CN110441279B - Application of phosphonic acid column [5] arene in recognition of ferrous ions, copper ions or aluminum ions - Google Patents

Abstract

The invention provides a phosphonic acid column [5]]Aromatic hydrocarbon in recognition of Fe²⁺、Cu²⁺Or Al³⁺Belonging to the technical field of metal ion detection. Phosphonic acid column [5] of the invention]Aromatic hydrocarbon can accurately and quickly identify and detect whether the solution contains Fe or not in 21 common metal ion solutions²⁺、Cu²⁺Or Al³⁺。

Description

Application of phosphonic acid column [5] arene in recognition of ferrous ions, copper ions or aluminum ions

Technical Field

The invention relates to the technical field of metal ion detection, in particular to a phosphonic acid column [5]]Aromatic hydrocarbon in recognition of Fe²⁺、Cu^{2 +}Or Al³⁺The use of (1).

Background

Iron is a trace element in the living body and is closely related to a plurality of metabolic activities in the cell. Abnormalities in the concentration of elemental iron in the human body can lead to parkinsonism, anemia, decreased immunity and alzheimer's disease. Due to the reducing environment of the cell itself, most of the iron in the cell is Fe²⁺The form exists, and when the iron in the hemoglobin is in a divalent state, reversible combination can be generated between the iron and oxygen.

As an important trace element and essential nutrient of the organism, the unbalance of copper element results in the inhibition of neurological diseases such as alzheimer's disease, Menkes ' melastoma syndrome and Wilson's disease, and thus the distribution of copper ions and ferrous ions in cells is strictly controlled.

Al³⁺Is not a necessary trace element for human body, wherein the aluminum product belongs to a class of carcinogen, the aluminum element added in food additives, cosmetics and other consumer products can cause osteomalacia, Alzheimer's disease and breast cancer, and the excessive exposure of the body to the aluminum environment can cause the damage of the nerve center of the human body. It also disturbs the growth of aquatic organisms and plants.

In conclusion, a method capable of effectively and selectively detecting Fe is developed²⁺、Cu²⁺Or Al³⁺Has great significance in the aspects of environment, health and medical treatment.

Disclosure of Invention

The invention aims to provide a phosphonic acid column [5]]Aromatic hydrocarbon (PP5A) in recognition of Fe²⁺、Cu²⁺Or Al³⁺The use of (1).

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a phosphonic acid column [5]]Aromatic hydrocarbon in recognition of Fe²⁺、Cu²⁺Or Al³⁺The phosphonic acid column [5]]The aromatic hydrocarbon has a structure shown in formula I

Preferably, the phosphonic acid column [5]]Aromatic hydrocarbon recognition of Fe²⁺、Cu²⁺Or Al³⁺The method comprises the following steps:

subjecting phosphonic acid column [5]]Aromatic hydrocarbons and compounds containing M⁺Mixing the solutions, and standing for 30min to obtain a solution to be detected;

performing fluorescence spectrum measurement on the solution to be measured;

the M is⁺Is Fe²⁺、Cu²⁺Or Al³⁺。

Preferably, when said M is⁺Is Al³⁺Then, the liquid to be detected is compared with a phosphonic acid column [5]]The fluorescence intensity of the aromatic hydrocarbon is enhanced;

when said M is⁺Is Cu²⁺Then, the liquid to be detected is compared with a phosphonic acid column [5]]The fluorescence intensity of the aromatic hydrocarbon decreases;

when said M is⁺Is Fe²⁺And then, quenching the fluorescence of the solution to be detected.

Preferably, when M is⁺Is Fe²⁺When said contains M⁺In solution of (2) M⁺The concentration of the active ingredient is more than or equal to 0.037 mu M;

when M is⁺Is Cu²⁺When said contains M⁺In solution of (2) M⁺The concentration of the sodium hydroxide is more than or equal to 0.057 mu M;

when M is⁺Is Al³⁺When said contains M⁺In solution of (2) M⁺The concentration of (B) is more than or equal to 0.102 mu M.

Preferably, the phosphonic acid column [5] in the liquid to be detected]The concentration of aromatic hydrocarbon is 1.2X 10^-5mol/L。

Preferably, the pH value of the solution to be detected is 1-12.

Preferably, the pH value of the solution to be detected is adjusted by using 0.1mol/L HCl solution or 0.1mol/L NaOH solution.

