CN108918495B - Method for quantitatively detecting cyanide ions based on spectrophotometry of 2-aldehyde rhodamine derivatives - Google Patents
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Abstract
The invention relates to a method for quantitatively detecting cyanide ions by a spectrophotometry based on 2-aldehyde rhodamine derivatives. Adding a solution to be detected containing cyanide ions into a buffer solution of the 2-aldehyde rhodamine derivative, uniformly mixing, and measuring the absorbance at the maximum absorption peak under a spectrophotometer. The buffer solution of the 2-aldehyde rhodamine derivative is prepared by sequentially adding ethanol and disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution into the 2-aldehyde rhodamine derivative and uniformly mixing. The method of the invention can be used for rapidly and accurately measuring cyanide ions.
Description
Technical Field
The invention belongs to the field of chemical analysis, and particularly relates to a method for rapidly detecting cyanide by using a colorless rhodamine leuco body generated by the reaction of a 2-aldehyde rhodamine derivative and cyanide.
Background
Cyanide is a highly toxic substance and can be divided into simple cyanide and complex cyanide, the toxicity of the cyanide is the greatest of cyanide ions, the cyanide is combined with human ferricytochrome oxidase to generate ferricytochrome oxidase cyanide and lose the effect of oxygen transfer, and hypoxia asphyxia is caused, and in addition, the cyanide also has great toxicity to aquatic organisms. At present, cyanides in the environment mainly come from electroplating wastewater, coal gas washing water of a coke oven and a blast furnace, and various industrial wastewater of synthetic ammonia, non-ferrous metal ore dressing, smelting, chemical fiber production, pharmacy and the like. The water contains 0.1mg/L cyanide to kill insects, 0.3mg/L cyanide to kill self-cleaning microbes, and 0.3-0.5 mg/L cyanide to kill fish. Human beings can kill the disease only by taking about 0.28g of potassium cyanide orally. Cyanide is extremely harmful and can produce toxic symptoms within seconds. After the cyanide-containing wastewater is discharged into a water body, acute poisoning and even death of aquatic animals can be caused immediately. At present, the detection method of cyanide in the environment mainly adopts a volumetric method and a spectrophotometry method specified by national standards, and the methods are interfered by anions such as hypochlorite, sulfite ions, sulfide ions and the like to different degrees.
Rhodamine is a dye with excellent optical properties, and compared with other common fluorescent dyes, the rhodamine fluorescent dye has the advantages of good photostability, long-wavelength absorption, large absorption coefficient, high photostability in an open-loop form, insensitivity to pH, wider wavelength range, higher fluorescence quantum yield, long fluorescence lifetime and the like. Therefore, the fluorescent dye is widely applied to the aspects of pharmacology, physiology, molecular biology, cell biology, molecular genetics, environmental chemistry, single molecule detection, information science, fluorescent labeling, laser dye and the like, and is the most commonly used fluorescent dye in the fields of analytical chemistry and biomedical science in the biotechnology field. In recent years, rhodamine is widely used for the design and synthesis of metal ions and small molecule fluorescent probes, and the reason is that 2-carboxyl rhodamine and primary amine are amidated to generate stable leuco spiroimide, and then color and fluorescence are recovered after encountering metal ions or small molecules, so that the color change and the fluorescence detection of the metal ions and the organic small molecules are realized.
Disclosure of Invention
The invention aims to provide a spectrophotometry method for quantitatively detecting cyanide ions based on 2-aldehyde rhodamine derivatives without being interfered by anions.
The technical scheme adopted by the invention is as follows: the method for quantitatively detecting cyanide ions by a spectrophotometry based on the 2-aldehyde rhodamine derivatives comprises the following steps: adding a solution to be detected containing cyanide ions into a buffer solution of the 2-aldehyde rhodamine derivative, uniformly mixing, and measuring the absorbance at the maximum absorption peak under a spectrophotometer. The buffer solution of the 2-aldehyde rhodamine derivative is prepared by sequentially adding ethanol and disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution into the 2-aldehyde rhodamine derivative and uniformly mixing.
