A kind of probe with terpyridine as recognition group and containing three electron donors and its preparation method and application

Abstract

The application discloses a kind of probe with terpyridine as recognition group and containing three electron donors and a preparation method and application thereof.The para position of the three pyridine nitrogens of the compound simultaneously contains a carbazole, 3,6-di-tert-butyl carbazole, diphenylamine, 4,4'-dimethoxytriphenylamine or 10-phenylphenothiazine electron donor;In the preparation method, with tris(dibenzylideneacetone) dipalladium, palladium catalyst such as tetra(triphenylphosphine) palladium or cuprous iodide as catalyst, with 4,4',4"-tribromo-2,2':6',2"-terpyridine or 4,4"-dibromo-[2,2':6',2"-terpyridine]-4'-yl trifluoromethanesulfonate as intermediate, the probe is prepared.The application realizes rapid visual sensitive detection of copper ions.

Description

Technical Field

[0001] This invention relates to the field of metal ion detection technology, specifically to a probe with terpyridine as the recognition group and containing three electron donors, its preparation method, and its application. Background Technology

[0002] Copper ions (Cu) 2+ Cu is an important transition metal ion that plays a crucial role in many physiological processes in organisms. However, an imbalance in its concentration within cells can affect normal cellular metabolism, leading to functional disorders and potentially inducing various diseases such as Parkinson's disease, Alzheimer's disease, and Wilson's disease. On the other hand, with the increasing prevalence of Cu... 2+ Widely used in industries and agriculture, many Cu 2+ When released into the environment, copper ions become a significant environmental and ecological pollutant. Therefore, it is essential to develop a simple, real-time, rapid, and reliable analytical method for copper ion detection.

[0003] Among various detection methods, probe technology based on small organic molecules has been widely used and developed in copper ion detection due to its advantages such as high selectivity, high sensitivity, in-situ real-time detection, simple operation, and fast response time. However, currently reported copper ion detection probes often exhibit relatively small changes in the molar extinction coefficient of the response absorption peak, resulting in inconspicuous color changes under natural light, which is not conducive to rapid and visual detection applications. For example, the copper ion probe reported in the Journal of Molecular Structure, 2023, 1271, 134015, showed a new absorption peak (515 nm) with a molar extinction coefficient of approximately 0.8 × 10⁻⁶ after saturation response to copper ions. 4 L / (mol·cm). Patent CN117801563A, entitled "A Copper Ion Probe and Its Preparation Method and Application," reports a copper ion probe with a long-wavelength absorption response (688nm). In the presence of copper ions, the molar extinction coefficient of its characteristic absorption peak is reduced by approximately 0.7*10⁻⁶. 4 L / (mol·cm). In other words, these methods have the limitation that the molar extinction coefficient of the characteristic absorption peak does not change much when visually detecting copper ions.

[0004] Therefore, developing probes that have a specific UV-Vis absorption spectrum response to copper ions, with the absorption peak located in the visible light region and a significant change in the molar extinction coefficient, is of great significance for achieving rapid, visual, and sensitive detection of copper ions. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of current technologies by providing a probe with terpyridine as the recognition group and containing three electron donors, along with its preparation method and applications. The compound contains a carbazole, 3,6-di-tert-butylcarbazole, diphenylamine, 4,4'-dimethoxytriphenylamine, or 10-phenylphenthiazine electron donor at the para position of each of its three pyridine nitrogen groups. In the preparation method, a palladium catalyst such as tris(dibenzylacetone)dipalladium or tetra(triphenylphosphine)palladium, or cuprous iodide, is used as the catalyst, and 4,4',4”-tribromo-2,2':6',2”-terpyridine or 4,4”-dibromo-[2,2':6',2”-terpyridine]-4'-yltrifluoromethanesulfonate is used as an intermediate to prepare the probe. This invention achieves rapid, visual, and sensitive detection of copper ions.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A probe with terpyridine as the recognition group and containing three electron donors has the general chemical structure shown in formula (I):

[0008]

[0009] Wherein, G can be any of the following structural formulas:

[0010]

[0011] In the structural formula, This represents the site where the aforementioned group is connected to the terpyridine unit.

