High-water-solubility rhodamine-based polyion liquid and preparation method and application thereof

Abstract

The invention belongs to the field of detection of heavy metal ions and particularly relates to high-water-solubility rhodamine-based polyion liquid and a preparation method thereof. The high-water-solubility rhodamine-based polyion liquid is applied to quick visual colorimetric detection of pure-water-phase copper ions. The rhodamine-based polyion liquid is formed by copolymerization of ion liquid monomers and salicylide-like rhodamine B hydrazide monomers, and has the advantages that the raw materials are low in cost and easy to obtain, preparation is easy and convenient, the rhodamine content is high, water solubility is excellent, and no nonspecific binding site exists; and efficient colorimetric detection of trace copper can be achieved in the environment of pure water, the detection limit of naked eyes and the detection limit of an ultraviolet-visible light spectrophotometric method are 0.5 micron and 0.15 micron correspondingly and are both far lower than 31 microns specified by the World Health Organization (WHO). In addition, the detection response time of detection of the rhodamine-based polyion liquid to copper ions is short, developing can be completed within 5s, and moreover, the rhodamine-based polyion liquid has excellent selectivity and is hardly influenced by other concomitant metal ions.

Description

technical field

[0001] The invention belongs to the field of detection of heavy metal ions, and in particular relates to a highly water-soluble rhodamine-based polyionic liquid and a preparation method thereof, and the application of rapid visual colorimetric detection of pure water-phase copper ions. Background technique

[0002] Copper is an indispensable trace element for human health, but when copper ions are taken in excess, it will cause dysfunction in organs such as liver, gallbladder, brain, cornea and heart. With the rapid development of modern industry (especially mining and metallurgy, mechanical processing, chemical industry, electronics and other industries), the problem of copper ion pollution in water environment has become increasingly serious. The World Health Organization (WHO) clearly stipulates that the copper ion content in drinking water should be lower than 2mg / L (ie 31μM). Therefore, the rapid detection of copper ions in water environment is of great...

Examples

Embodiment 1

[0036] A highly water-soluble rhodamine-based polyionic liquid, the molecular structure of which is shown in Formula 1, where m / (n+m)=0.02-0.05, and the abbreviation is P(RhBHSA-co-META).

[0037]

[0038] Formula 1 Structural formula of highly water-soluble rhodamine-based polyionic liquid

[0039] The synthetic method of above-mentioned rhodamine-based polyionic liquid P (RhBHSA-co-META), main steps are as follows:

[0040] 1) Synthesis of RhBH: Dissolve 4.8g of rhodamine B (RhB) and 12mL of hydrazine hydrate in 130mL of absolute ethanol, heat to reflux at 80°C, react for 2.5h, cool to room temperature, and rotate to evaporate, then add water and adjust the pH to about 8.5 , suction filtered and washed with distilled water for purification, and vacuum dried to obtain RhBH, yield: 90.1%;

[0041] 2) Synthesis of RhBHS: 2.3g of rhodamine B hydrazide (RhBH) and 1.6g of 2,4-dihydroxybenzaldehyde were dissolved in 120mL of absolute ethanol, heated to 80°C and refluxed under n...

Embodiment 2

[0049] Determination of Functional Group Concentration of Rhodamine B Derivatives in Rhodamine-Based Polyionic Liquid P(RhBHSA-co-META)

[0050] Synthesized rhodamine derivative monomer RhBHSA and Cu in embodiment 1 2+ Dissolve in a mixed solvent (acetonitrile / water, v / v=3:1) to prepare 20μM RhBHSA and 20mM Cu 2+ The standard mother liquor (note, where Cu 2+ Large excess compared to RhBHSA).

[0051] Take 8 100mL volumetric flasks, dilute them to the standard solution with RhBHSA content of 10, 8, 6, 5, 4, 3, 2, 1 μM respectively, and carry out UV-Vis spectrophotometric test, and make a standard curve: A= 0.10694c-0.00118 (R 2 = 0.99993).

[0052] Synthesized rhodamine-based polyionic liquid P (RhBHSA-co-META) and Cu 2+ Dissolve in deionized water to make 100mg / L rhodamine-based polyionic liquid and 100mM Cu 2+ Aqueous solutions were subjected to UV-Vis spectrophotometric testing.

[0053] Combined with the calculation of the standard curve, it is determined that the mo...

Embodiment 3

[0055] Selectivity of rhodamine-based polyionic liquid P(RhBHSA-co-META) for colorimetric detection of copper ions

[0056] The rhodamine-based polyionic liquid P (RhBHSA-co-META) synthesized in Example 1 was dissolved in deionized water to form a 90 mg / L rhodamine-based polyionic liquid stock solution, and the rhodamine B derivative was measured in Example 2 The functional group concentration was 12.5 μM.