Further, in the method for quantitatively detecting cyanide ions by spectrophotometry based on the 2-aldehyde rhodamine derivative, the pH of the buffer solution of the 2-aldehyde rhodamine derivative is 9.0.
Further, in the method for quantitatively detecting cyanide ions by spectrophotometry based on the 2-aldehyde rhodamine derivative, the concentration of the 2-aldehyde rhodamine derivative in the buffer solution of the 2-aldehyde rhodamine derivative is (1-5) × 10-5mol/L。
Further, in the method for quantitatively detecting cyanide ions by spectrophotometry based on the 2-aldehyde rhodamine derivative, the volume ratio of ethanol to disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution is 3: 7.
Further, in the method for quantitatively detecting cyanide ions by spectrophotometry based on the 2-aldehyde rhodamine derivative, the 2-aldehyde rhodamine derivative has a structural general formula shown as (I):
wherein the content of the first and second substances,
R1＝R2＝R3＝R4＝H；
or R1＝R4＝H，R2＝-CH2CH3，R3＝-CH3；
Or R1＝R2＝-CH3，R3＝R4＝H；
Or R1＝R2＝-CH2CH3，R3＝R4＝H；
Or R1And R4Together form- (CH)2)3-，R2And R3Together form- (CH)2)3-。
Further, in the method for quantitatively detecting cyanide ions by spectrophotometry based on the 2-aldehyde rhodamine derivative, the preparation method of the 2-aldehyde rhodamine derivative comprises the following steps: taking rhodamine compounds, ethanolamine and absolute ethyl alcohol, reacting for 8-12h at 75-85 ℃, cooling to room temperature, filtering, dissolving the obtained solid in tetrahydrofuran solution, adding a reducing agent, stirring for 1-8 h at room temperature, adding water for quenching, extracting by dichloromethane, and purifying by column chromatography to obtain the 2-aldehyde rhodamine derivatives.
Further, in the method for quantitatively detecting cyanide ions by using the spectrophotometry based on the 2-aldehyde rhodamine derivative, the rhodamine compound is rhodamine B, rhodamine 6G, tetramethyl rhodamine TMR, rhodamine 110 or rhodamine 101.
Further, in the method for quantitatively detecting cyanide ions by spectrophotometry based on the 2-aldehyde rhodamine derivative, the reducing agent is lithium aluminum hydride, lithium tri-tert-butoxyaluminum hydride, lithium triethoxyaluminum hydride, lithium diethoxyaluminum hydride or borane.
Furthermore, the method for quantitatively detecting cyanide ions by spectrophotometry based on the 2-aldehyde rhodamine derivative comprises the following steps of (3-6) according to molar ratio, wherein the rhodamine compound is ethanolamine.
Furthermore, the method for quantitatively detecting cyanide ions by spectrophotometry based on the 2-aldehyde rhodamine derivative comprises the following steps of (1-10) based on the molar ratio of the rhodamine compound and the reducing agent.
The invention has the beneficial effects that: the 2-aldehyde rhodamine compound is different from commercial 2-carboxyl rhodamine, and the mechanism for detecting cyanide is also different from that of 2-carboxyl rhodamine spiroimide. The 2-aldehyde rhodamine derivative has active aldehyde group and can perform nucleophilic reaction with cyanide ions, the generated oxyanion can further form a leuco body with a closed ring structure with rhodamine xanthene ring, and quantitative detection can be performed on the cyanide by respectively utilizing the change of absorbance in the reaction process.
Drawings
FIG. 1 is the color response of 2-aldehyde rhodamine derivative prepared in example 1 to cyanide in ultraviolet-visible absorption spectrum detection;
wherein, a is RhB-CHO; rh 6G-CHO; c is TMR-CHO; d is Rh 110-CHO; e, Rh 101-CHO.
FIG. 2 is the absorbance spectral response of RhB-CHO prepared in example 1 to cyanide.
FIG. 3 is a standard curve of RhB-CHO vs. cyanide ions prepared in example 1.