[0012] Preferably, G is Chemical structures such as TPy- were obtained. t The probes shown in BuCz or TPy-OMeTPA:

[0013]

[0014] The method for preparing the probe with terpyridine as the recognition group and containing three electron donors includes any one of the following two methods:

[0015] Method 1, the TPy- t The synthesis of BuCz includes the following steps:

[0016] Under inert gas protection, the compound shown in formula (IIa), 3,6-di-tert-butylcarbazole, catalyst, ligand, base, and first solvent were added to a reactor and reacted at 80–170 °C for 10–48 h to obtain the probe TPy- t BuCz;

[0017]

[0018] The molar ratio of the compound shown in formula (IIa), 3,6-di-tert-butylcarbazole, catalyst, ligand and base is 1:(3-6):(0.02-0.20):(0.1-4.5):(3-90);

[0019] The catalyst is at least one of tris(dibenzylacetone)palladium, tetra(triphenylphosphine)palladium, palladium acetate, [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride and cuprous iodide;

[0020] The ligand is at least one of triphenylphosphine, 1,1'-bis(diphenylphosphine)ferrocene, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, tri(o-tolyl)phosphine, tri-tert-butylphosphine, tri-tert-butylphosphine tetrafluoroborate and 18-crown-6;

[0021] The alkali is at least one of sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, lithium bis(trimethylsilyl)amino and sodium bis(trimethylsilyl)amino.

[0022] The first solvent is at least one selected from benzene, toluene, xylene, 1,4-dioxane, ethylene glycol dimethyl ether, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and tert-butanol.

[0023] Alternatively, Method 2, the synthesis of TPy-OMeTPA includes the following steps:

[0024] Under inert gas protection, substance A, the compound shown in formula (III), the catalyst, the base and the second solvent were added to the reactor and reacted at 60-140°C for 10-48 h to obtain the probe TPy-OMeTPA.

[0025] Wherein, substance A is a compound represented by formula (IIa) or formula (IIb);

[0026] The molar ratio of substance A, the compound shown in formula (III), the catalyst, and the base is 1:(3-6):(0.02-0.20):(1.5-40);

[0027]

[0028] The catalyst is at least one of tetrakis(triphenylphosphine)palladium, tris(dibenzylacetone)palladium, palladium acetate, [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride, and palladium dichloride;

[0029] The alkali is at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium tert-butoxide, and potassium tert-butoxide.

[0030] The second solvent is at least one of tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, benzene, toluene, xylene, N,N-dimethylformamide, and dimethyl sulfoxide.

[0031] The inert gas mentioned in the above reaction steps is argon or nitrogen.

[0032] The compound represented by formula (IIb) above was prepared using methods known in the art, specifically including the following steps:

[0033] S1: In the presence of a base, methyl 4-bromopyridine-2-carboxylate undergoes a ketone-ester condensation reaction with acetone to give the compound shown in formula (IV).

[0034]

[0035] The reaction is carried out at a temperature of 60–100°C for a time of 2–24 hours.

[0036] The reaction is carried out in solution, and the solvent is at least one of ethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane.

[0037] The alkali is at least one of sodium hydride, sodium tert-butoxide, or potassium tert-butoxide.

[0038] The molar ratio of methyl 4-bromopyridine-2-carboxylate, acetone, and base is 1:(0.15–0.6):(0.3–4).

[0039] S2: The compound shown in formula (IV) is reacted with ammonium acetate to obtain the compound shown in formula (V);

[0040]

[0041] The reaction is carried out at a temperature of 60–83°C for 2–12 hours.

[0042] The reaction is carried out in solution, and the solvent is at least one of methanol, ethanol and isopropanol;

[0043] The molar ratio of the compound shown in formula (IV) to ammonium acetate is 1:(1-10).

[0044] S3: The compound shown in formula (V) is reacted with trifluoromethanesulfonic anhydride to obtain the compound shown in formula (IIb);

[0045] The reaction temperature is -10 to 60°C, and the time is 4 to 48 hours;

[0046] The reaction is carried out in solution, and the solvent is at least one of pyridine and triethylamine;

[0047] The molar ratio of the compound shown in formula (V) to trifluoromethanesulfonic anhydride is 1:(0.5-4).