The invention provides a phosphonic acid column [5]]Aromatic hydrocarbon in recognition of Fe²⁺、Cu²⁺Or Al³⁺The phosphonic acid column [5]]The aromatic hydrocarbon has a structure shown in formula I

Phosphonic acid column [5] of the invention]Aromatic hydrocarbon can accurately and quickly identify and detect whether the solution contains Fe or not in the common metal ion solution in 21²⁺、Cu²⁺Or Al³⁺。

Drawings

Fig. 1 is a graph of the fluorescent response of PP5A to 21 metal ions at pH 7;

FIG. 2 identifies Cu for PP5A²⁺The kinetic curve of (a);

FIG. 3 is a graph showing the recognition of Fe by PP5A²⁺The kinetic curve of (a);

FIG. 4 is a Job's plot of PP5A versus M +;

FIG. 5 shows PP5A and Fe²⁺Fluorescence ofTitrimetric chart and standard curve;

FIG. 6 shows PP5A and Cu²⁺A fluorescence titration plot and a standard curve of (a);

FIG. 7 shows PP5A and Al³⁺A fluorescence titration plot and a standard curve of (a);

FIG. 8 is a graph of PP5A recognizing Fe²⁺The anti-interference test of (2);

FIG. 9 identifies Cu for PP5A²⁺The anti-interference test of (2);

FIG. 10 identification of Al for PP5A³⁺The anti-interference test of (2);

FIG. 11 shows the recognition of Fe by PP5A for different pH²⁺、Cu²⁺Or Al³⁺The influence curve of (c).

Detailed Description

The invention provides a phosphonic acid column [5]]Aromatic hydrocarbon in recognition of Fe²⁺、Cu²⁺Or Al³⁺The phosphonic acid column [5]]The aromatic hydrocarbon has a structure shown in formula I

In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.

In the present invention, the phosphonic acid column [5] arene is preferably obtained by preparation, and the preparation method of the phosphonic acid column [5] arene preferably comprises the following steps:

a compound having a structure represented by formula 1 (2.00g, 10.09mmol), PPh₃(5.29g,20.18mmol) and 50mL of CH was added₃After CN, 10mL of CBr was added dropwise under nitrogen atmosphere₄(6.69g, 20.18mmol) of CH₃CN solution, reacting at room temperature for 5h, pouring ice water, filtering, and washing with petroleum ether/methanol (V: V ═ 1:1) to obtain a compound (white flaky crystal) having a structure shown in formula 2;

the compound (1.62g, 5mmol) having the structure shown in formula 2 and (CH)₃O)_n(0.4504g, 15mmol, "n" is the degree of polymerization, and n is not particularly limited) and 20mL of 1, 2-dichloroethane were mixed, and added dropwise under a nitrogen atmosphereBoron trifluoride diethyl etherate (0.70g, 5mmol) was added, reacted at room temperature for 6h, and quenched with water. Adding saturated saline solution for extraction, collecting the lower organic phase, drying (drying agent: anhydrous sodium sulfate), concentrating under reduced pressure, and purifying by column chromatography (petroleum ether: dichloromethane ═ 1:1) to obtain a compound (white powdery solid) having a structure represented by formula 3;

mixing the compound (2.50g, 1.49mmol) with the structure shown in the formula 3 and triethyl phosphite (24.71g, 149mmol), stirring for 72h at 165 ℃ under a nitrogen atmosphere, concentrating, and purifying by column chromatography to obtain a compound (light yellow oily substance) with the structure shown in the formula 4;

TMSBr (14.25g, 93.1mmol), the compound having the structure represented by formula 4 (3.0g, 1.33mmol) and dichloromethane were mixed at 0 ℃ under a nitrogen atmosphere, stirred at room temperature for 72 hours, after the reaction was completed, the solvent was distilled off under reduced pressure, water (30mL) was added and stirring was continued for 30 minutes, followed by concentration and drying, and then washed with acetone to obtain phosphonic acid column [5] arene (white solid).

