A multi-stimulus responsive photochemical sensor and its preparation method and application

Abstract

The present invention provides a multiple stimulus-responsive photochemical sensor and its preparation method and application, belonging to the field of multiple stimulus-responsive material technology. Under a protective atmosphere, the present invention performs a Suzuki coupling reaction on 2-bromo-1,1,2-triphenylethylene, 2-formyl-4-thiopheneboronic acid, a palladium catalyst, an alkaline compound and a solvent to obtain 4-(1,2,2-triphenylethylene)thiophene-2-carboxaldehyde; under a protective atmosphere, 4-(1,2,2-triphenylethylene)thiophene-2-carboxaldehyde, 2-amino-4,6-dimethylpyrimidine, tetrabutylammonium hydrogen sulfate and a solvent are mixed to perform a condensation reaction to obtain a multiple stimulus-responsive photochemical sensor. The present invention provides applications of the obtained compound in acid-base response, ion sensing, photochromism, safety ink and cell fluorescence imaging. The preparation method has simple steps, low cost, mild preparation conditions, is suitable for industrial production, and has great application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of multiple stimulus-responsive materials, and in particular to a multiple stimulus-responsive optical chemical sensor and a preparation method and application thereof. Background Art

[0002] In recent years, the unique advantages and exciting application prospects of stimuli-responsive materials have triggered a booming development in this field. Among them, multi-stimuli-responsive materials have received particular attention and achieved remarkable progress. They have demonstrated great potential in a wide range of fields, including physical chemistry, materials science, biology, and medicine. In particular, compounds with responsive properties to light, temperature, ions, mechanical forces, pH, force, and solvent polarity are particularly promising. Light is a non-invasive stimulus with high spatiotemporal resolution. By irradiating light of different wavelengths, dynamic photoreversible luminescent materials can be effectively constructed. Photochromic diarylethenes are ideal building blocks for constructing photostimuli-responsive functional materials. Upon exposure to light of a certain wavelength (hv), the ring-opened molecules undergo photocyclization to form closed ring states, resulting in changes in molecular structure and spectral changes. Upon exposure to light of another wavelength (hv') or heat, they reversibly return to their initial state. Therefore, these compounds serve as ideal photoresponsive building blocks and are often used to construct photostimuli-responsive functional molecules.

[0003] Tetrarylethylene (TAE) compounds are the most typical aggregation-induced emission (AIEgens) molecules, with a core of C=C surrounded by four freely rotatable propeller-like aromatic rings. Under aggregated or solid conditions, due to intramolecular motion restrictions (RIMs), strong fluorescence emission is guaranteed in the aggregated and solid states. Currently, stimulus-responsive luminescent materials designed with tetraphenylethylene as the core have been widely reported. For example, Wang et al. explored a tetraphenylethylene AIEgens fluorescence sensor modified with 2,6-pyridinedicarboxylic acid, which can intuitively distinguish Th among lanthanides, transition metals and alkali metals under ultraviolet light. 4+ In 2019, Lin et al. developed a TPE-BSA sensor with good AIEgens properties for uranyl ion detection. By adding the salt benzene part to the active tetraphenylethylene part of AIE, the sensor was sensitive to UO 2+ The detection limit was low (3.9×10 -8 molL -1 However, there are few reports in the prior art on integrating a TAE unit and an acceptor group into a molecule with multicolor switching and multiple stimulus responses. Therefore, the design and development of high-contrast multi-stimulus responsive emission materials based on tetraarylethenes is of great significance. Summary of the Invention

[0004] The purpose of the present invention is to provide a multi-stimulus responsive optical chemical sensor and its preparation method and application, so as to make up for the deficiencies of the prior art.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a multi-stimulus responsive photochemical sensor comprising

[0007]

[0008] The present invention also provides a method for preparing the multi-stimulus-responsive photochemical sensor, comprising the following steps: (1) mixing 2-bromo-1,1,2-triphenylethylene, 2-formyl-4-thiopheneboronic acid, a palladium catalyst, an alkaline compound and a solvent under a protective atmosphere to carry out a Suzuki coupling reaction to obtain 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde; and (2) mixing 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde, 2-amino-4,6-dimethylpyrimidine, tetrabutylammonium hydrogen sulfate and a solvent under a protective atmosphere to carry out a condensation reaction to obtain the multi-stimulus-responsive photochemical sensor.

[0009] Preferably, in step (1), the molar ratio of 2-bromo-1,1,2-triphenylethylene and 2-formyl-4-thiopheneboronic acid is 1:1.5-2; the molar concentration of the palladium catalyst in the reaction solution is 8-12%; the amount ratio of the 2-bromo-1,1,2-triphenylethylene and the solvent is 10 mmol-0.1 mol:80-250 mL; the alkaline compound is added in the form of an aqueous solution, the equivalent concentration of the alkaline compound solution is 3-7 equiv., and the amount ratio of the 2-bromo-1,1,2-triphenylethylene and the alkaline compound solution is 10 mmol-0.1 mol:60-120 mL.

[0010] Preferably, the temperature of the Suzuki coupling reaction in step (1) is 78-82° C., and the time is 11-13 h; and the protective atmosphere is nitrogen atmosphere.