[0048] The synthetic steps of the compound shown in formula (IIa) above are as follows:

[0049] The compound shown in formula (IIb) was reacted with hydrobromic acid to obtain the compound shown in formula (IIa);

[0050] The reaction temperature is 90–140°C, and the time is 4–24 hours;

[0051] The reaction is carried out in solution, and the solvent is at least one of acetic acid and propionic acid;

[0052] The molar ratio of the compound shown in formula (IIb) to hydrogen bromide is 1:(15-70).

[0053] The aforementioned probe, which uses terpyridine as a recognition group and contains three electron donors, is used to detect copper ions in solution.

[0054] Specifically, one of the following two methods:

[0055] Method 1 includes the following steps:

[0056] The probe, which uses terpyridine as a recognition group and contains three electron donors, was dissolved in tetrahydrofuran to prepare a solution of 10... -3 ~10 -5 Prepare a colorless probe solution at mol / L. Mix the probe solution and the test solution for 5–60 seconds. If the mixed solution changes from colorless to yellow, it indicates that the test sample contains copper ions; if the mixed solution does not change color, it indicates that it does not contain copper ions.

[0057] The volume ratio of the probe solution to the test solution is 1:0.1 to 9.0; the measurable copper ion concentration in the test solution is not less than 5 μM.

[0058] Alternatively, the second method includes the following steps:

[0059] Take 1 mL of the probe prepared in step (1) 10 -3 ~10 -5 Add 1 mL of distilled water and 8 mL of tetrahydrofuran solution to a colorimetric tube and mix. Record this mixture as a standard solution and test its UV-Vis absorption spectrum. Then take 1 mL of the probe prepared in step (1) and add 10 mol / L tetrahydrofuran solution. -3 ~10 -5 Add 1 mL of the test sample and 8 mL of tetrahydrofuran to a colorimetric tube, and mix them together. This mixture is called the test sample solution. Measure its UV-Vis absorption spectrum.

[0060] The absorption intensities of the standard solution and the test sample solution at 405 nm are compared to determine whether the sample contains copper ions. The judgment criterion is that if the absorption intensity of the test sample solution at 405 nm is higher than that of the standard solution, it indicates that the sample contains copper ions.

[0061] The measurable concentration of copper ions in the test solution is not less than 3.09 × 10⁻⁶. -7 mol / L.

[0062] The beneficial effects of this invention are as follows:

[0063] 1. The probe provided by this invention, which uses terpyridine as a recognition group and contains three electron donors, improves the complexation reaction ability of terpyridine with copper ions by introducing three electron-donating groups, and enhances the "push-pull" effect of the molecule, which is conducive to shifting the absorption spectrum to longer wavelengths and entering the visible light region. In addition, after the terpyridine unit complexes with copper ions, its planarity is improved, which helps to obtain a high molar extinction coefficient.

[0064] 2. The probe provided by this invention, which uses terpyridine as a recognition group and contains three electron donors, has an absorption spectrum in solution that is mainly or entirely located in the ultraviolet region. After the addition of copper ions, a new absorption peak appears in the visible region, and its molar extinction coefficient can reach 2.77*10. 4 The solution color changed significantly with a concentration of L / (mol·cm), enabling rapid, visual, and sensitive detection of copper ions. Attached Figure Description

[0065] Figure 1 The normalized UV-Vis absorption spectrum of the probe (10 μM) prepared in Example 1 in tetrahydrofuran;

[0066] Figure 2 The normalized UV-Vis absorption spectrum of the probe (10 μM) prepared in Example 2 in tetrahydrofuran;

[0067] Figure 3 The UV-Vis absorption spectra of the probe (10 μM) prepared in Example 1 before and after the addition of copper ions (20 μM);

[0068] Figure 4 The graph shows the relationship between the absorbance of the probe (10 μM) prepared in Example 1 at 405 nm and the concentration of copper ions (0-40 μM);

[0069] Figure 5 The probe (10 μM) prepared for Example 1 was used with different analytes (blank, Ag) + Al 3+ Ca 2+ Cd 2+ Cr2+ Fe 2+ Fe 3+ Mg 2+ Mn 2+ Pb 2+ Zn 2+ Cl - CF3CO2 - BF4 - NO3 - The change in absorbance at 405 nm before and after the addition of copper ions in the presence of copper ions;

[0070] Figure 6 The probe prepared in Example 1 1 H NMR spectrum;

[0071] Figure 7 The probe prepared in Example 1 13 C NMR spectrum;

[0072] Figure 8 The probe prepared in Example 2 1 H NMR spectrum;

[0073] Figure 9 The probe prepared in Example 2 13 C10 NMR spectrum. Detailed Implementation

[0074] The present invention will be further described below through specific embodiments to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following embodiments.