¹H NMR(400MHz,DMSO-d 6,298K)δ(ppm):10.30(s,20H),6.87(s,10H),4.10-4.03(m,20H),3.67(s,10H),2.36-2.16(m,20H).¹³C NMR(75MHz,DMSO-d6,298K)δ(ppm):149.3,128.1,114.4,63.1,31.1,28.3.³¹P NMR(162MHz,DMSO-d 6,298K)

The above synthetic route is specifically represented by the following formula:

in the present invention, the phosphonic acid column [5]]Aromatic hydrocarbon recognition of Fe²⁺、Cu²⁺Or Al³⁺Preferably comprising the steps of:

subjecting phosphonic acid column [5]]Aromatic hydrocarbons and compounds containing M⁺Mixing the solutions, and standing for 30min to obtain a solution to be detected;

performing fluorescence spectrum measurement on the solution to be measured;

the M is⁺Is Fe²⁺、Cu²⁺Or Al³⁺。

In the present invention, when M⁺Is Fe²⁺When said contains M⁺In solution of (2) M⁺The concentration of (A) is preferably more than or equal to 0.037 mu M; when M is⁺Is Cu²⁺When said contains M⁺In solution of (2) M⁺The concentration of (b) is preferably more than or equal to 0.057 mu M; when M is⁺Is Al³⁺When said contains M⁺In solution of (2) M⁺The concentration of (b) is preferably not less than 0.102. mu.M; in the invention, the phosphonic acid column [5] in the liquid to be detected]The concentration of aromatic hydrocarbon is 1.2X 10^-5mol/L. In the invention, the pH value of the liquid to be detected is preferably 1-12, and more preferably 3-10; in the present invention, the pH value is preferably selected such that the phosphonic acid column [5] is used when the pH value is 3 to 10]Aromatic hydrocarbon P Fe²⁺、Cu²⁺Or Al³⁺All have recognition function, when the pH value is 1-3 or 10-12, the phosphonic acid column [5]]Aromatic only to Al³⁺Has recognition function and needs to be used for Fe under the condition that the pH value is 3-10²⁺Or Cu²⁺Further identification is performed. In the present invention, the pH of the solution to be measured is preferably adjusted by using 0.1mol/L HCl solution or 0.1mol/L NaOH solution.

The present invention does not have any particular limitation on the condition parameters for the fluorescence spectroscopic measurement, and the measurement may be carried out under conditions well known to those skilled in the art.

In the present invention, when said M is⁺Is Al³⁺Then, the liquid to be detected is compared with a phosphonic acid column [5]]The fluorescence intensity of the aromatic hydrocarbon is enhanced;

when said M is⁺Is Cu²⁺Then, the liquid to be detected is compared with a phosphonic acid column [5]]The fluorescence intensity of the aromatic hydrocarbon decreases;

when said M is⁺Is Fe²⁺And then, quenching the fluorescence of the solution to be detected.

The following phosphonic acid column [5] provided by the present invention is illustrated in connection with the examples]Aromatic hydrocarbon in recognition of Fe²⁺、Cu²⁺Or Al³⁺The applications in (1) are explained in detail, but they should not be construed as limiting the scope of the invention.

In the following examples, all of the phosphonic acid column [5] arenes were prepared by the foregoing preparation methods;

the reagent involved is: AgNO₃，Al(NO₃)₃·9H₂O，BaCl₂·2HO₂，CaCl₂，CdCl₂，CoCl₂·6H₂O，Cs₂CO₃，CuSO₄·5H₂O，FeSO₄·7HO₂，FeCl₃·6H₂O，HgCl₂，KCl，LiF，MgSO₄·7H₂O，Na₂SO₄，SbCl₃，SnCl₂·2H₂O，SrCl₂·6H₂O，NiCl₂·6H₂O，ZnSO₄·7H₂O and CH₄CH₆MnO₄Are purchased from national chemical reagent limited company, and are analytically pure, and the water is ultrapure water;

containing M⁺Preferably, the solution of (A) is a simulated solution, i.e. a solution prepared at a concentration of 1.8X10^-5mol/L of a compound containing M⁺In a solution or concentration of 4.8X10^-5mol/L of a compound containing M⁺The solution of (1).

Examples 1 to 12

Subjecting phosphonic acid column [5]]Aromatic hydrocarbons and concentration of 1.8X10^-5mol/L of Al-containing³⁺The solution is mixed, the pH value of the solution is adjusted to 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 by adopting 0.1mol/L HCl solution or 0.1mol/L NaOH solution, and the solution is kept stand for 30min to obtain a solution to be detected;

and performing fluorescence spectrum determination on the solution to be detected.

