1. A compound for rapidly detecting zinc ions, which is characterized in that the system is named as 9, 10-bis [ bis (2-picolyl) aminomethyl ] anthracene, and the structural formula is as follows:

2. the method for preparing a compound for rapid detection of zinc ions according to claim 1, comprising the steps of:

(1) dissolving anthracene in acetic acid solution of hydrogen bromide;

(2) adding 1,3, 5-trioxymethylene and N, N, N-trimethyl-1-tetradecyl ammonium bromide into the system obtained in the step (1) for reaction to obtain yellow solid;

(3) and (3) dissolving the yellow solid obtained in the step (2), bis (2-pyridylmethyl) amine and triethylamine in tetrahydrofuran to react, and using the compound for rapidly detecting zinc ions.

3. The method for preparing a compound for rapid detection of zinc ions according to claim 2, wherein: in the step (1), the mass ratio of anthracene to hydrogen bromide is 10:298, and the volume ratio of hydrogen bromide to acetic acid in an acetic acid solution of hydrogen bromide is 4: 1.

4. The method for preparing a compound for rapid detection of zinc ions according to claim 2, wherein: in the step (2), the mass ratio of anthracene, 1,3, 5-trioxymethylene and N, N, N-trimethyl-1-tetradecyl ammonium bromide is 25:25:1-15:15: 6.

5. The method for preparing a compound for rapid detection of zinc ions according to claim 2, wherein: in the step (2), the yellow solid is washed by ethanol.

6. The method for preparing a compound for rapid detection of zinc ions according to claim 2, wherein: the reaction temperature of the step (2) is 80-90 ℃, and the reaction time is 18-24 h.

7. The method for preparing a compound for rapid detection of zinc ions according to claim 2, wherein: the reaction temperature of the step (3) is 25-30 ℃, and the reaction time is 3-5 h.

8. The method for preparing a compound for rapid detection of zinc ions according to claim 2, wherein: in the step (3), the mass ratio of the yellow solid to the bis (2-pyridylmethyl) amine is 5:2-3:1, and the mass ratio of the triethylamine to the bis (2-pyridylmethyl) amine is 3:1-5: 1.

Background

The zinc ion has important significance for maintaining biological functions, and the zinc ion directly participates in enzyme synthesis, and has multiple important functions of promoting the growth and development of organisms and tissue regeneration, protecting skin health, maintaining immune functions and the like. However, the environment in animals and human bodies is very complex, and the influence of factors such as blood brain barrier and the like exists, so that the method for properly measuring zinc ions is few. At present, the zinc ion content of a human body is generally measured by an atomic absorption detection method for taking blood samples or hair, or a gas chromatography; the two methods have the problems of low speed, poor selectivity, low result sensitivity, high cost and the like.

Disclosure of Invention

The invention aims to provide a compound for rapidly detecting zinc ions and a preparation method thereof, and the compound has the advantages of high detection speed, high selectivity, high sensitivity and low cost when being used for detecting the zinc ions.

The first purpose of the invention is realized by the following technical scheme that the compound for rapidly detecting the zinc ions has the following structural formula:

the second purpose of the invention is realized by the following technical scheme:

a preparation method of a compound for rapidly detecting zinc ions comprises the following steps:

(1) dissolving anthracene in acetic acid solution of hydrogen bromide;

(2) adding 1,3, 5-trioxymethylene and N, N, N-trimethyl-1-tetradecyl ammonium bromide into the system obtained in the step (1) for reaction to obtain yellow solid;

(3) and (3) dissolving the yellow solid obtained in the step (2), bis (2-pyridylmethyl) amine and triethylamine in tetrahydrofuran to react, and using the compound for rapidly detecting zinc ions.

Preferably, in the step (1), the mass ratio of the acetic acid solution of anthracene to hydrogen bromide is 10:298, and the volume ratio of hydrogen bromide to acetic acid in the acetic acid solution of hydrogen bromide is 4: 1.