[0075] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; the reagents and materials described are commercially available unless otherwise specified.

[0076] Example 1: Probe TPy- t Preparation of BuCz.

[0077] probe TPy- t The synthetic route for BuCz is as follows:

[0078]

[0079] (1) Synthesis of intermediate IV:

[0080] Sodium hydride (60.0%, 3.40 g, 85.0 mmol) and dimethyl ethylene glycol ether (DME, 34 mL) were sequentially added to a 250 mL three-necked flask. Then, methyl 4-bromopyridine-2-carboxylate (10.80 g, 50.0 mmol), acetone (1.00 g, 17.2 mmol), and DME (34 mL) were added to a 100 mL constant-pressure dropping funnel and slowly added dropwise to the suspension under an argon atmosphere. The mixture was heated to reflux, and the brown suspension turned dark red. The reaction mixture was then cooled to room temperature and stirred for 2 hours. The solvent was removed under reduced pressure, and distilled water (100 mL) was slowly added to adjust the pH to 6.5. A large amount of yellow solid precipitated out. The solid was filtered, washed with water, and dried under vacuum to obtain 7.01 g of yellow product, with a yield of 95.6%, which was used directly in the next reaction.

[0081] (2) Synthesis of intermediate V:

[0082] A suspension consisting of intermediate IV (3.7750 g, 8.9 mmol), ammonium acetate (4.78 g, 62.0 mmol), and ethanol (100 mL) was heated to reflux for 6 h. After the reaction was complete, the mixture was cooled to room temperature, and the ethanol was distilled off under reduced pressure. The crude product was purified by column chromatography (dichloromethane: anhydrous methanol = 30:1) to give 2.50 g of a white solid, with a yield of 69.3%. 1 H NMR (400MHz, DMSO-d6) δ (ppm): 11.13 (s, 1H), 8.69 (s, 2H), 8.57 (d, J = 5.2Hz, 2H), 7.86 (s, 2H), 7.75 (d, J = 4.8Hz, 2H). 13 C NMR (101MHz, DMSO-d6) δ (ppm): 166.56, 156.97, 155.77, 151.01, 133.83, 127.75, 124.11, 109.67.

[0083] (3) Synthesis of intermediate IIb:

[0084] Trifluoromethanesulfonic anhydride (0.96 g, 3.4 mmol) was added dropwise to a pyridine (10 mL) solution of intermediate V (1.02 g, 2.5 mmol) under stirring at 0 °C. After stirring for 0.5 hours, the mixture was allowed to rise to room temperature and reacted for 48 hours. The reaction was quenched with distilled water, filtered, and washed to give 1.20 g of a white solid, with a yield of 89.0%. 1 H NMR (400MHz, CDCl3) δ (ppm): 8.73 (s, 2H), 8.53 (d, J = 5.2Hz, 2H), 8.42 (s, 2H), 7.58 (d, J = 8.0Hz, 2H). 13C NMR (101MHz, CDCl3) δ (ppm): 157.69, 155.20, 150.16, 134.25, 128.13, 124.83, 117.13, 114.25.

[0085] (4) Synthesis of intermediate IIa:

[0086] A solution of intermediate IIb (0.5381 g, 1.0 mmol), 40% hydrobromic acid (7 mL, i.e., 49.1 mmol), and acetic acid (9 mL) was heated to reflux for 13 hours. After the reaction was completed, the mixture was cooled to room temperature, 25 mL of distilled water was added, and the pH was adjusted to 7 with sodium hydroxide solution. The mixture was filtered and washed to give 0.44 g of a white solid, with a yield of 93.8%. 1 H NMR (400MHz, CDCl3) δ (ppm): 8.74 (s, 2H), 8.68 (s, 2H), 8.54 (d, J = 4.0Hz, 2H), 7.57 (s, 2H). 13 C NMR (101MHz, CDCl3) δ (ppm): 155.94, 155.35, 150.00, 134.10, 127.66, 125.22, 124.81.