[0011] Preferably, the palladium catalyst in step (1) comprises one or more of Pd(PPh3)4, PdCl2(dppf)2, Pd(dppf)Cl2 and Pd(OAc)2; the alkaline compound comprises one or more of Na2CO3, Ba(OH)2, K3PO4, Cs2CO3, K2CO3, TiOH, KF, CsF, Bu4F, NaOH and i-PrNEt2; and the solvent comprises one or more of tetrahydrofuran, CH2Cl2, N,N-dimethylformamide and CH3CN.

[0012] Preferably, in step (2), the molar ratio of 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde to tetrabutylammonium hydrogen sulfate is 1.0-1.2:1; the molar ratio of 2-amino-4,6-dimethylpyrimidine to tetrabutylammonium hydrogen sulfate is 5-6:2.5-3; and the amount ratio of 2-amino-4,6-dimethylpyrimidine to solvent is 5-6 mmol:70-90 mL.

[0013] Preferably, the temperature of the condensation reaction in step (2) is 115-125° C., and the time is 4-8 h; the protective atmosphere is a nitrogen atmosphere; and the solvent is a sodium hydroxide solution or a potassium hydroxide solution with a concentration of 4-6 mol / L.

[0014] The present invention also provides the multiple stimulus responsive photochemical sensor or the multiple stimulus responsive photochemical sensor obtained by the preparation method in acid-base response, ion sensing, photochromism, Cr 3+ Applications in “naked eye” identification, cell fluorescence imaging, security ink or anti-counterfeiting.

[0015] Beneficial effects of the present invention:

[0016] The compound PAs provided by the present invention comprises 4-methyl-6-(2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (TPT-2-PA) and 4,6-bis-2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (BTPT-2-PA). The compound PAs provided by the present invention has significant photochromism, photofluorescence enhancement, acid-induced color change, Cr 3+ The "naked eye" recognition feature enables optical anti-counterfeiting applications in materials without fluorescent background, and can stain biological cells and serve as a cell marker; and the preparation method of the compound provided by the present invention is simple and low-cost.

[0017] Under irradiation with 297nm ultraviolet light, the fluorescence of 4-methyl-6-(2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine in n-hexane solution was significantly enhanced by about 12 times, and the fluorescence of 4,6-bis-2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine in n-hexane solution was significantly enhanced by about 5.5 times.

[0018] The main advantages of the symmetrical / asymmetrical tetraarylethene multi-stimulus-responsive fluorescent dyes containing 2-aminopyrimidine units of the present invention are: PAs have significant photochromic and photofluorescence enhancement properties and multi-stimulus-responsive properties, and possess high thermal and chemical stability; as an acid / base-responsive luminescent material, they have significant acid-induced chromic properties, which have potential applications in high-contrast, readily available safety inks; the cost of preparing raw materials is relatively low, the synthesis is simple, and they are conducive to industrial production and have great application prospects. In addition, PAs also have low cytotoxicity and good biocompatibility, can enter HeLa cells, and exhibit good cell staining function. Therefore, this type of compound can be used as a cell fluorescence marker and has potential application value in the field of cell dyes.

[0019] The main uses of the symmetrical / asymmetrical tetraarylethene multi-stimulus responsive fluorescent dye containing 2-aminopyrimidine units of the present invention are as follows: utilizing its significant photochromic and photofluorescence enhancement behavior, as well as its high thermal stability and chemical stability, it can be used to prepare blue light OLED materials and design small molecule biological fluorescent probes; utilizing its acid-induced fluorescence color change property, its color under natural light and fluorescence emission under ultraviolet light can be controllably adjusted, and its acid / base multicolor response property can be widely used in multicolor fluorescent dyes and anti-counterfeiting applications without fluorescence background; PAs can also be used as a selective and sensitive colorimetric and fluorescence ratio sensor to prepare test strips using it as a luminescent source for acid or Cr 3+ Detection.

[0020] The inventors have found that TAE compounds containing 3-thiophene substitution have high photoreactivity and can be used as a relatively ideal photoresponse unit to construct light stimulus responsive materials. 2-aminopyrimidine has good coplanarity and high electron affinity, and is an excellent ligand for constructing optical sensors and pH responsive materials. Therefore, combining 3-thiophene-substituted TAE with 2-aminopyrimidine receptors can achieve multiple stimulus responses and high-contrast multicolor displays. The tetraarylethylene fluorescent compound with multiple stimulus response characteristics protected by the present invention is different from the traditional tetraarylethylene AIEgens compound in that a strong electron-withdrawing pyrimidine unit is introduced. Through research, it was found that solvent polarity, acid / base response, light and metal ions (Cr 3+ 、Al 3+ and Fe 3+) and other stimuli can effectively regulate its luminescence properties. This type of compound has a simple molecular structure, mature synthesis method, low raw material cost, and significant multiple stimulus response characteristics. It has good application prospects in the fields of organic optoelectronic materials, biochemical detection, anti-counterfeiting and cell imaging. Therefore, the present invention is the first to apply for protection of the preparation method of symmetrical / asymmetrical tetraarylethenes with 2-aminopyrimidine units, the application in security inks and cell fluorescence imaging technology, which show significant photochromism, photofluorescence enhancement, acid-induced color change, Cr 3+ "Naked eye" recognition and other multi-color state change characteristics. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Absorption and emission spectra of compound PAs in THF and solid state;

