Ga < 3 + > fluorescent probe in acid environment and application of Ga < 3 + > fluorescent probe

Abstract

The invention provides an application of a compound as shown in a formula (L) as a Ga < 3 + > fluorescent probe. The fluorescent probe can recognize Ga < 3 + > ions with high selectivity and high sensitivity under an acidic condition.

Description

Technical Field

[0001] This invention belongs to the field of fluorescent probe technology, specifically relating to a Ga in an acidic environment. 3+ Fluorescent probes and their applications. Background Technology

[0002] Fluorescent molecular probes are a novel method for molecular and ion detection that has emerged in recent years. They possess characteristics such as high selectivity, high sensitivity, and rapid and convenient real-time detection. The detection process is visualized through changes in output signals such as fluorescence, ultraviolet light, and color, overcoming the shortcomings of traditional molecular and ion detection methods. Fluorescent molecular probes offer advantages such as strong biological applicability and represent a leap forward in detection technology. They are widely used in fields such as molecular and ion identification, detection of bioactive substances, bioimaging, near-infrared fluorescence, and time-resolved testing.

[0003] Gallium is a very important rare metal element with wide applications in metal catalysts, semiconductor manufacturing, solar cells, pharmaceuticals, and diagnostic reagents; gallium citrate is often used as a contrast agent in magnetic resonance imaging. However, with the widespread use of gallium compounds in human life and industrial production, the amount of gallium in the environment is increasing. 3+ The increasing accumulation of Ga₂O₃ is inevitably causing harm to the ecological environment and may lead to ecological and human health risks, such as nephrotoxicity and metabolic disorders. Therefore, the development of sensitive and highly selective Ga₂O₃ is crucial. 3+ Detection methods play a crucial role in environmental monitoring and toxicological assessment. Fluorescent probes, with their high sensitivity, real-time monitoring capabilities, and non-invasive characteristics, have become important analytical tools in the field of ion detection.

[0004] 2,2′:6′,2″ terpyridine and its derivatives can form stable complexes with a variety of metal ions, possessing rigid tripenteric ligands with extended π-conjugation, exhibiting a strong binding affinity for metal ions (such as Fe). 3+ ,Zn 2+ Co 2+ Ni 2+ Hg 2+ Cd 2+ ), is the most widely used chelating ligand in modern coordination chemistry. Although significant progress has been made in fluorescent probe design, the detection of Ga in acidic environments remains a challenge. 3+ Challenges remain. Existing Ga 3+ Probes generally suffer from two major drawbacks: firstly, they are susceptible to other metal ions (such as Mn). 2+ Mg 2+ Al3+, Cd2+, Cr 3+ Fe 3+Firstly, interference occurs; secondly, fluorescence efficiency decreases significantly under low pH conditions, as acidic media quench the excited state of fluorophores and destroy ion binding sites. Therefore, it is crucial to develop Gao molecules that maintain high stability and selectivity under acidic conditions. 3+ Specific fluorescent probes have become a critical issue that urgently needs to be addressed. Summary of the Invention

[0005] This invention provides a compound of formula (I) as Ga 3+ The fluorescent probe is used in applications where it can selectively and sensitively identify Ga under acidic conditions. 3+ ion.

[0006] This invention provides any of the following applications of the compound represented by formula (I):

[0007] (i) In the preparation, detection, identification, and tracing of Ga 3+ Applications of fluorescent probes for ions;

[0008] (ii) In the detection, identification, and tracing of Ga 3+ Applications in ions;

[0009] (iii) In the preparation, detection, identification, and tracing of Ga 3+ Applications of ions in products or reagents;

[0010]

[0011] Among them, R0 may be the same or different, and are independently selected from H and C. 1-10 alkyl.

[0012] According to embodiments of the present invention, R0 may be the same or different, and is independently selected from H and C. 1-6 Alkyl or C 1-3 Alkyl (e.g., C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl); preferably, R0 is the same; preferably, R0 is methyl.

[0013] According to an embodiment of the present invention, the compound represented by formula (I) is selected from the following compounds:

[0014]

[0015] According to an embodiment of the present invention, the application is for detecting, identifying, and tracing Ga in environmental samples and biological samples. 3+ ion.