[0057] Take 16 5mL sample bottles, add 2mL rhodamine-based polyionic liquid stock solution, and then add 0.5mL 500μM Ag + 、Al 3+ 、Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2+ 、Cr 2+ 、Cu 2+ 、K + , Mg 2+ , Mn 2+ 、Na + 、Ni 2+ , Pb 2+ , Zn 2+ and H 2 O, the final solution contains 72 mg / L of rhodamine-based polyionic liquid (the functional group concentration of rhodamine B derivatives is 10 μM) and 100 μM of one of the above metal ions. UV-visible spectrophotometric tests were carried out on the solutions to verify the selective detection effect of rhodamine-based polyionic li...

technical field

[0001] The invention belongs to the field of detection of heavy metal ions, and in particular relates to a highly water-soluble rhodamine-based polyionic liquid and a preparation method thereof, and the application of rapid visual colorimetric detection of pure water-phase copper ions. Background technique

[0002] Copper is an indispensable trace element for human health, but when copper ions are taken in excess, it will cause dysfunction in organs such as liver, gallbladder, brain, cornea and heart. With the rapid development of modern industry (especially mining and metallurgy, mechanical processing, chemical industry, electronics and other industries), the problem of copper ion pollution in water environment has become increasingly serious. The World Health Organization (WHO) clearly stipulates that the copper ion content in drinking water should be lower than 2mg / L (ie 31μM). Therefore, the rapid detection of copper ions in water environment is of great...

Examples

Embodiment 1

[0036] A highly water-soluble rhodamine-based polyionic liquid, the molecular structure of which is shown in Formula 1, where m / (n+m)=0.02-0.05, and the abbreviation is P(RhBHSA-co-META).

[0037]

[0038] Formula 1 Structural formula of highly water-soluble rhodamine-based polyionic liquid

[0039] The synthetic method of above-mentioned rhodamine-based polyionic liquid P (RhBHSA-co-META), main steps are as follows:

[0040] 1) Synthesis of RhBH: Dissolve 4.8g of rhodamine B (RhB) and 12mL of hydrazine hydrate in 130mL of absolute ethanol, heat to reflux at 80°C, react for 2.5h, cool to room temperature, and rotate to evaporate, then add water and adjust the pH to about 8.5 , suction filtered and washed with distilled water for purification, and vacuum dried to obtain RhBH, yield: 90.1%;

[0041] 2) Synthesis of RhBHS: 2.3g of rhodamine B hydrazide (RhBH) and 1.6g of 2,4-dihydroxybenzaldehyde were dissolved in 120mL of absolute ethanol, heated to 80°C and refluxed under n...

Embodiment 2

[0049] Determination of Functional Group Concentration of Rhodamine B Derivatives in Rhodamine-Based Polyionic Liquid P(RhBHSA-co-META)

[0050] Synthesized rhodamine derivative monomer RhBHSA and Cu in embodiment 1 2+ Dissolve in a mixed solvent (acetonitrile / water, v / v=3:1) to prepare 20μM RhBHSA and 20mM Cu 2+ The standard mother liquor (note, where Cu 2+ Large excess compared to RhBHSA).

[0051] Take 8 100mL volumetric flasks, dilute them to the standard solution with RhBHSA content of 10, 8, 6, 5, 4, 3, 2, 1 μM respectively, and carry out UV-Vis spectrophotometric test, and make a standard curve: A= 0.10694c-0.00118 (R 2 = 0.99993).

[0052] Synthesized rhodamine-based polyionic liquid P (RhBHSA-co-META) and Cu 2+ Dissolve in deionized water to make 100mg / L rhodamine-based polyionic liquid and 100mM Cu 2+ Aqueous solutions were subjected to UV-Vis spectrophotometric testing.

[0053] Combined with the calculation of the standard curve, it is determined that the mo...

Embodiment 3

[0055] Selectivity of rhodamine-based polyionic liquid P(RhBHSA-co-META) for colorimetric detection of copper ions

[0056] The rhodamine-based polyionic liquid P (RhBHSA-co-META) synthesized in Example 1 was dissolved in deionized water to form a 90 mg / L rhodamine-based polyionic liquid stock solution, and the rhodamine B derivative was measured in Example 2 The functional group concentration was 12.5 μM.

[0057] Take 16 5mL sample bottles, add 2mL rhodamine-based polyionic liquid stock solution, and then add 0.5mL 500μM Ag + 、Al 3+ 、Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2+ 、Cr 2+ 、Cu 2+ 、K + , Mg 2+ , Mn 2+ 、Na + 、Ni 2+ , Pb 2+ , Zn 2+ and H 2 O, the final solution contains 72 mg / L of rhodamine-based polyionic liquid (the functional group concentration of rhodamine B derivatives is 10 μM) and 100 μM of one of the above metal ions. UV-visible spectrophotometric tests were carried out on the solutions to verify the selective detection effect of rhodamine-based polyionic li...

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