[0087] (5) Probe TPy- t Synthesis of BuCz:

[0088] A suspension of intermediate IIa (0.1614 g, 0.3 mmol), 3,6-di-tert-butylcarbazole (0.4190 g, 1.5 mmol), tris(benzylacetone)palladium (0.0551 g, 0.06 mmol), sodium tert-butoxide (0.2980 g, 3.1 mmol), and tri-tert-butylphosphine tetrafluoroborate (0.0420 g, 0.14 mmol) in toluene (10 mL) was heated to reflux for 36 h under an Ar atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography (dichloromethane), and further purified by recrystallization from dichloromethane and anhydrous methanol to give 0.20 g of a white solid, with a yield of 54.7%. 1 H NMR (400MHz, CDCl3) δ (ppm): 8.95 (s, 2H), 8.89-8.85 (m, 4H), 8.19 (s, 2H), 8.07 (s, 4H), 7. 80(d,J=8.0Hz,2H),7.62-7.58(m,8H),7.20(d,J=8.0Hz,4H),1.52(s,18H),1.37(s,36H). 13C NMR(101MHz, CDCl3)δ(ppm):158.15,157.57,151.03,148.35,147.13,144.21,138.20,137.84,124.60,124.53,1 24.28,124.15,119.83,117.80,116.61,110.09,109.70,77.36,34.97,34.80,32.14,31.99.HRMS(ESI)m / z:calcd for C 75 H 80 N6[M+H] + 1065.6517, found 1065.6596. This indicates that the target product was obtained.

[0089] Figure 1 The probe TPy- prepared in Example 1 t The normalized UV-Vis absorption spectrum of BuCz in tetrahydrofuran shows that the absorption spectrum of this probe is in the ultraviolet region (not exceeding 400 nm), with three relatively obvious absorption bands at 292 nm, 330 nm, and 341 nm. Therefore, the probe TPy- t The BuCz solution was colorless. Furthermore, TPy- was tested. t The fluorescence emission of BuCz in tetrahydrofuran has a maximum emission wavelength of 445 nm; however, the fluorescence intensity at 445 nm decreases or even quenches in the presence of copper ions, indicating that TPy- t BuCz can also be used as a fluorescent probe for copper ion detection.

[0090] Example 2: Preparation of probe TPy-OMeTPA.

[0091] The synthetic route for the probe TPy-OMeTPA is as follows:

[0092]

[0093] Intermediate IIb (0.4843 g, 0.9 mmol), compound III (1.5530 g, 3.6 mmol), tetra(triphenylphosphine)palladium (0.1832 g, 0.16 mmol), and tetrahydrofuran (23 mL) were added to a three-necked flask. Under an argon atmosphere, 11 mL of an aqueous solution of potassium carbonate (3.60 g, 26.0 mmol) was added to the above solution, and the mixture was heated to reflux for 48 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation. The crude product was purified by alkaline alumina column chromatography, and further purified by recrystallization from a mixed solvent of dichloromethane and anhydrous methanol to give 0.50 g of a yellow solid, with a yield of 48.7%. 1H NMR (400MHz, DMSO-d6) δ (ppm): 8.69-8.57 (m, 6H), 7.72-7.64 (m, 8H), 7.10 (d, J = 8.0Hz, 4H), 7.02 (d, J = 8. 0Hz, 8H), 6.94 (d, J = 8.0Hz, 4H), 6.89 (d, J = 8.0Hz, 10H), 6.77 (d, J = 8.0Hz, 4H), 3.75 (s, 6H), 3.70 (s, 12H). 13 C NMR(101MHz,DMSO-d6)δ(ppm):156.21,156.11,155.96,155.76,149.65,149.42,147.70,139.43,12 7.95,127.56,127.32,127.10,118.56,117.27,115.05,114.96,55.22,55.18.HRMS(ESI)m / z:calcd for C 75 H 64 N6O6[M+H] + The result 1043.4804, found 1043.4884, indicates that the target product was obtained.