[0022] Figure 2 The normalized fluorescence emission spectra of compound TPT-2-PA in different solvents;

[0023] Figure 3 The normalized fluorescence emission spectra of the compound BTPT-2-PA in different solvents;

[0024] Figure 4 This is the UV absorption spectrum of the compound TPT-2-PA acid / base titration;

[0025] Figure 5 is the UV absorption spectrum of compound TPT-2-PA at different pH in THF;

[0026] Figure 6 is the fluorescence emission spectrum of compound TPT-2-PA at different pH in THF;

[0027] Figure 7 This is the UV absorption spectrum of the compound BTPT-2-PA by acid / base titration;

[0028] Figure 8 Fluorescence emission spectrum of compound BTPT-2-PA by acid / base titration;

[0029] Figure 9 is the UV absorption spectrum of compound BTPT-2-PA at different pH in THF;

[0030] Figure 10 is the fluorescence emission spectrum of compound BTPT-2-PA at different pH in THF;

[0031] Figure 11 The UV-visible absorption spectrum of compound TPT-2-PA changes with 297nm ultraviolet irradiation time;

[0032] Figure 12 The UV-visible absorption spectrum of compound BTPT-2-PA changes with 297nm ultraviolet irradiation time;

[0033] Figure 13 is the fluorescence emission spectrum of compound TPT-2-PA as a function of 297nm ultraviolet irradiation time;

[0034] Figure 14 is the fluorescence emission spectrum of compound BTPT-2-PA as a function of 297nm ultraviolet irradiation time;

[0035] Figure 15 The UV absorption spectrum of compound TPT-2-PA for different cation selectivity;

[0036] Figure 16 The compound TPT-2-PA is 3+ UV titration absorption spectrum;

[0037] Figure 17 The compound TPT-2-PA is used to treat Cr 3+ UV titration absorption spectrum;

[0038] Figure 18 The compound TPT-2-PA reacts with Fe 3+ UV titration absorption spectrum;

[0039] Figure 19 The compound TPT-2-PA is 3+ Histogram of competition experiments;

[0040] Figure 20 The compound TPT-2-PA is used to treat Cr 3+ Histogram of competition experiments;

[0041] Figure 21 The compound TPT-2-PA reacts with Fe 3+ Histogram of competition experiments;

[0042] Figure 22 The compound TPT-2-PA is 3+ Job's complex diagram;

[0043] Figure 23 The compound TPT-2-PA is used to treat Cr 3+ Job's complex diagram;

[0044] Figure 24 The compound TPT-2-PA reacts with Fe 3+ Job's complex diagram;

[0045] Figure 25 The compound TPT-2-PA is 3+ (A), Cr 3+ (B) and Fe 3+ (C) Limit of detection (LOD) plot;

[0046] Figure 26 The compound TPT-2-PA is 3+ (A), Cr 3+ (B) and Fe 3+ (C) Binding constant plot;

[0047] Figure 27 The UV absorption spectrum (A) and fluorescence emission spectrum (B) of the compound BTPT-2-PA for different cation selectivities;

[0048] Figure 28 The compound BTPT-2-PA is 3+ UV titration absorption spectrum;

[0049] Figure 29 The compound BTPT-2-PA is used to treat Cr 3+ UV titration absorption spectrum;

[0050] Figure 30 The compound BTPT-2-PA is 3+ UV titration absorption spectrum;

[0051] Figure 31 The compound BTPT-2-PA is 3+ Fluorescence titration emission spectrum of

[0052] Figure 32 The compound BTPT-2-PA is used to treat Cr 3+ Fluorescence titration emission spectrum of

[0053] Figure 33 The compound BTPT-2-PA is 3+ Fluorescence titration emission spectrum of

[0054] Figure 34 The compound BTPT-2-PA is 3+ Histogram of competition experiments;

[0055] Figure 35 The compound BTPT-2-PA is used to treat Cr 3+ Histogram of competition experiments;

[0056] Figure 36 The compound BTPT-2-PA is 3+ Histogram of competition experiments;

[0057] Figure 37 The compound BTPT-2-PA is 3+ (A), Cr 3+ (B) and Fe 3+ (C) Job's complex diagram;

[0058] Figure 38 The compound BTPT-2-PA is 3+ (A), Cr 3+ (B) and Fe 3+ (C) Limit of detection (LOD) plot;

[0059] Figure 39 The compound BTPT-2-PA is 3+ (A), Cr 3+ (B) and Fe 3+ (C) Binding constant plot;

[0060] Figure 40 White light and fluorescence color images of compound PAs in solid state under TFA / TEA fumigation at different times: TPT-2-PA (A); BTPT-2-PA (B);

[0061] Figure 41 Anti-counterfeiting application of compound PAs with TFA / TEA fumigation of "single" (compound TPT-2-PA) and "double" (compound BTPT-2-PA) without interference from fluorescent background;

[0062] Figure 42 The test strips for the pH and cation selectivity of compound PAs are shown as follows: TPT-2-PA (A); BTPT-2-PA (B);

[0063] Figure 43 The bar graphs are the cytotoxicity experiments of compound PAs within 10 h: TPT-2-PA (A); BTPT-2-PA (B);

[0064] Figure 44 Cell fluorescence imaging of compound PAs. DETAILED DESCRIPTION

[0065] The present invention provides a multi-stimulus responsive optical chemical sensor, the open-loop and closed-loop changes of which are shown in Formula I:

[0066]

[0067] The present invention also provides a method for preparing the multi-stimulus-responsive optical chemical sensor.