[0016] According to an embodiment of the present invention, the compound represented by formula (I) can detect, identify, and trace Ga under acidic conditions. 3+Ions. According to embodiments of the present invention, the acidic condition is a pH less than or equal to 4; for example, pH is 4.0, 3.8, 3.5, 3.2, 3.0, 2.8, 2.5, 2.2, 2.0, 1.8, 1.5, 1.2, 1.0, 0.8, 0.5, 0.2.

[0017] According to an embodiment of the present invention, the working concentration of the compound shown in formula (I) is 0.01 mmol / L-50 mmol / L, preferably 0.1 mmol / L-20 mmol / L, for example 0.1 mmol / L, 0.2 mmol / L, 0.4 mmol / L, 0.5 mmol / L, 0.8 mmol / L, 1 mmol / L, 3 mmol / L, 5 mmol / L, 8 mmol / L, 10 mmol / L, 15 mmol / L, 20 mmol / L, 30 mmol / L, 40 mmol / L, 50 mmol / L.

[0018] According to an embodiment of the present invention, Ga 3+ The concentration of the ions is 0.01 mmol / L to 50 mmol / L, preferably 0.1 mmol / L to 20 mmol / L, for example 0.1 mmol / L, 0.2 mmol / L, 0.4 mmol / L, 0.5 mmol / L, 0.8 mmol / L, 1 mmol / L, 3 mmol / L, 4 mmol / L, 5 mmol / L, 8 mmol / L, 10 mmol / L, 15 mmol / L, 20 mmol / L, 30 mmol / L, 40 mmol / L, and 50 mmol / L.

[0019] According to an embodiment of the present invention, the compound shown in formula (I) reacts with Ga 3+ The molar ratio of ions is 0.01-10:10, preferably 0.1-8:10, for example 0.3:10, 0.5:10, 0.8:10, 1:10, 2:10, 3:10, 4:10, 5:10, 6:10, 7:10, 8:10.

[0020] According to an embodiment of the present invention, the fluorescence emission wavelength of the compound shown in formula (I) is 510nm-530nm, for example 515nm, 518nm, 519nm, 520nm, and 525nm.

[0021] This invention also provides a method for detecting, identifying, and tracing Ga. 3+ The products or reagents containing ions, said products or reagents include:

[0022] (1) The compound shown in formula (I);

[0023] (2) Acidic reagents;

[0024]

[0025] Among them, R0 may be the same or different, and are independently selected from H and C. 1-10 alkyl.

[0026] According to embodiments of the present invention, R0 may be the same or different, and is independently selected from H and C. 1-6 Alkyl or C 1-3 Alkyl (e.g., C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl); preferably, R0 is the same; preferably, R0 is methyl.

[0027] According to an embodiment of the present invention, the compound represented by formula (I) is selected from the following compounds:

[0028]

[0029] According to embodiments of the invention, the product or reagent optionally further comprises a solvent; the solvent is, for example, DMSO. The solvent is used to prepare a stock solution or working solution of a suitable concentration from the compound represented by formula (I).

[0030] According to embodiments of the present invention, the concentration of the solution of the compound shown in formula (I) is 0.01 mmol / L to 1 mol / L, preferably 0.1 mmol / L to 1 mol / L, for example 0.1 mmol / L, 0.2 mmol / L, 0.4 mmol / L, 0.5 mmol / L, 0.8 mmol / L, 1 mmol / L, 3 mmol / L, 5 mmol / L, 8 mmol / L, 10 mmol / L, 15 mmol / L, 20 mmol / L, 30 mmol / L, 40 mmol / L, 50 mmol / L, 80 mmol / L, 100 mmol / L, 200 mmol / L, 500 mmol / L, 800 mmol / L, or 1 mol / L. Optionally, the solution of the compound shown in formula (I) can be used after dilution.

