Triphenylamine two-photon fluorescence probe compound and preparation method and application thereof

Abstract

The invention belongs to the field of organic nonlinear optical materials, and particularly relates to a triphenylamine two-photon fluorescence probe compound and a preparation method and an application thereof. The preparation method of the triphenylamine two-photon fluorescence probe compound comprises the following steps of: injecting anhydrous benzene into 4-nitrapyrin-2, 6-dimethyl isophthalate and triphenylphosphine under the protection of nitrogen; increasing temperature, refluxing, and cooling; filtering and washing to obtain chlorination-4-methylene triphenylphosphine group-pyridine-2,6-dimethyl isophthalate, and dissolving into methanol; mixing and stirring tri(4-formylphenyl)amine and absolute methanol; adding the methanol solution of the chlorination-4-methylene triphenylphosphine group-pyridine-2,6-dimethyl isophthalate and the methanol solution of sodium methylate; stirring at 0-5 DEG C for 1-2 hours, stirring at normal temperature for 3-4 hours; separating through column chromatography. The triphenylamine two-photon fluorescence probe compound disclosed by the invention has the advantages of outstandingly enhanced two-photon absorption section, good water solubility, higher reaction activity and very high coordination capacity and can be applied to silver ion detection and pH detection.

Description

technical field

[0001] The invention belongs to the field of organic nonlinear optical materials, in particular to a triphenylamine two-photon fluorescent probe compound and its preparation method and application. Background technique

[0002] In 1990, Denk of Cornell University in the United States proposed to apply the two-photon excitation phenomenon to the confocal laser scanning microscope, which opened up a new field of two-photon fluorescence microscopy and imaging. Two-photon fluorescence microscopy has features such as near-infrared excitation, dark-field imaging, avoidance of fluorescence bleaching and phototoxicity, targeted excitation, high horizontal and vertical resolution, reduced biological tissue absorption coefficient, and reduced tissue autofluorescence interference. It is significantly better than single-photon fluorescence microscopy imaging, providing a sharper tool for life sciences. In order to achieve the maximum range of applications of two-photon ...

Examples

Embodiment 1

[0043] 1. Synthesis of dimethyl chloride-4-methylenetriphenylphosphino-pyridine-2,6-dicarboxylate

[0044] (1) Synthesis of pyridine-2,6-dicarboxylic acid

[0045]Put 500mL of distilled water and 12mL (92mmol) of 2,6-lutidine in a 1000mL round-bottomed flask, slowly add 80g (506mmol) of potassium permanganate under magnetic stirring, and insert a reflux condenser. Reflux at 110°C-115°C for 3.5h. The reaction was stopped, cooled to room temperature, and the black solid was removed by suction filtration. The colorless filtrate was collected, and four fifths of the filtrate was removed under reduced pressure. With continuous stirring, slowly pour about 20 mL of sulfuric acid with a volume concentration of 70%, and a large amount of white crude product is precipitated. After cooling, filter with suction to obtain pyridine-2,6-dicarboxylic acid.

[0046] (2) Synthesis of dimethyl pyridine-2,6-dicarboxylate

[0047] Put 33.5g (200mmol) of pyridine-2,6-dicarboxylic acid, 120mL (1...

Embodiment 2

[0061] The selectivity of compound I to silver ion

[0062] Using the probe compound I synthesized in Example 1, the selectivity to silver ions was evaluated by absorption spectroscopy. Dissolve compound I in a mixed solvent of dimethyl sulfoxide: distilled water = 5:95 (volume ratio), and prepare compound I with a concentration of 1×10 -5 mol / L mixed solution, add different metal ions respectively, so that the concentration of metal ions is 1×10 -5 mol / L, test its single-photon absorption spectrum, the specific results are as follows image 3 shown, from image 3 It can be seen that compound I has high selectivity to silver ions (the metal ion is Ag + 、Na + , Ca 2+ 、Cd 2+ , Fe 2+ , Zn 2+ , Hg 2+ , Mg 2+ , Pb 2+ , Mn 2+ ), when silver ions were added to the solution of compound I, the absorbance of the solution around 305nm increased significantly; while other metal ions were added to the solution of compound I, the absorbance hardly changed.

[0063] It is 1×10 t...