[0068] In the present invention, the molar ratio of 2-bromo-1,1,2-triphenylethylene and 2-formyl-4-thiopheneboronic acid in step (1) is 1:1.5-2, preferably 1:1.6-1.9, and more preferably 1:1.7-1.8; the molar concentration of the palladium catalyst in the reaction solution is 8-12%, preferably 9-11%, and more preferably 10%; the amount ratio of the 2-bromo-1,1,2-triphenylethylene and the solvent is 10 mmol-0.1 mol: 80-250 mL, preferably 50 mmol-80 mmol: 100- 200mL:130~160mL; the alkaline compound is added in the form of an aqueous solution, the equivalent concentration of the alkaline compound solution is 3~7equiv., preferably 4~6equiv., and more preferably 5equiv., and the amount ratio of the 2-bromo-1,1,2-triphenylethylene to the alkaline compound solution is 10mmol~0.1mol:60~120mL, preferably 30mmol~0.08mol:80~100mL, and more preferably 50mmol~0.06mol:85~90mL.

[0069] In the present invention, the temperature of the Suzuki coupling reaction in step (1) is 78-82° C., preferably 80° C., and the time is 11-13 h, preferably 12 h.

[0070] After the Suzuki coupling reaction is completed, the present invention preferably performs post-treatment on the reaction solution, and the post-treatment preferably includes the following steps:

[0071] The Suzuki coupling reaction solution was cooled to room temperature and then the solvent was removed by rotary evaporation to obtain a rotary evaporation residue;

[0072] Extracting the residue from the rotary evaporation, and sequentially drying and filtering the obtained organic phase to obtain a filtrate;

[0073] The filtrate was rotary evaporated to remove the solvent and then subjected to column chromatography to obtain pure 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde.

[0074] In the present invention, the extraction solvent is preferably dichloromethane; the drying desiccant is preferably anhydrous sodium sulfate; the eluent for column chromatography separation is preferably a petroleum ether-ethyl acetate mixture; the volume ratio of petroleum ether to ethyl acetate in the mixture is preferably 15:1. The present invention has no particular requirements for the specific methods of the rotary evaporation and filtration operations; methods well known to those skilled in the art can be used. In the present invention, the 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde obtained after column chromatography separation is a light yellow solid.

[0075] In the present invention, in step (2), the molar ratio of 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde to tetrabutylammonium hydrogen sulfate is 1.0-1.2:1, preferably 1.1:1; the molar ratio of 2-amino-4,6-dimethylpyrimidine to tetrabutylammonium hydrogen sulfate is 5-6:2.5-3, preferably 5.5-5.8:2.6-2.7; the amount ratio of 2-amino-4,6-dimethylpyrimidine to solvent is 5-6 mmol:70-90 mL, preferably 5.5-5.6 mmol:75-85 mL.

[0076] In the present invention, the temperature of the condensation reaction in step (2) is 115-125° C., preferably 116-123° C., more preferably 120-121° C., and the time is 4-8 h, preferably 5-7 h; the solvent is sodium hydroxide solution or potassium hydroxide solution, and the concentration is 4-6 mol / L, preferably 5 mol / L.

[0077] After the condensation reaction is completed, the present invention preferably performs post-treatment on the reaction solution, and the post-treatment preferably includes the following steps:

[0078] The condensation reaction solution was cooled to room temperature and then filtered to remove the solvent to obtain a black block solid;

[0079] Extracting the black block solid, and sequentially drying and filtering the obtained organic phase to obtain a filtrate;

[0080] The filtrate was rotary evaporated to remove the solvent and then separated by column chromatography. The obtained substance was recrystallized to obtain pure 4-methyl-6-(2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (TPT-2-PA) and 4,6-bis-2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (BTPT-2-PA).

[0081] In the present invention, the extraction agent is preferably dichloromethane; the drying agent is preferably anhydrous sodium sulfate; the eluent for column chromatography separation is preferably a petroleum ether-ethyl acetate mixture and a dichloromethane-ethyl acetate mixture; the volume ratio of petroleum ether and ethyl acetate in the mixture is preferably 5:1, and the volume ratio of dichloromethane-ethyl acetate mixture is preferably 10:1; the present invention has no special requirements for the specific methods of the rotary evaporation, filtration and other operations, and methods familiar to those skilled in the art can be used. In the present invention, the 4-methyl-6-(2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (TPT-2-PA) obtained after recrystallization is a light yellow solid, and the 4,6-bis-2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (BTPT-2-PA) is a yellow solid.