[0094] Figure 2 The normalized UV-Vis absorption spectrum of the probe TPy-OMeTPA prepared in Example 2 in tetrahydrofuran is shown. This probe exhibits two absorption bands near 290 nm and 365 nm, with the 365 nm absorption band attributed to intramolecular charge transfer absorption, and a small portion extending into the visible light region. Furthermore, the fluorescence emission of TPy-OMeTPA in tetrahydrofuran was tested, with a maximum emission wavelength of 507 nm.

[0095] Example 3: Probe TPy- t BuCz UV-Vis absorption spectrum response to copper ions.

[0096] Using tetrahydrofuran as a solvent, prepare 10 -4 mol / L probe TPy- t BuCz mother liquor; weigh out copper chloride to prepare 10 - 3A mol / L distilled aqueous solution was prepared, and then diluted to prepare solutions of 1 μM, 2 μM, 3 μM, 4 μM, 5 μM, 6 μM, 7 μM, 8 μM, 9 μM, 10 μM, 15 μM, 20 μM, 30 μM, and 40 μM. 1 mL of the probe stock solution was added to several parallel 10 mL colorimetric tubes. 1 mL of copper chloride solution of different concentrations was then transferred to each of the colorimetric tubes and shaken thoroughly. 8 mL of tetrahydrofuran was then added, and the absorption spectrum changes were measured using a UV-Vis spectrophotometer. Cu was added... 2+ Subsequently, a new absorption peak appeared at 405 nm on the probe (see...). Figure 3 Furthermore, as the concentration of copper ions increases, the absorbance initially gradually increases, while the color of the solution (yellow) gradually deepens under natural light; when 2 equivalents of Cu are added... 2+ After ionization, the absorption peak intensity at 405 nm and the color of the solution hardly change, therefore the probe TPy- t BuCz can visually detect copper ions, and the lowest copper ion concentration that can be detected by the naked eye is approximately 5 μM. Figure 4 It can be seen that the absorbance (405nm) is related to Cu 2+ The concentration exhibits a good linear relationship in the range of 0-15 μM (R0). 2 =0.992), indicating that the probe can quantitatively detect copper ions. The calculated detection limit (LOD) is 3σ / K, where σ is the standard deviation of the absorbance at 405 nm of the probe solution, and K is the standard deviation of the absorbance at 405 nm. Figure 4 The linear slope in the equation is 3.09 × 10⁻⁶. -7 mol / L.

[0097] like Figure 5 As shown, blank, silver ions (Ag) + ), aluminum ions (Al) 3+ ), calcium ions (Ca 2+ ), cadmium ions (Cd) 2+ ), chromium ions (Cr 2+ ), ferrous ions (Fe) 2+ ), iron ions (Fe 3+ ), magnesium ions (Mg 2+ ), manganese ions (Mn) 2+ ), lead ions (Pb) 2+ ), zinc ions (Zn) 2+ ), chloride ions (Cl) - ), trifluoroacetate (CF3CO2) - ), tetrafluoroborate (BF4) - ), nitrate (NO3) -The probe was used as an analyte (two equivalents of the probe) and its selectivity and anti-interference were tested (the absorption peak intensity at 405 nm was measured using a UV-Vis spectrophotometer and a bar chart was plotted). It can be seen that the probe has high selectivity and good anti-interference properties for copper ions.

[0098] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. It should be noted that for those skilled in the art, several changes, substitutions and modifications can be made without departing from the concept of the present invention, and these changes, substitutions and modifications should all be included within the scope of protection of the present invention.

[0099] Matters not covered in this invention are common knowledge.