Preferably, in the step (2), the mass ratio of anthracene, 1,3, 5-trioxymethylene and N, N, N-trimethyl-1-tetradecylammonium bromide is 25:25: 1.

Preferably, in the step (2), the yellow solid is washed with ethanol.

Preferably, the reaction temperature of the step (2) is 80-90 ℃, and the reaction time is 18-24 h.

Preferably, the reaction temperature of the step (3) is 25-30 ℃, and the reaction time is 3-5 h.

Preferably, in the step (3), the mass ratio of the yellow solid to the bis (2-pyridylmethyl) amine is 5:2, and the mass ratio of triethylamine to the bis (2-pyridylmethyl) amine is 5: 1.

The invention has the following advantages:

(1) the compound prepared by the invention can break through blood brain barrier through animal model and living body imaging verification, shows good detection signals under complex biological background in brain, and is expected to be used as a reliable depression detection probe.

(2) The invention utilizes the fluorescence spectrum technology for detection, the method is simple, and the identification process does not need pretreatment operation; the detection range is wide, and the method can be used in a plurality of different fields such as in vivo detection, environmental detection and the like.

(3) The compound prepared by the invention realizes better selectivity to zinc ions in an organic solvent environment, and is not easy to interfere; the lower detection limit is low, and trace (ppm level) zinc ions can be detected; in the experiment, zinc ions are added in a trace amount, so the experiment has high sensitivity and high selectivity.

(4) The preparation raw materials of the invention are anthracene, 1,3, 5-trioxymethylene, N, N, N-trimethyl-1-tetradecyl ammonium bromide and the like, and the raw materials have low price; and the synthesis route is simple, the reaction condition is mild, and no by-product is generated.

Drawings

FIG. 1 is a structural formula of a target compound of the present invention;

FIG. 2 is a reaction scheme for the synthesis of a target compound according to the present invention;

FIG. 3 is a drawing showing the preparation of a target compound of the present invention¹H NMR chart;

FIG. 4 shows a compound of interest according to the present invention¹³C NMR chart;

FIG. 5 is a fluorescence spectrum of molecular recognition of a target compound of the present invention with zinc ion as a guest, where Blank (i.e., 0 in the figure) represents the fluorescence spectrum of the target compound without zinc ion, and 0.2ml of the target compound is added to a cuvette at a concentration of 1X 10^-5The fluorescence spectrum scanning of the zinc ion solution of mol/L is carried out nine times to obtain a spectrum curve with the equivalent weight of 0-9, and the figure shows that the fluorescence intensity is continuously enhanced along with the enhancement of the zinc ion concentration.

Detailed Description

The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. The drawings are only for purposes of illustration and are not intended to be limiting, and are merely schematic and non-limiting. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

EXAMPLE 1 preparation of the object Compound

The preparation method of the target compound for detecting the zinc ions is shown in figure 2, and specifically comprises the following steps:

step (1): anthracene was dissolved in hydrogen bromide in acetic acid. The volume ratio of hydrogen bromide to acetic acid is 4: 1.

Step (2): adding 1,3, 5-trioxymethylene and N, N, N-trimethyl-1-tetradecyl ammonium bromide into the system in the step (1), and stirring and reacting at the temperature of 80-90 ℃ for 18-24 h; take yellow solid.

The mass ratio of anthracene to 1,3, 5-trioxymethylene and N, N, N-trimethyl-1-tetradecyl ammonium bromide is 25:25: 1.

And (3): and (3) carrying out suction filtration on the yellow solid precipitated in the step (2) by using a Buchner funnel, and washing filter residues by using ethanol to obtain a light yellow solid.