[0082] The preparation method of the above-mentioned symmetrical / asymmetrical tetraarylethene multi-stimulus-responsive fluorescent dye containing a 2-aminopyrimidine unit provided by the present invention only involves Suzuki coupling reaction and condensation reaction. Compared with common tetraphenylethylene and distyryl anthracene compounds, the raw material cost is low, the synthesis method and steps are simpler, the preparation conditions are milder, it is suitable for industrial production, and has broad application prospects.

[0083] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0084] Example 1

[0085] Preparation of symmetrical / asymmetrical tetraarylethene multi-stimulus-responsive fluorescent dye PAs containing 2-aminopyrimidine units (asymmetrical 4-methyl-6-(2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (TPT-2-PA) and symmetrical 4,6-bis-2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (BTPT-2-PA)):

[0086] (1) Preparation of 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde:

[0087] Under nitrogen, 2-bromo-1,1,2-triphenylethylene (2.011 g, 6.0 mmol) and Pd(PPh3)4 (10 mol%) were dissolved in 80.0 mL of THF. After stirring for 30 min, 2-formyl-4-thiopheneboronic acid (1.40 g, 9.0 mmol) and 60 mL of a 5.0 equiv. Na2CO3 solution were added. The mixture was heated to 80°C and refluxed for 12 h. The reaction was stopped and cooled to room temperature. The solvent was removed by rotary evaporation, and the mixture was extracted with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate. The filtrate was filtered, the solvent removed by rotary evaporation, and column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent afforded a light-colored solid (1.65 g, 4.50 mmol) in a 75% yield.

[0088] (2) Preparation of 4-methyl-6-(2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (TPT-2-PA) and 4,6-bis-2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (BTPT-2-PA) (as shown in Formula II):

[0089]

[0090] Under nitrogen, dissolve 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde (1.0 g, 2.70 mmol) and TBAHS (0.92 g, 2.70 mmol) in 80.0 mL of 5.0 mol / L NaOH solution. Stir for 10 minutes, then add 2-amino-4,6-dimethylpyrimidine (0.67 g, 5.40 mmol). Heat to 120°C and reflux for 6 hours to stop the reaction. Cool to room temperature, remove the solvent by filtration, extract with dichloromethane, combine the organic phases, and dry over anhydrous magnesium sulfate. The filtrate was filtered and the solvent was evaporated. The product was separated by column chromatography using a petroleum ether-ethyl acetate mixture as the eluent, and recrystallized from n-hexane to obtain a light yellow solid TPT-2-PA (0.40 g, 0.85 mmol) with a yield of 31%. The product was further separated by column chromatography using a dichloromethane-ethyl acetate mixture as the eluent, and recrystallized from n-hexane to obtain a yellow solid BTPT-2-PA (0.35 g, 0.43 mmol) with a yield of 16%.

[0091] TPT-2-PA structure identification: 1H NMR (500MHz, CDCl3): δ2.33(s,3H),5.03(s,2H),6.43(s,1H),6.49(s,1H),6.53(s,1H),6.66(s,1H),6.71(s,1H ),6.97–6.99(m,2H),7.07–7.10(m,5H),7.14(d,J=5.0Hz,5H),7.21(t,J=5.0Hz,3H),7.60(s,1H),7.63(s,1H).

[0092] BTPT-2-PA structure identification: 1 H NMR (500MHz, CDCl3): δ4.90(s,2H),6.47(s,1H),6.52(s,1H),6.55(s,1H),6.65(s,2H),6.70(s,2H),6.97– 9.99(m,4H),7.07–7.10(m,10H),7.14(d,J=5.0MHz,10H),7.21(t,J=5.0MHz,6H),7.58(s,1H),7.62(s,1H).

[0093] Example 2

[0094] (1) Preparation of 4-methyl-6-(2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (TPT-2-PA) (as shown in Formula III):

[0095]

[0096] Under nitrogen, 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde (prepared according to Example 1, 1.0 g, 2.70 mmol) and TBAHS (0.92 g, 2.70 mmol) were dissolved in 80.0 mL of 5.0 mol / L NaOH solution. After stirring for 10 minutes, 2-amino-4,6-dimethylpyrimidine (1.0 g, 8.1 mmol) was added. The mixture was heated under reflux for 3 hours, stopped, and cooled to room temperature. The solvent was removed by filtration, and the mixture was extracted with dichloromethane. The combined organic phases were dried over anhydrous magnesium sulfate. The filtrate was filtered, the solvent was evaporated, and the mixture was separated by column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent. The mixture was recrystallized from n-hexane to obtain TPT-2-PA (0.70 g, 1.49 mmol) as a pale yellow solid in a 55% yield.

[0097] Example 3

[0098] (1) Preparation of 4,6-bis-2-(4-(1,2,2-triphenylvinyl)thiophen-2-yl)vinyl)pyrimidin-2-amine (BTPT-2-PA) (as shown in Formula IV):

[0099]

[0100] Under nitrogen, 4-(1,2,2-triphenylvinyl)thiophene-2-carbaldehyde (prepared according to Example 1, 2.0 g, 5.40 mmol) and TBAHS (1.84 g, 5.40 mmol) were dissolved in 100.0 mL of 5.0 mol / L NaOH solution. After stirring for 10 minutes, 2-amino-4,6-dimethylpyrimidine (0.34 g, 2.70 mmol) was added. The mixture was heated at reflux for 8 hours, stopped, and cooled to room temperature. The solvent was removed by filtration, and the mixture was extracted with dichloromethane. The combined organic phases were dried over anhydrous magnesium sulfate. The filtrate was filtered, the solvent was evaporated, and the mixture was separated by column chromatography using a dichloromethane-ethyl acetate mixture as the eluent. BTPT-2-PA was obtained as a yellow solid (0.82 g, 1.0 mmol) in a 29% yield.