[0031] According to an embodiment of the present invention, the working concentration of the compound shown in formula (I) is 0.01 mmol / L-50 mmol / L, preferably 0.1 mmol / L-20 mmol / L, for example 0.1 mmol / L, 0.2 mmol / L, 0.4 mmol / L, 0.5 mmol / L, 0.8 mmol / L, 1 mmol / L, 3 mmol / L, 5 mmol / L, 8 mmol / L, 10 mmol / L, 15 mmol / L, 20 mmol / L, 30 mmol / L, 40 mmol / L, 50 mmol / L.

[0032] According to an embodiment of the present invention, the acidic reagent is selected from organic acids and inorganic acids; for example, hydrochloric acid.

[0033] According to an embodiment of the present invention, the pH of the reaction system for detection, identification, and tracing is adjusted by an acidic reagent to be less than or equal to 4; the pH is, for example, 4.0, 3.8, 3.5, 3.2, 3.0, 2.8, 2.5, 2.2, 2.0, 1.8, 1.5, 1.2, 1.0, 0.8, 0.5, or 0.2.

[0034] According to an embodiment of the present invention, the product or reagent is a test kit.

[0035] According to an embodiment of the present invention, the fluorescence emission wavelength is 510nm-530nm, for example 515nm, 518nm, 519nm, 520nm, and 525nm.

[0036] According to embodiments of the present invention, the product or reagent can be used to detect, identify, and trace Ga in environmental samples and biological samples. 3+ ion.

[0037] This invention also provides the above-mentioned products or reagents for detecting, identifying, and tracing Ga in environmental and biological samples. 3+ Applications in ions.

[0038] Beneficial effects

[0039] This invention provides a compound of formula (I) as Ga 3+ The fluorescent probe is used in applications where it can selectively and sensitively identify Ga under acidic conditions. 3+ ion.

[0040] The fluorescent probe molecule L emits a strong emission band centered at 510 nm in DMSO. When these metal ions (Cd) are placed in the DMSO, the fluorescence band is similar to that emitted by the probe molecule L. 2+ Hg 2+ Al 3+ Mg 2+ Na + Pb 2+ Ag + Ce 3+ Mn 2+ Cr 3+ Zn 2+ Cu 2+ Ga 3+ Fe 3+ Co 2+ Ni 2+When added to a neutral aqueous solution of the probe molecule, the fluorescence emission peak of the fluorescent probe molecule L at 510 nm disappears. Under acidic conditions, the fluorescent probe molecule L exhibits weak fluorescence emission at 510 nm; when Ga is added... 3+ After the ions enter this acidic solution, the fluorescence emission intensity of the fluorescent probe molecule L at 519 nm increases significantly. Therefore, the fluorescent probe molecule L exhibits high sensitivity and selectivity in recognizing Ga under acidic conditions. 3+ It is not affected by various metal ions. Attached Figure Description

[0041] Figure 1 The color changes of each solution under neutral and acidic conditions are shown in Figure (1a). Figure (1b) shows the color of the solution under neutral conditions. ex = Fluorescence visible to the naked eye under 365nm light; Figure (1c) Color of the solution under acidic conditions; Figure (1d) λ under acidic conditions ex Fluorescence visible to the naked eye at 365nm.

[0042] Figure 2 The fluorescence spectra of fluorescent probe molecule L under neutral conditions are shown in DMSO and aqueous solutions of fluorescent probe molecule L and metal ions (approximately 2% DMSO) (excitation wavelength 365 nm).

[0043] Figure 3 The fluorescence spectrum of the fluorescent probe molecule L with metal ions under acidic conditions (excitation wavelength 365 nm).

[0044] Figure 4 Under acidic conditions, the fluorescent probe molecule L (excitation wavelength 365 nm) in the absence / presence of Ga 3+ Comparison of fluorescence intensity at 519 nm with that of metal ions when present. (Green bars: fluorescence intensity of fluorescent probe molecules L containing different metal ions; Red bars: fluorescence intensity of molecules containing different metal ions and Ga) 3+ (The fluorescence intensity of the fluorescent probe molecule L). Detailed Implementation

[0045] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0046] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0047] The preparation process of fluorescent probe molecule L can be found in patent CN202311783864.0.