And (4): dissolving the yellow solid obtained in the step (3), bis (2-pyridylmethyl) amine and triethylamine in tetrahydrofuran to react for 3h, wherein the mass ratio of the yellow solid to the bis (2-pyridylmethyl) amine is 5: 2.

and (5): gradually precipitating the reaction in the step (4) to obtain a yellow solid; and (3) completely carrying out rotary evaporation on the solvent by using a rotary evaporator at the temperature of 38-39 ℃, the pressure of 160-180r/min and the pressure of 0.08MPa to obtain a yellow solid.

And (6): stirring the yellow solid obtained by the reaction in the step (5) with ethyl acetate and silica gel, filling the mixture into a column, passing through a chromatographic column (the ground opening of the Xinweier company is 24/40), removing impurity points, wherein the solvent for stirring the sample is ethyl acetate, the solvent for passing through the column is a mixed solvent consisting of methanol and ethyl acetate, the volume ratio of the ethyl acetate to the solvent for passing through the column is 1:10, the impurity points are removed, and the volume ratio of the ethyl acetate to the solvent for passing through the column is 1:5 for a target compound for zinc ion detection.

The structure of the target compound is shown in figure 1, and the yield is 12.5%.

Performing nuclear magnetic resonance detection on the target compound,¹h NMR and¹³the results of C NMR measurements are shown in FIGS. 3 and 4, respectively; the nuclear magnetic resonance results are as follows:

m.p:165.4-166.5℃.¹H NMR(500MHz,CDCl₃)δ8.44(d,J＝4.7Hz,8H),8.40(d,J＝9.5Hz,4H),7.52(t,J＝7.6Hz,4H),7.42(d,J＝9.3Hz,4H),7.29(d,J＝7.8Hz,4H),7.09–6.99(m,4H),4.63(s,1H),3.87(s,8H).¹³C NMR(126MHz,CDCl₃)δ159.7,148.7,136.1,131.1,130.5,125.5,124.9,123.5,121.9。

example 2 Rapid detection method for Zinc ions

Step (1): the target compound obtained in example 1 was used as a detection reagent (solute) with a solvent of acetonitrile to water in a volume ratio of 1:1, and the amount concentration of the prepared substance was 5X 10^-5A solution of mol/L was used as a detection solution.

Zinc sulfate heptahydrate is used as zinc ion source (solute), acetonitrile and water are used as solvent in the volume ratio of 1:1, and the quantity concentration of the prepared material is 1 x 10^-5mol/L solution.

Step (2): adding the detection solution prepared in the step (1) into a fluorescent sample cell (2ml) by using a molecular fluorescence method, and gradually dropwise adding zinc ions with the concentration of 1 multiplied by 10^-5And (3) matching zinc ions with the detection solution by using the mol/L solution, and observing the change of the fluorescence intensity along with the gradual addition of the zinc ion solution. The emission spectrum of molecular fluorescence is selected at E_XThe scanning speed is 1500nm/min between 250 and 270nm, the fluorescence spectrum scanning is faster than the gas chromatography analysis, the result is sensitive, and the selectivity is good.

As a result, as shown in FIG. 5, Blank shows the fluorescence spectrum of the objective compound in the absence of added zinc ion, and 0.2ml of 1X 10 solution was added to each cuvette^-5And (3) carrying out fluorescence spectrum scanning on the zinc ion solution of mol/L for nine times to obtain a spectrum curve with the equivalent weight of 0-9, wherein the fluorescence intensity of the target compound is continuously enhanced along with the increase of the zinc ion solution.

EXAMPLE 3 preparation of the object Compound

The preparation method of the target compound for detecting the zinc ions is shown in figure 2, and specifically comprises the following steps:

step (1): anthracene was dissolved in hydrogen bromide in acetic acid.

The volume ratio of hydrogen bromide to acetic acid is 4:1, and the mass of acetic acid is 6 times that of anthracene.

Step (2): adding 1,3, 5-trioxymethylene and N, N, N-trimethyl-1-tetradecyl ammonium bromide into the system in the step (1), and stirring and reacting for 24 hours at the temperature of 80 ℃; take yellow solid.