Examples 13 to 20

Subjecting phosphonic acid column [5]]Aromatic hydrocarbons and concentration of 1.8X10^-5mol/L Fe-containing²⁺The solution is mixed, the pH value of the solution is adjusted to 3, 4, 5, 6, 7, 8, 9 and 10 by adopting 0.1mol/L HCl solution or 0.1mol/L NaOH solution, and the solution is kept stand for 30min to obtain a solution to be tested;

and performing fluorescence spectrum determination on the solution to be detected.

Examples 21 to 28

Subjecting phosphonic acid column [5]]Aromatic hydrocarbons and concentration of 1.8X10^-5mol/L of Cu²⁺The solution is mixed, the pH value of the solution is adjusted to 3, 4, 5, 6, 7, 8, 9 and 10 by adopting 0.1mol/L HCl solution or 0.1mol/L NaOH solution, and the solution is kept stand for 30min to obtain a solution to be tested;

and performing fluorescence spectrum determination on the solution to be detected.

Examples 29 to 40

Subjecting phosphonic acid column [5]]Aromatic hydrocarbons and concentration of 4.8X10^-5mol/L of Cu²⁺The solution is mixed, the pH value of the solution is adjusted to 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 by adopting 0.1mol/L HCl solution or 0.1mol/L NaOH solution, and the solution is kept stand for 30min to obtain a solution to be detected;

and performing fluorescence spectrum determination on the solution to be detected.

Comparative examples 1 to 18

Subjecting phosphonic acid column [5]]The aromatic hydrocarbons respectively have a concentration of 1.8X10^-5mol/L of a compound containing N⁺(Ag⁺,Ba²⁺,Ca²⁺,Cd²⁺,Co³⁺,Cs⁺,Fe³⁺,Hg²⁺,K⁺,Li⁺,Mg²⁺,Na⁺,Sb²⁺,Sn²⁺,Sr²⁺,Ni²⁺,Zn²⁺And Mn²⁺) Mixing the solutions, adjusting the pH value to 7 with 0.1mol/L HCl solution and 0.1mol/L NaOH solution, and standing for 30min to obtain a solution to be detected;

and performing fluorescence spectrum determination on the solution to be detected.

FIG. 1 is a graph of the fluorescent response of PP5A to 21 metal ions at pH 7 (where M is⁺At a concentration of 1.8X10^-5mol/L), Fe is shown in FIG. 1²⁺Quenching the fluorescence of PP5A, Cu²⁺Can reduce the fluorescence of PP5A, and Al³⁺The fluorescence of PP5A can be enhanced; the other metal ions had no significant effect on the fluorescence intensity of PP 5A.

Comparative examples 19 to 22

Subjecting phosphonic acid column [5]]Aromatic hydrocarbons and concentration of 1.8X10^-5mol/L Fe-containing²⁺The solution is mixed, the pH value of the solution is adjusted to 1,2, 11 and 12 by adopting 0.1mol/L HCl solution or 0.1mol/L NaOH solution, and the solution is kept stand for 30min to obtain a solution to be detected;

and performing fluorescence spectrum determination on the solution to be detected.

Comparative examples 23 to 26

Subjecting phosphonic acid column [5]]Aromatic hydrocarbons and concentration of 4.8X10^-5mol/L of Cu²⁺The solution is mixed, the pH value of the solution is adjusted to 1,2, 11 and 12 by adopting 0.1mol/L HCl solution or 0.1mol/L NaOH solution, and the solution is kept stand for 30min to obtain a solution to be detected;

and performing fluorescence spectrum determination on the solution to be detected.

FIG. 11 shows the recognition of Fe by PP5A for different pH²⁺、Cu²⁺Or Al³⁺The influence curves of (1) and (30) (where a is PP5A, b is examples 1 to 12, c is examples 13 to 20 and comparative examples 19 to 22, and d is examples 29 to 44 and comparative examples 27 to 30) are shown in FIG. 11, in which Fe²⁺And Cu²⁺The fluorescence of PP5A can be weakened or quenched in the pH range of 3-10; al (Al)³⁺The fluorescence of PP5A can be enhanced in the pH range of 1-12.