[0048]

[0049] Example 1: Fluorescent probe molecule L against Ga 3+ Fluorescence recognition detection

[0050] Prepare a DMSO solution (10 mmol / L) of fluorescent probe molecule L at room temperature and sonicate until completely dissolved.

[0051] Preparation of Cd at room temperature 2+ Hg 2+ Al 3+ Mg 2+ Na + Pb 2+ Ag + Ce 3+ Mn 2+ Cr 3+ Zn 2+ Cu 2+ Ga 3+ Fe 3+ Co 2+ Ni 2+ A nitrate aqueous solution (1 mmol / L, water as solvent).

[0052] Take 2 mL of water and Cd respectively 2+ Hg 2+ Al 3+ Mg 2+ Na + Pb 2+ Ag + Ce 3+ Mn 2+ Cr 3+ Zn 2+ Cu 2+ Ga 3+ Fe 3+ Co 2+ and Ni 2+ A 1 mmol / L aqueous solution of nitrate was prepared, and 40 μL of DMSO solution (10 mmol / L) containing L of the fluorescent probe molecule was added sequentially. Fluorescence emission and intensity were observed under a 365 nm UV lamp. Fluorescence spectra in the 400-750 nm wavelength range were detected using an F7000 fluorescence spectrometer under excitation at 365 nm.

[0053] Take 2 mL of water and Cd respectively 2+ Hg 2+ Al3+ Mg 2+ Na + Pb 2+ Ag + Ce 3+ Mn 2+ Cr 3+ Zn 2+ Cu 2+ Ga 3+ Fe 3+ Co 2+ and Ni 2+ A 1 mmol / L nitrate aqueous solution was prepared, followed by the addition of 40 μL of DMSO solution (10 mmol / L) containing L of the fluorescent probe molecule. Finally, 20 μL of dilute hydrochloric acid (8% by mass) was added to adjust the pH to 4. Fluorescence emission and intensity were observed under a 365 nm UV lamp. Fluorescence spectra in the 400-750 nm wavelength range were detected using an F7000 fluorescence spectrometer under 365 nm excitation.

[0054] The results showed that the fluorescent probe molecule L emitted a strong emission band centered at 510 nm in DMSO. Figure 2 When these metal ions (Cd) 2+ Hg 2+ Al 3+ Mg 2+ Na + Pb 2+ Ag + Ce 3+ Mn 2+ Cr 3+ Zn 2+ Cu 2+ Ga 3+ Fe 3+ Co 2 + Ni 2+ When added to a neutral aqueous solution (approximately 2% DMSO) of the probe molecule, the fluorescence emission peak of the fluorescent probe molecule L at 510 nm disappears. Figure 2 Under acidic conditions (pH = 4, approximately 2% DMSO), the fluorescent probe molecule L exhibits weak fluorescence emission at 510 nm. Figure 3 When Ga is added 3+ When ions are introduced into this acidic solution, the yellow fluorescence is visibly enhanced. Figure 1 d) This observation is consistent with the detection data, after adding Ga 3+ Subsequently, the fluorescence emission intensity of the fluorescent probe molecule L at 519 nm increased significantly. Figure 3 ).

[0055] Example 2: Fluorescent probe molecule L against Ga 3+ Fluorescence recognition is affected by interference from other metal ions.

[0056] Prepare a DMSO solution (10 mmol / L) of fluorescent probe molecule L at room temperature and sonicate until completely dissolved.

[0057] Preparation of Cd at room temperature 2+ Hg 2+ Al 3+ Mg 2+ Na + Pb 2+ Ag + Ce 3+ Mn 2+ Cr 3+ Zn 2+ Cu 2+ Ga 3+ Fe 3+ Co 2+ Ni 2+ A nitrate aqueous solution (1 mmol / L, water as solvent).

[0058] Take 2 mL of Cd 2+ Hg 2+ Al 3+ Mg 2+ Na + Pb 2+ Ag + Ce 3+ Mn 2+ Cr 3+ Zn 2+ Cu 2+ Fe 3+ Co 2+ and Ni 2+ A 1 mmol / L nitrate aqueous solution was prepared, followed by the addition of 40 μL of DMSO solution (10 mmol / L) containing the fluorescent probe molecule L, and then 20 μL of dilute hydrochloric acid (8% by mass) was added to adjust the pH to 4. The fluorescence intensity at 519 nm was detected using an F7000 fluorescence spectrometer under excitation at 365 nm.