The mass ratio of anthracene to 1,3, 5-trioxymethylene and N, N, N-trimethyl-1-tetradecyl ammonium bromide is 25:25: 1.

And (3): and (3) carrying out suction filtration on the yellow solid precipitated in the step (2) by using a Buchner funnel, and washing filter residues by using ethanol to obtain a light yellow solid.

And (4): dissolving the yellow solid obtained in the step (3), bis (2-pyridylmethyl) amine and triethylamine in tetrahydrofuran to react for 5h, wherein the mass ratio of the yellow solid to the bis (2-pyridylmethyl) amine is 5: 2.

And (5): gradually precipitating the reaction in the step (4) to obtain a yellow solid; and (3) completely carrying out rotary evaporation on the solvent by using a rotary evaporator at the temperature of 38-39 ℃, the pressure of 160-180r/min and the pressure of 0.08MPa to obtain a yellow solid.

And (6): stirring the yellow solid obtained by the reaction in the step (5) with ethyl acetate and silica gel, filling the mixture into a column, passing through a chromatographic column (the ground opening of the Xinweier company is 24/40), removing impurity points, wherein the solvent for stirring the sample is ethyl acetate, the solvent for passing through the column is a mixed solvent consisting of methanol and ethyl acetate, the volume ratio of the ethyl acetate to the solvent for passing through the column is 1:15, the impurity points are removed, and the volume ratio of the ethyl acetate to the solvent for passing through the column is 1:10 for a target compound for zinc ion detection.

The structure of the target compound is shown in figure 1, and the yield is 13.5%.

The nuclear magnetic resonance detection of the target compound was performed, and the result was the same as in example 1.

EXAMPLE 4 preparation of the object Compound

The preparation method of the target compound for detecting the zinc ions is shown in figure 2, and specifically comprises the following steps:

step (1): anthracene was dissolved in hydrogen bromide in acetic acid.

The volume ratio of hydrogen bromide to acetic acid is 4:1, and the mass of acetic acid is 5.5 times that of anthracene.

Step (2): adding 1,3, 5-trioxymethylene and N, N, N-trimethyl-1-tetradecyl ammonium bromide into the system in the step (1), and stirring and reacting for 22 hours at the temperature of 80 ℃; take yellow solid.

The mass ratio of anthracene to 1,3, 5-trioxymethylene and N, N, N-trimethyl-1-tetradecyl ammonium bromide is 23:25: 1.

And (3): and (3) carrying out suction filtration on the yellow solid precipitated in the step (2) by using a Buchner funnel, and washing filter residues by using ethanol to obtain a light yellow solid.

And (4): dissolving the yellow solid obtained in the step (3), bis (2-pyridylmethyl) amine and triethylamine in tetrahydrofuran to react for 4h, wherein the mass ratio of the yellow solid to the bis (2-pyridylmethyl) amine is 3: 1.

And (5): gradually precipitating the reaction in the step (4) to obtain a yellow solid; and (3) completely carrying out rotary evaporation on the solvent by using a rotary evaporator at the temperature of 38-39 ℃, the pressure of 160-180r/min and the pressure of 0.08MPa to obtain a yellow solid.

And (6): stirring the yellow solid obtained by the reaction in the step (5) with ethyl acetate and silica gel, filling the mixture into a column, passing through a chromatographic column (the ground opening of the Xinweier company is 24/40), removing impurity points, wherein the solvent for stirring the sample is ethyl acetate, the solvent for passing through the column is a mixed solvent consisting of methanol and ethyl acetate, the volume ratio of the ethyl acetate to the solvent for passing through the column is 1:30, the impurity points are removed, and the volume ratio of the ethyl acetate to the solvent for passing through the column is 1:15 for a target compound for zinc ion detection.

The structure of the target compound is shown in figure 1, and the yield is 15.1%.

The nuclear magnetic resonance detection of the target compound was performed, and the result was the same as in example 1.