Verification example

And (3) dynamic testing:

200. mu.L of 1mmol/L PP5A was transferred into a 10mL volumetric flask, and 180. mu.L of 1mmol/L Fe-containing solution was transferred separately^{2 +}、Cu²⁺The solution is put into a volumetric flask, timing is started at the moment of moving in, the solution is poured into a fluorescence cuvette after constant volume shaking is carried out uniformly, the fluorescence intensity is measured every 1min, and the measurement is carried out continuously for 30 min. After the measurement, the fluorescence intensity was plotted as ordinate and the time as abscissa, and PP5A was plotted to identify Fe²⁺And Cu²⁺The kinetic curves of (2) and (3) show that PP5A is against Cu as shown in FIGS. 2 and 3²⁺Is almost instantaneously complete for Fe²⁺The identification of (1) needs 30min to reach the identification balance, which indicates that Fe²⁺And Cu²⁺There was a large difference in the fluorescence kinetic response to PP 5A.

And (3) determining the complex ratio:

the preparation concentrations are all 1.2 multiplied by 10^-5mol/L PP5A and M⁺Each solution was 50 mL. The PP5A solution (5.0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5 and 0mL) and M were removed separately⁺The solutions (0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 and 5mL) were placed in a 5mL volumetric flask and shaken well before waiting for 30min for their fluorescence spectra to be measured. Will M⁺The molar fraction of (3) as X-coordinate and the fluorescence intensity multiplied by the molar fraction as Y-coordinate, and plotting the Job's curve, as shown in FIG. 4As can be seen from FIG. 4, PP5A is blended with Al³⁺When the molar ratio is equal to 0.5, the difference between the corresponding fluorescence intensities reaches the maximum, PP5A and Al³⁺The complexation ratio of (A) to (B) is 1: 1; PP5A and Fe²⁺And Cu²⁺The maximum value of the difference between the fluorescence intensities corresponding to a large molar ratio equal to 0.3 is PP5A and Fe²⁺And Cu²⁺The complexation ratio of (A) to (B) is 2: 1.

Fluorescence titration:

the fixed PP5A concentration was 1.2X 10^-50 to 6.0eq (eq is 1 equivalent of PP5A) of Fe is added to each L of the mixture²⁺And 0 to 6.0eq of Cu²⁺: the fixed PP5A concentration was 6X 10^-6mol/L, then adding 0-3.0 eq of Al³⁺. FIG. 5 shows PP5A and Fe²⁺A fluorescence titration plot and a standard curve of (a); FIG. 6 shows PP5A and Cu²⁺A fluorescence titration plot and a standard curve of (a); FIG. 7 shows PP5A and Al³⁺A fluorescence titration plot and a standard curve of (a); as can be seen from FIGS. 5 to 7, with Fe²⁺And Cu²⁺The emission peak of PP5A at 328nm gradually decreases to quench with increasing concentration, for Al³⁺To be precise, with Al³⁺The emission peak of PP5A at 328nm is gradually enhanced with the red shift phenomenon. At the same time, PP5A is mixed with Fe²⁺、Cu²⁺And Al³⁺The linear equation and detection limit for the timing of the fluorescent droplets are shown in Table 1. The detection limit is calculated according to the equations (1) and (2).

The standard curve equations corresponding to the standard curves shown in fig. 5 to 7 are shown in table 1:

TABLE 1 PP5A with Fe²⁺、Cu²⁺And Al³⁺Linear equation, correlation coefficient and detection limit for fluorescent drop timing

And (3) anti-interference test:

PP5A recognizes Fe²⁺The anti-interference test comprises the following steps: to PP5A (1.2X 10)^-5mol/L) and PP5A/Fe²⁺System (1.2X 10)^{- 5}mol/LPP5A+1.5eq Fe²⁺) Adding 1.5eq of other metal ions (Ag)⁺,Ba²⁺,Ca²⁺,Cd²⁺,Co³⁺,Cs⁺,Fe³⁺,Hg²⁺,K⁺,Li⁺,Mg²⁺,Na⁺,Sb²⁺,Sn²⁺,Sr²⁺,Ni²⁺,Zn²⁺And Mn²⁺)；

PP5A identifies Cu²⁺The anti-interference test comprises the following steps: to PP5A (1.2X 10)^-5mol/L) and PP5A/Cu²⁺System (1.2X 10)^{- 5}mol/LPP5A+4.0eq Cu²⁺) Adding 4eq of other metal ions (Ag)⁺,Ba²⁺,Ca²⁺,Cd²⁺,Co³⁺,Cs⁺,Fe³⁺,Hg^{2 +},K⁺,Li⁺,Mg²⁺,Na⁺,Sb²⁺,Sn²⁺,Sr²⁺,Ni²⁺,Zn²⁺And Mn²⁺)；