[0059] Take 1 mL of Cd 2+ Hg 2+ Al 3+ Mg 2+ Na + Pb 2+ Ag + Ce 3+ Mn2+ Cr 3+ Zn 2+ Cu 2+ Fe 3+ Co 2+ and Ni 2+ A 1 mmol / L nitrate aqueous solution was added, followed by 40 μL of DMSO solution (10 mmol / L) containing the fluorescent probe molecules, and then 1 mL of Ga was added. 3+ A 1 mmol / L nitrate aqueous solution was prepared, and then 20 μL of dilute hydrochloric acid (8% by mass) was added to adjust the pH to 4. The fluorescence intensity at 519 nm was detected by an F7000 fluorescence spectrometer under excitation at a wavelength of 365 nm.

[0060] Fluorescent probe molecule L exhibits high sensitivity and selectivity in recognizing Ga under acidic conditions. 3+ Unaffected by metal ions (Cd) 2 + Hg 2+ Al 3+ Mg 2+ Na + Pb 2+ Ag + Ce 3+ Mn 2+ Cr 3+ Zn 2+ Cu 2+ Ga 3+ Fe 3+ Co 2+ Ni 2+ Interference () Figure 4 ).

[0061] Example 3 Ga 3+ Application of fluorescent probes in industrial sludge

[0062] Prepare a DMSO solution (10 mmol / L) of fluorescent probe molecule L at room temperature and sonicate until completely dissolved.

[0063] Preparation of Ga at room temperature 3+ A nitrate aqueous solution (1 mmol / L, water as solvent).

[0064] Prepare the following aqueous solutions of industrial sludge (based on the highest concentration of metal ions): 0.1 mmol / L, 1 mmol / L, 2 mmol / L, 3 mmol / L, 4 mmol / L, 5 mmol / L, 6 mmol / L, 10 mmol / L, 100 mmol / L, and 1 mol / L, at room temperature; sonicate until the metal ions are fully dissolved, then filter and use as needed.

[0065] Item 1: Add 1 μL of DMSO solution (10 mmol / L) of fluorescent probe molecules to 2 mL of industrial sludge aqueous solution (0.1 mmol / L), and adjust the pH to 4 with dilute hydrochloric acid.

[0066] Item 2: 2 mL of industrial sludge aqueous solution (1 mmol / L), add 10 μL of fluorescent probe molecule L of DMSO solution (10 mmol / L), and add dilute hydrochloric acid to adjust the pH to 4.

[0067] 3: Add 2 mL of an aqueous solution of industrial sludge (2 mmol / L), 20 μL of a DMSO solution of fluorescent probe molecules (10 mmol / L), and adjust the pH to 4 with dilute hydrochloric acid.

[0068] 4: Add 2 mL of an aqueous solution of industrial sludge (3 mmol / L), 30 μL of DMSO solution of fluorescent probe molecules (10 mmol / L), and adjust the pH to 4 with dilute hydrochloric acid.

[0069] 5: Add 2 mL of an aqueous solution of industrial sludge (4 mmol / L), 40 μL of DMSO solution of fluorescent probe molecules (10 mmol / L), and adjust the pH to 4 with dilute hydrochloric acid.

[0070] 6: Add 2 mL of an aqueous solution of industrial sludge (5 mmol / L), 50 μL of DMSO solution of fluorescent probe molecules (10 mmol / L), and adjust the pH to 4 with dilute hydrochloric acid.

[0071] 7: Add 60 μL of DMSO solution (10 mmol / L) containing 2 mL of industrial sludge (6 mmol / L), and adjust the pH to 4 with dilute hydrochloric acid.

[0072] 8: Add 2 mL of an aqueous solution of industrial sludge (10 mmol / L), 100 μL of DMSO solution of fluorescent probe molecules (10 mmol / L), and adjust the pH to 4 with dilute hydrochloric acid.