[0101] Characterization data of each compound in Example 1:

[0102] Figure 1 Absorption and emission spectra of compound PAs in THF and solid state; Figure 2 The normalized fluorescence emission spectra of compound TPT-2-PA in different solvents; the concentration of TPT-2-PA is 2.0×10 -5 mol / L, compared with the non-polar solvent n-hexane, the emission wavelength in highly polar solvents is more red-shifted, showing an obvious solvent effect; Figure 3 The normalized fluorescence emission spectra of the compound BTPT-2-PA in different solvents; the concentration of BTPT-2-PA is 2.0×10 -5 mol / L, compared with the non-polar solvent n-hexane, the emission wavelength in highly polar solvents is more red-shifted, showing an obvious solvent effect; Figure 4 The UV absorption spectrum of the compound TPT-2-PA was obtained by acid / base titration. A good linear relationship curve was found between the absorption intensity ratio and the hydrochloric acid concentration. The results showed that TPT-2-PA can be used as a quantitative detection method for H + Colorimetric chemical sensors; Figure 5 The UV absorption spectra of compound TPT-2-PA at different pH values ​​in THF are shown below. The absorption intensity changes slightly between pH 7 and 11, and the spectral distribution does not change significantly. The absorption intensity at pH < 7 undergoes a significant red shift. Figure 6Figure 2 shows the fluorescence emission spectra of compound TPT-2-PA at different pH values ​​in THF. At alkaline pH values ​​> 7.0, the fluorescence of TPT-2-PA does not change significantly to a certain extent (<4-fold). When the pH value drops below 7.0, a red shift occurs, and when the pH reaches 1, the fluorescence is essentially completely quenched. Figure 7 The UV absorption spectrum of the compound BTPT-2-PA was obtained by acid / base titration. A good linear relationship curve was found between the absorption intensity ratio and the concentration of hydrochloric acid. The results showed that BTPT-2-PA can be used as a quantitative detection method for H + Colorimetric chemical sensors; Figure 8 The fluorescence emission spectrum of the compound BTPT-2-PA in acid / base titration is shown in Figure 2. There is a good linear relationship between the emission intensity ratio and the hydrochloric acid concentration. The results show that BTPT-2-PA can be used as a quantitative detection method for H + The fluorescence chemical sensor is almost completely quenched with the increase of acidic environment. Figure 9 The UV absorption spectra of the compound BTPT-2-PA at different pH values ​​in THF are shown below. The absorption intensity changes slightly between pH 7 and 11, but the spectral distribution does not change significantly. When the pH is less than 7, the absorption intensity at 310 nm decreases significantly, showing a clear red shift, and a strong absorption peak appears at 464 nm. Figure 10 Figure 2 shows the fluorescence emission spectra of the compound BTPT-2-PA at different pH values ​​in THF. At alkaline pH values ​​> 7.0, the fluorescence of BTPT-2-PA does not change significantly to a certain extent. However, when the pH value drops below 7.0, a red shift occurs, and the fluorescence intensity decreases significantly. When the pH reaches 1, the fluorescence is essentially completely quenched. Figure 11 The UV-visible absorption spectrum of compound TPT-2-PA changes with 297nm ultraviolet irradiation time. As the irradiation time increases, the absorption peak at 314nm gradually decreases, an isosbestic point appears at 381nm, and a new absorption peak gradually appears at 521nm. After 200s of irradiation, the light saturation state is reached. Figure 12 The UV-visible absorption spectrum of the compound BTPT-2-PA changes with 297nm ultraviolet irradiation time. As the irradiation time increases, the absorption peaks at 310 / 390 / 411nm gradually decrease, an isosbestic point appears at 420nm, and a new absorption peak gradually emerges at 529nm. After 200s of irradiation, the light saturation state is reached. Figure 13 The fluorescence emission spectrum of compound TPT-2-PA in n-hexane solution changes with 297nm ultraviolet irradiation time. As the irradiation time increases, the emission wavelength blue-shifts from 472nm to 452nm, the fluorescence significantly increases, and reaches saturation at 250s. Figure 14The fluorescence emission spectrum of the compound BTPT-2-PA in n-hexane solution changes with 297nm ultraviolet irradiation time. As the irradiation time increases, the emission wavelength red-shifts from 469nm to 474nm, the fluorescence significantly increases, and reaches saturation in 200s. Figure 15 is the UV absorption spectrum of compound TPT-2-PA for different cation selectivity; 3+ Cr 3+ and Fe 3+ UV selective; Figure 16 The compound TPT-2-PA is 3+ UV titration absorption spectrum; Figure 17 The compound TPT-2-PA is used to treat Cr 3+ UV titration absorption spectrum; Figure 18 The compound TPT-2-PA reacts with Fe 3+ UV titration absorption spectrum; Figure 19 The compound TPT-2-PA is 3+ Histogram of competition experiments; Figure 20 The compound TPT-2-PA is used to treat Cr 3+ Histogram of competition experiments; Figure 21 The compound TPT-2-PA reacts with Fe 3+ Competition experiment bar graph of TPT-2-PA against Al 3+ Cr 3+ and Fe 3+ The UV response has good anti-interference performance; Figure 22 The compound TPT-2-PA is 3+ Job's complex diagram; Figure 23 The compound TPT-2-PA is used to treat Cr 3+ Job's complex diagram;