Claims

1. A probe with terpyridine as the recognition group and containing three electron donors, characterized in that: The chemical structure of the probe is shown in formula (I): Formula (I) G is any one of the following structures: 。 2. The probe with terpyridine as recognition group and three electron donors according to claim 1, characterized in that G is or , resulting in a probe with the chemical structure as shown in TPy- t BuCz or TPy-OMeTPA. or 。 3. The method for preparing the probe with terpyridine as the recognition group and containing three electron donors according to claim 2, characterized in that the method comprises one of the following two methods: Method one, the TPy- t Synthesis of BuCz, including the following steps: The compound shown in formula (IIa), 3,6-di-tert-butylcarbazole, a catalyst, a ligand, a base and a first solvent are added into a reactor under inert gas protection, and reacted at 80-170 °C for 10-48 h to obtain the probe TPy- t BuCz; Formula (IIa); wherein, The molar ratio of the compound shown in formula (IIa), 3,6-di-tert-butylcarbazole, the catalyst, the ligand and the base is 1: (3-6): (0.02-0.20): (0.1-4.5): (3-90); The catalyst is at least one of tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, palladium acetate, [1, 1'-bis (diphenylphosphino) ferrocene] dichloropalladium and cuprous iodide; The ligand is at least one of triphenylphosphine, 1, 1'-bis (diphenylphosphino) ferrocene, 1, 1'-binaphthalene-2, 2'-bisdiphenylphosphine, tri (o-tolyl) phosphine, tri-tert-butylphosphine, tri-tert-butylphosphine tetrafluoroborate and 18-crown-6; The base is at least one of sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, lithium bis (trimethylsilyl) amide and sodium bis (trimethylsilyl) amide; The first solvent is at least one of benzene, toluene, xylene, 1, 4-dioxane, ethylene glycol dimethyl ether, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and tert-butanol; Alternatively, method two, the synthesis of TPy-OMeTPA, comprises the following steps: Under the protection of inert gas, substances A, the compound shown in formula (III), the catalyst, the base and the second solvent are added to a reactor, and reacted at 60-140℃ for 10-48h to obtain the probe TPy-OMeTPA; Substance A is the compound shown in formula (IIa) or formula (IIb); The molar ratio of substance A, the compound shown in formula (III), the catalyst and the base is 1: (3-6): (0.02-0.20): (1.5-40); Formula (IIb); Formula (III); The catalyst is at least one of tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, [1, 1'-bis (diphenylphosphino) ferrocene] dichloropalladium and dichloropalladium; The base is at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium tert-butoxide and potassium tert-butoxide; The second solvent is at least one of tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, benzene, toluene, xylene, N, N-dimethylformamide and dimethyl sulfoxide; The inert gas in the above reaction step is argon or nitrogen.

4. The probe with terpyridine as the recognition group and containing three electron donors according to claim 1 for the purpose of diagnosis or treatment of non-diseases, characterized in that it is used for detecting copper ions in solution.

5. The use according to claim 4, characterized in that it comprises one of the following two methods: Method one, comprising the following steps: The probe with terpyridine as recognition group and containing three electron donors is dissolved in tetrahydrofuran to prepare a 10 -3 ~10 -5 mol / L colorless probe solution. Mix the probe solution and the sample to be tested for 5-60 seconds. When the mixed solution changes from colorless to yellow, it indicates that the sample to be tested contains copper ions; If the mixed solution does not change color, it indicates that it does not contain copper ions; The volume ratio of the probe solution and the to-be-tested solution is 1:0.1-9.0; the concentration of the detectable copper ions in the to-be-tested solution is not less than 5 μM; Or, the second kind, comprising the following steps: Take 1 mL of the prepared probe 10 -3 ~10 -5 mol / L tetrahydrofuran solution in a colorimetric tube and add 1 mL distilled water and 8 mL tetrahydrofuran, marked as: contrast standard solution, test its ultraviolet-visible absorption spectrum; Take 1 mL of the prepared probe 10 -3 ~10 -5 mol / L tetrahydrofuran solution in a colorimetric tube and add 1 mL of the sample to be tested and 8 mL of tetrahydrofuran, marked as: test sample solution, test its ultraviolet-visible absorption spectrum; Comparing the absorption intensity of the contrast standard solution and the test sample solution at 405 nm, judging whether the to-be-tested sample contains copper ions by the change of the absorption intensity; the judgment standard is that the absorption intensity of the test sample solution at 405 nm is higher than that of the contrast standard solution, which indicates that the to-be-tested sample contains copper ions; The concentration of the detectable copper ions in the solution to be measured is not less than 3.09 x 10 -7 mol / L.

6. The use as claimed in claim 4, characterised in that The solution to be tested also contains Ag + , Al 3+ , Ca 2+ , Cr 2+ , Mg 2+ , Mn 2+ or Pb 2+ ions.

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