[0073] 9: Add 2 mL of an aqueous solution of industrial sludge (100 mmol / L), 1 mL of DMSO solution of fluorescent probe molecules (10 mmol / L), and adjust the pH to 4 with dilute hydrochloric acid.

[0074] 10: Add 2 mL of an aqueous solution of industrial sludge (1 mol / L), 2 mL of DMSO solution of fluorescent probe molecules (10 mmol / L), and add dilute hydrochloric acid to adjust the pH to 4.

[0075] Fluorescence spectra in the wavelength range of 400-750 nm were detected by an F7000 fluorescence spectrometer under excitation wavelength of 365 nm.

[0076] The results showed that the fluorescence emission of the probe was significant starting from probe number 5, and the fluorescence intensity increased linearly with increasing concentration, indicating that this industrial sludge contained Ga. 3+ ion.

[0077] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. Any of the following applications of the compound shown in formula (I): (i) In the preparation, detection, identification, and tracing of Ga 3+ Applications of fluorescent probes for ions; (ii) In the detection, identification, and tracing of Ga 3+ Applications in ions; (iii) In the preparation, detection, identification, and tracing of Ga 3+ Applications of ions in products or reagents; in, R0 may be the same or different, and are independently selected from H and C. 1-10 alkyl.

2. The application according to claim 1, characterized in that, R0 may be the same or different, and are independently selected from H and C. 1-6 Alkyl; preferably, R0 are the same; preferably, R0 are all methyl; Preferably, the compound represented by formula (I) is selected from the following compounds:

3. The application according to claim 1 or 2, characterized in that, The application is for detecting, identifying, and tracing Ga in environmental and biological samples. 3+ ion.

4. The application according to any one of claims 1-3, characterized in that, The compound shown in formula (I) can be used to detect, identify, and trace Ga under acidic conditions. 3+ ion; Preferably, the acidic condition is a pH value less than or equal to 4.

5. The application according to any one of claims 1-4, characterized in that, The working concentration of the compound shown in formula (I) is 0.01 mmol / L-50 mmol / L, preferably 0.1 mmol / L-20 mmol / L; Preferably, Ga 3+ The concentration of ions is 0.01 mmol / L-50 mmol / L, preferably 0.1 mmol / L-20 mmol / L; Preferably, the compound shown in formula (I) is combined with Ga 3+ The molar ratio of ions is 0.01-10:10, preferably 0.1-8:10; Preferably, the fluorescence emission wavelength of the compound shown in formula (I) is 510 nm-530 nm.

6. A detection, identification, and tracing method for Ga 3+ The products or reagents containing ions, said products or reagents include: (1) The compound shown in formula (I); (2) Acidic reagents; Among them, R0 may be the same or different, and are independently selected from H and C. 1-10 alkyl.

7. The product or reagent according to claim 6, characterized in that, R0 may be the same or different, and are independently selected from H and C. 1-6 Alkyl; preferably, R0 are the same; preferably, R0 are all methyl; Preferably, the compound represented by formula (I) is selected from the following compounds:

8. The product or reagent according to claim 6 or 7, characterized in that, The product or reagent may optionally further include a solvent; the solvent may be, for example, DMSO; Preferably, the concentration of the solution of the compound shown in formula (I) is 0.01 mmol / L-1 mol / L, more preferably 0.1 mmol / L-1 mol / L; Preferably, the solution of the compound shown in formula (I) can be diluted before use; Preferably, the working concentration of the compound shown in formula (I) is 0.01 mmol / L-50 mmol / L, and more preferably 0.1 mmol / L-20 mmol / L.

9. The product or reagent according to any one of claims 6-8, characterized in that, Acidic reagents are selected from organic acids and inorganic acids; inorganic acids include hydrochloric acid. Preferably, the pH of the reaction system for detection, identification, and tracing is adjusted to be less than or equal to 4 using an acidic reagent; Preferably, the product or reagent is a test kit.

10. The product or reagent according to any one of claims 6-9 for detecting, identifying, and tracing Ga in environmental or biological samples. 3+ Applications in ions.

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