[0103] Figure 24 The compound TPT-2-PA reacts with Fe 3+ Job's complex diagram; Compound TPT-2-PA to Al 3+ Cr 3+ and Fe 3+ All complexes were carried out in a stoichiometric ratio of 1:1; Figure 25 The compound TPT-2-PA is 3+ (A), Cr 3+ (B) and Fe 3+ (C) Detection limit (LOD) diagram of compound TPT-2-PA for Al 3+ Cr 3+ and Fe 3+ The detection limits were 2.88×10-7 mol / L, 1.96×10 -8 mol / L, 8.45×10 -7 mol / L; Figure 26 The compound TPT-2-PA is 3+ (A), Cr 3+ (B) and Fe 3+ (C) Binding constant diagram of compound TPT-2-PA for Al 3+ Cr 3+ and Fe 3+ The binding constants are 4.80×10 5 L / mol, 5.10×10 5 L / mol, 4.08×10 5 L / mol; Figure 27 The UV absorption spectrum (A) and fluorescence emission spectrum (B) of the compound BTPT-2-PA for different cation selectivities are shown. 3+ Cr 3+ and Fe 3+ With UV and fluorescence selectivity; Figure 28 The compound BTPT-2-PA is 3+ UV titration absorption spectrum; Figure 29 The compound BTPT-2-PA is used to treat Cr 3+ UV titration absorption spectrum; Figure 30 The compound BTPT-2-PA is 3+ UV titration absorption spectrum; Figure 31 The compound BTPT-2-PA is 3+ Fluorescence titration emission spectrum of Figure 32 The compound BTPT-2-PA is used to treat Cr 3+ Fluorescence titration emission spectrum of Figure 33 The compound BTPT-2-PA is 3+ Fluorescence titration emission spectrum of Figure 34 The compound BTPT-2-PA is 3+ Histogram of competition experiments; Figure 35 The compound BTPT-2-PA is used to treat Cr 3+ Histogram of competition experiments; Figure 36 The compound BTPT-2-PA is 3+ The competitive experiment bar graph of BTPT-2-PA on Al 3+ Cr 3+ and Fe 3+ The UV response has good anti-interference performance; Figure 37The compound BTPT-2-PA is 3+ (A), Cr 3+ (B) and Fe 3+ (C) Job's complex diagram; Compound BTPT-2-PA to Al 3+ Cr 3+ and Fe 3+ All complexes were carried out in a stoichiometric ratio of 1:1; Figure 38 The compound BTPT-2-PA is 3+ (A), Cr 3+ (B) and Fe 3+ (C) Detection limit (LOD) diagram of compound BTPT-2-PA for Al 3+ Cr 3+ and Fe 3+ The detection limits were 1.18×10 -7 mol / L, 1.49×10 -7 mol / L, 2.08×10 -7 mol / L. Figure 39 The compound BTPT-2-PA is 3+ (A), Cr 3+ (B) and Fe 3+ (C) Binding constant diagram of compound BTPT-2-PA for Al 3+ Cr 3+ and Fe 3+ The binding constants are 4.09×10 3 L / mol, 8.45×10 3 L / mol, 1.55×10 3 L / mol; Figure 40 Images of the white light and fluorescence colors of solid-state PAs after TFA / TEA fumigation at different times: TPT-2-PA (A); BTPT-2-PA (B). Both the white light and fluorescence colors of solid-state PAs exhibit multicolor effects, and this is a reversible process. Figure 41 The anti-counterfeiting application of the words "single" (compound TPT-2-PA) and "double" (compound BTPT-2-PA) written on PAs compounds under TFA / TEA fumigation without interference from fluorescence background; under TFA / TEA fumigation, the color of the words written on the PAs compounds changed visibly to the naked eye, and the fluorescence was completely quenched after acid fumigation in the absence of fluorescence background. Figure 42The test strips for the selectivity of compound PAs for pH and cations are shown in Figure 1: TPT-2-PA (A); BTPT-2-PA (B). When the test strips impregnated with PAs compounds were placed in different pH environments, their white light and fluorescence changed significantly. When a drop of Al was added to the test strips impregnated with PAs compounds, 3+ Cr 3+ and Fe 3+ After the solution is dissolved, color and fluorescence changes can be observed immediately. Figure 43 The bar graphs show the cytotoxicity of PAs within 10 hours: TPT-2-PA (A); BTPT-2-PA (B). The bar graphs show that PAs compounds exhibit low cytotoxicity at low concentrations within 10 hours, indicating good cytocompatibility.

