H), 7.49 (d, J = 8.4 Hz, 1H), 7.45 - 7.42 (m, 1H), 7.39 (d, J = 2.4 Hz, 2H);

[0064] 13 13C NMR (126 MHz, CDCl3) δ (ppm): 176.14, 156.01, 152.65, 133.68, 131.65, 126.47, 126.30, 125.61, 125.37, 124.50, 124.41, 120.47, 118.14;

[0065] High-resolution mass spectrometry (EIS, m / z) For C 13 H8O2S, Cal.: 228.0245. Found: 228.0238;

[0066] Elemental analysis For C 13 H8O2S, Cal.: C, 68.40; H, 3.53. Found: C, 68.48; H, 3.53

[0067] Figure 1 The single crystal structure of the molecule is shown in, and the distance between S···O is less than the sum of the van der Waals radii of the two atoms indicating the existence of intermolecular forces. In Figure 2 and Figure 3The photoluminescence and delayed luminescence spectra of the small molecule are shown. It can be seen from the luminescence spectra that the molecule has two discrete luminescence peaks, and the long-wavelength luminescence peak can still be detected after delay, indicating that it is a long-lived component. The two luminescence peaks are fluorescence and phosphorescence respectively, with lifetimes of 1.02 ns and 6 ms, and the lifetime ratio is as high as 10 to the sixth power. Moreover, the overlap of the luminescence bands between the dual emissions is small, and the wavelength difference reaches 188 nm. The wavelength of the phosphorescence extends to the near-infrared region. Therefore, when detecting the intensities of the dual emissions, they will not affect each other, greatly improving the detection accuracy of the ratio-type temperature probe.

[0068] Example 2

[0069] In this example, the method for using the organic small molecule to prepare the ratio-type temperature probe includes:

[0070] As Figure 4 shown, 3TC molecular single crystals are obtained by the method of slow evaporation in a n-hexane solution. By testing the photoluminescence spectra and lifetimes of 3TC molecules at different temperatures, ratio processing is performed on the intensities and lifetimes of the dual emissions to obtain the relationship between the dual ratios of light intensity and lifetime and temperature as Figure 5 shown, and the luminescence colors of the probe at each temperature are as Figure 6 shown. Therefore, for an unknown ambient temperature, specific temperature information can be obtained by simply measuring the intensities and lifetimes of the two luminescence peaks of the probe at its temperature, which is convenient and fast, and can be applied to large-area temperature detection and precise detection at positions such as cells / animal in vivo that cannot be reached by ordinary temperature detectors.

[0071] Although the embodiments of the present invention are disclosed for illustrative purposes, those skilled in the art can understand that: within the spirit and scope of the present invention and the appended claims, various substitutions, changes, and modifications are possible. Therefore, the scope of the present invention is not limited to the content disclosed in the embodiments.

Claims

1. Use of chromone-based organic small molecules in the fabrication of temperature detection devices; the structural formula of the chromone-based organic small molecules is shown in Formula I:

2. The application according to claim 1, wherein: The temperature detection device is a temperature sensor and / or a temperature probe for the intensity and lifetime ratio of fluorescence and phosphorescence dual emission.

3. The application according to claim 1, wherein: The chromone-based organic small molecule is used as a temperature-sensing luminescent material for preparing a temperature detection device.

4. A dual-ratio type temperature sensor based on the dual emission intensity and lifetime of organic small molecules prepared from organic small molecules, characterized in that: The preparation method includes the following steps: An organic small molecule single crystal is obtained by a method of slow evaporation in a n-hexane solution, which is a dual-ratio type temperature sensor; The structural formula of the organic small molecule is shown in Formula I:

5. A method for using the dual-ratio type temperature sensor according to claim 4, characterized in that: including the following steps: By testing the photoluminescence spectra and lifetimes of the dual-ratio type temperature sensor at different temperatures, ratio processing is performed on the intensities and lifetimes of the dual emissions. For an unknown ambient temperature, specific temperature information can be obtained by measuring the intensities and lifetimes of the two emission peaks of the dual-ratio type temperature sensor at this temperature.

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