PP5A recognizes Al³⁺The anti-interference test comprises the following steps: to PP5A (1.2X 10)^-5mol/L) and PP5A/Al³⁺System (1.2X 10)^{- 5}mol/L PP5A+1.5eqAl³⁺) Adding 1.5eq of other metal ions (Ag)⁺,Ba²⁺,Ca²⁺,Cd²⁺,Co³⁺,Cs⁺,Fe³⁺,Hg²⁺,K⁺,Li⁺,Mg²⁺,Na⁺,Sb²⁺,Sn²⁺,Sr²⁺,Ni²⁺,Zn²⁺And Mn²⁺). Using deionized water to fix the volume, and measuring the fluorescence spectrum after standing for 30 min.

FIG. 8 is a graph of PP5A recognizing Fe²⁺The anti-interference test of (2); FIG. 9 identifies Cu for PP5A²⁺The anti-interference test of (2); FIG. 10 identification of Al for PP5A³⁺The anti-interference test of (2); as can be seen from FIGS. 8 to 10, the other metal cation pairs PP5A/Fe²⁺、Cu²⁺And Al³⁺The interference of the recognition system is small, which shows that PP5A can be applied to Fe²⁺、Cu²⁺And Al³⁺And (4) specific recognition.

From the above examples, phosphonic acid column [5]]Aromatic hydrocarbon can accurately and quickly identify and detect whether the solution contains Fe or not in the common metal ion solution in 21²⁺、Cu²⁺Or Al³⁺。

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (4)

1. Phosphonic acid column [5]]Aromatic hydrocarbon in recognition of Fe²⁺、Cu²⁺And Al³⁺Characterized in that the phosphonic acid column [5]]The aromatic hydrocarbon has a structure shown in formula I:

the phosphonic acid column [5]]Aromatic hydrocarbon recognition of Fe²⁺、Cu²⁺Or Al³⁺The method comprises the following steps:

subjecting phosphonic acid column [5]]Aromatic hydrocarbons and compounds containing M⁺Mixing the solutions, and standing for 30min to obtain a solution to be detected;

performing fluorescence spectrum measurement on the solution to be measured;

the M is⁺Is Fe²⁺、Cu²⁺Or Al³⁺；

When said M is⁺Is Al³⁺Then, the liquid to be detected is compared with a phosphonic acid column [5]]The fluorescence intensity of the aromatic hydrocarbon is enhanced;

when said M is⁺Is Cu²⁺Then, the liquid to be detected is compared with a phosphonic acid column [5]]The fluorescence intensity of the aromatic hydrocarbon decreases;

when said M is⁺Is Fe²⁺Quenching the fluorescence of the solution to be detected;

said Fe²⁺And Cu²⁺The phosphonic acid column [5] is used in the range of pH 3-10 of the solution to be detected]The fluorescence of the aromatic hydrocarbon is weakened or quenched; the Al is³⁺Leading phosphonic acid column [5] in the range of pH 1-12 of the solution to be detected]Fluorescence enhancement of aromatic hydrocarbons;

the phosphonic acid column [5]]Aromatic hydrocarbon and Al³⁺The complexing molar ratio is 1: 1; the phosphonic acid column [5]]Aromatic hydrocarbons and Fe²⁺The complexing molar ratio is 2: 1; the phosphonic acid column [5]]Aromatic hydrocarbons and Cu²⁺The complexing molar ratio was 2: 1.

2. The use of claim 1, wherein when M is⁺Is Fe²⁺When said contains M⁺In solution of (2) M⁺The concentration of the active ingredient is more than or equal to 0.037 mu M;

when M is⁺Is Cu²⁺When said contains M⁺In solution of (2) M⁺The concentration of the sodium hydroxide is more than or equal to 0.057 mu M;

when M is⁺Is Al³⁺When said contains M⁺In solution of (2) M⁺The concentration of (B) is more than or equal to 0.102 mu M.

3. The use of claim 1, wherein the test solution comprises a column [5] of phosphonic acid]The concentration of aromatic hydrocarbon is 1.2X 10^-5mol/L。

4. The use of claim 1, wherein the pH of the test solution is adjusted using a 0.1mol/LHCl solution or a 0.1mol/LNaOH solution.

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