[0104] Experimental example: Cell imaging experiment:

[0105] HeLa cells were cultured in bovine serum supplemented with 10% (mass fraction) DMEM at 37°C in an atmosphere of 5% CO2-95% air. The cells were placed in a 20mm cell culture dish and allowed to stand overnight before the experiment. After rinsing the HeLa cells with phosphate-buffered saline (PBS), the HeLa cells were stained with compounds TPT-2-PA and BTPT-2-PA (at a concentration of 20 μM), respectively, and incubated in culture medium for 30 minutes. After rinsing the HeLa cells three times with PBS, the cells were imaged using an OLYMPUS FV1000 confocal laser scanning microscope, using the fluorescence emission at 430-530 nm as the collection channel. The results are shown in Figure 2. Figure 44 shown. Figure 44 The fluorescence imaging diagrams of compound PAs cells are shown in Figure 1, where A1–A3 correspond to the fluorescence dark field imaging diagram, bright field imaging diagram and superposition field imaging diagram of blank control group cells, respectively; B1–B3 correspond to the fluorescence dark field imaging diagram, bright field imaging diagram and superposition field imaging diagram of compound TPT-2-PA, respectively; C1–C3 correspond to the fluorescence dark field imaging diagram, bright field imaging diagram and superposition field imaging diagram of BTPT-2-PA, respectively. Figure 44 It can be seen that the compound PAs provided by the present invention can effectively enter HeLa cells and exhibit good cell staining function. Therefore, the compound provided by the present invention can be used as a cell fluorescence marker and has potential application value in the field of cell dyes.

Claims

1. A multi-stimulus responsive photochemical sensor, characterized in that: Include and .

2. The method for preparing the multi-stimulus responsive optical chemical sensor according to claim 1, characterized in that: The following steps are included: (1) Under a protective atmosphere, 2-bromo-1,1,2-triphenylethylene, 2-formyl-4-thiopheneboronic acid, a palladium catalyst, a basic compound, and a solvent are mixed to undergo a Suzuki coupling reaction to obtain 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde; (2) Under a protective atmosphere, 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde, 2-amino-4,6-dimethylpyrimidine, tetrabutylammonium hydrogen sulfate and a solvent were mixed and condensed to obtain a multi-stimulus responsive photochemical sensor.

3. The preparation method according to claim 2, characterized in that In step (1), the molar ratio of 2-bromo-1,1,2-triphenylethylene to 2-formyl-4-thiopheneboronic acid is 1:1.5-2; The molar concentration of the palladium catalyst in the reaction solution is 8-12%; The ratio of 2-bromo-1,1,2-triphenylethylene to solvent is 10 mmol to 0.1 mol: 80 to 250 mL; The alkaline compound is added in the form of an aqueous solution, the equivalent concentration of the alkaline compound solution is 3 to 7 equiv., and the amount ratio of the 2-bromo-1,1,2-triphenylethylene to the alkaline compound solution is 10 mmol to 0.1 mol: 60 to 120 mL.

4. The preparation method according to claim 2 or 3, characterized in that The temperature of the Suzuki coupling reaction in step (1) is 78-82°C and the reaction time is 11-13 hours; The protective atmosphere is a nitrogen atmosphere.

5. The preparation method according to claim 4, characterized in that The palladium catalyst in step (1) comprises one or more of Pd(PPh3)4, PdCl2(dppf)2, Pd(dppf)Cl2 and Pd(OAc)2; Alkaline compounds include Na2CO3, Ba(OH)2, K3PO4, Cs2CO3, K2CO3, TiOH, KF, CsF, Bu4F, NaOH and i -One or more of PrNEt2; The solvent comprises one or more of tetrahydrofuran, CH2Cl2, N,N-dimethylformamide and CH3CN.

6. The preparation method according to claim 2, 3 or 5, characterized in that: In step (2), the molar ratio of 4-(1,2,2-triphenylvinyl)thiophene-2-carboxaldehyde to tetrabutylammonium hydrogen sulfate is 1.0-1.2:1; The molar ratio of 2-amino-4,6-dimethylpyrimidine to tetrabutylammonium hydrogen sulfate is 5-6:2.5-3; The usage ratio of 2-amino-4,6-dimethylpyrimidine and solvent is 5~6mmol:70~90mL.

7. The preparation method according to claim 6, characterized in that The condensation reaction temperature in step (2) is 115-125°C and the reaction time is 4-8 hours; The protective atmosphere is a nitrogen atmosphere; The solvent is a sodium hydroxide solution or a potassium hydroxide solution with a concentration of 4-6 mol / L.

8. The multiple stimulus-responsive photochemical sensor according to claim 1 or the multiple stimulus-responsive photochemical sensor prepared by the method according to any one of claims 2 to 7 in the preparation of acid-base response, photochromic, Cr 3+ Applications in "naked eye" identification, reagents for cell fluorescence imaging, security inks, or anti-counterfeiting.

9. Use of the multi-stimulus-responsive optical chemical sensor according to claim 1 or the multi-stimulus-responsive optical chemical sensor prepared by the method according to any one of claims 2 to 7 in preparing ion sensing reagents, characterized in that: The ion is Al 3+ Cr 3+ and Fe 3+ .

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