Embodiment 3

[0065] Absorption responses of compound I to different concentrations of silver ions

[0066] Using the probe compound I synthesized in Example 1, dissolve compound I in a mixed solvent of dimethyl sulfoxide:distilled water=5:95 (volume ratio), and prepare the compound I with a concentration of 1×10 -5 mol / L mixed solution, adding different concentrations of silver ions, the concentration of silver ions changes from small to large in order of 0, 1×10 -7 mol / L, 5×10 -7 mol / L, 1×10 -6 mol / L, 2×10 -6 mol / L, 4×10 -6 mol / L, 6×10 -6 mol / L, 8×10 -6 mol / L, 1×10 -5 mol / L, 2×10 -5 mol / L, 4×10 -5 mol / L, 6×10 -5 mol / L, 8×10 -5 mol / L and 1×10 -4 mol / L, specifically as Figure 5 As can be seen from the figure, the single-photon absorbance of Compound I of the present invention is positively related to the concentration of silver ions.

technical field

[0001] The invention belongs to the field of organic nonlinear optical materials, in particular to a triphenylamine two-photon fluorescent probe compound and its preparation method and application. Background technique

[0002] In 1990, Denk of Cornell University in the United States proposed to apply the two-photon excitation phenomenon to the confocal laser scanning microscope, which opened up a new field of two-photon fluorescence microscopy and imaging. Two-photon fluorescence microscopy has features such as near-infrared excitation, dark-field imaging, avoidance of fluorescence bleaching and phototoxicity, targeted excitation, high horizontal and vertical resolution, reduced biological tissue absorption coefficient, and reduced tissue autofluorescence interference. It is significantly better than single-photon fluorescence microscopy imaging, providing a sharper tool for life sciences. In order to achieve the maximum range of applications of two-photon ...

Examples

Embodiment 1

[0043] 1. Synthesis of dimethyl chloride-4-methylenetriphenylphosphino-pyridine-2,6-dicarboxylate

[0044] (1) Synthesis of pyridine-2,6-dicarboxylic acid

[0045]Put 500mL of distilled water and 12mL (92mmol) of 2,6-lutidine in a 1000mL round-bottomed flask, slowly add 80g (506mmol) of potassium permanganate under magnetic stirring, and insert a reflux condenser. Reflux at 110°C-115°C for 3.5h. The reaction was stopped, cooled to room temperature, and the black solid was removed by suction filtration. The colorless filtrate was collected, and four fifths of the filtrate was removed under reduced pressure. With continuous stirring, slowly pour about 20 mL of sulfuric acid with a volume concentration of 70%, and a large amount of white crude product is precipitated. After cooling, filter with suction to obtain pyridine-2,6-dicarboxylic acid.

[0046] (2) Synthesis of dimethyl pyridine-2,6-dicarboxylate

[0047] Put 33.5g (200mmol) of pyridine-2,6-dicarboxylic acid, 120mL (1...

Embodiment 2

[0061] The selectivity of compound I to silver ion

[0062] Using the probe compound I synthesized in Example 1, the selectivity to silver ions was evaluated by absorption spectroscopy. Dissolve compound I in a mixed solvent of dimethyl sulfoxide: distilled water = 5:95 (volume ratio), and prepare compound I with a concentration of 1×10 -5 mol / L mixed solution, add different metal ions respectively, so that the concentration of metal ions is 1×10 -5 mol / L, test its single-photon absorption spectrum, the specific results are as follows image 3 shown, from image 3 It can be seen that compound I has high selectivity to silver ions (the metal ion is Ag + 、Na + , Ca 2+ 、Cd 2+ , Fe 2+ , Zn 2+ , Hg 2+ , Mg 2+ , Pb 2+ , Mn 2+ ), when silver ions were added to the solution of compound I, the absorbance of the solution around 305nm increased significantly; while other metal ions were added to the solution of compound I, the absorbance hardly changed.

[0063] It is 1×10 t...

Embodiment 3

[0065] Absorption responses of compound I to different concentrations of silver ions

[0066] Using the probe compound I synthesized in Example 1, dissolve compound I in a mixed solvent of dimethyl sulfoxide:distilled water=5:95 (volume ratio), and prepare the compound I with a concentration of 1×10 -5 mol / L mixed solution, adding different concentrations of silver ions, the concentration of silver ions changes from small to large in order of 0, 1×10 -7 mol / L, 5×10 -7 mol / L, 1×10 -6 mol / L, 2×10 -6 mol / L, 4×10 -6 mol / L, 6×10 -6 mol / L, 8×10 -6 mol / L, 1×10 -5 mol / L, 2×10 -5 mol / L, 4×10 -5 mol / L, 6×10 -5 mol / L, 8×10 -5 mol / L and 1×10 -4 mol / L, specifically as Figure 5 As can be seen from the figure, the single-photon absorbance of Compound I of the present invention is positively related to the concentration of silver ions.

Images