FIG. 4 is a standard plot of Rh6G-CHO versus cyanide ion prepared in example 1.
FIG. 5 is a standard curve of TMR-CHO prepared in example 1 against cyanide ions.
FIG. 6 is a standard curve of Rh110-CHO versus cyanide ion prepared in example 1.
FIG. 7 is a standard plot of Rh101-CHO versus cyanide ion prepared in example 1.
Detailed Description
The method for quantitatively detecting cyanide ions by a spectrophotometry based on the 2-aldehyde rhodamine derivatives comprises the following steps:
1. preparing a buffer solution of the 2-aldehyde rhodamine derivative, namely adding ethanol and disodium hydrogen phosphate-sodium dihydrogen phosphate (ethanol: disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution is 3:7 in volume ratio) into the 2-aldehyde rhodamine derivative in sequence, and uniformly mixing to obtain the 2-aldehyde rhodamine derivative with the concentration of (1-5) × 10-5And (3) 2-aldehyde rhodamine derivative buffer solution with mol/L and pH of 9.0.
2. Drawing a standard curve with the concentration of (1-5) × 10-5moAdding known cyanide ion solutions with different concentrations into buffer solutions of the 2-aldehyde rhodamine derivative with the concentration of L/L and the pH value of 9.0, measuring the absorbance at the maximum absorption peak of the 2-aldehyde rhodamine derivative, and drawing a standard curve with the cyanide ion concentration as the abscissa and the absorbance at the maximum absorption peak of the 2-aldehyde rhodamine derivative as the ordinate.
3. The determination is carried out by adding solution to be determined containing cyanide ions into solution with concentration of (1-5) × 10-5And (2) uniformly mixing the materials in a buffer solution of the 2-aldehyde rhodamine derivative with the mol/L and the pH value of 9.0, measuring the absorbance at the maximum absorption peak under a spectrophotometer, and finally calculating the concentration of cyanide ions in the solution to be detected through a standard curve.
The 2-aldehyde rhodamine derivative has a structural general formula shown as (I):
wherein the content of the first and second substances,
R1＝R2＝R3＝R4＝H；
or R1＝R4＝H，R2＝-CH2CH3，R3＝-CH3；
Or R1＝R2＝-CH3，R3＝R4＝H；
Or R1＝R2＝-CH2CH3，R3＝R4＝H；
Or R1And R4Together form- (CH)2)3-，R2And R3Together form- (CH)2)3-。
The reaction general formula of the 2-aldehyde rhodamine derivative is as follows:
the preparation method of the 2-aldehyde rhodamine derivative comprises the following steps: weighing 1mol of rhodamine compound into a round-bottom flask, adding anhydrous ethanol and 3-6 times of ethanolamine by mol weight, heating at 75-85 ℃ for reaction for 8-12h, and cooling to room temperature to obtain light pink solid; dissolving the light pink solid in tetrahydrofuran solution, adding a reducing agent with the molar weight of 1-10 times, stirring at room temperature for 1-8 hours, adding water for quenching, extracting by dichloromethane, and purifying by column chromatography to obtain the 2-aldehyde rhodamine derivative.
The reducing agent is lithium aluminum hydride, lithium tri-tert-butoxyaluminum hydride, lithium triethoxyaluminum hydride, lithium diethoxyaluminum hydride or borane.
The rhodamine compound is rhodamine B, rhodamine 6G, tetramethyl rhodamine TMR, rhodamine 110 or rhodamine 101.
Example 12 qualitative and quantitative detection of Cyanid ions by Formylrhodamine derivatives
Preparation of (I) 2-aldehyde rhodamine derivatives
1. Preparation method of 2-aldehyde rhodamine B (RhB-CHO)
Adding 1mol of rhodamine B and 3mol of ethanolamine into dry 20mL of absolute ethanol in a round-bottom flask, carrying out oil bath reaction at 80 ℃ for 8-12h, cooling to room temperature, filtering, and washing the solid with ethanol for several times to obtain light pink solid; and dissolving the light pink solid in a tetrahydrofuran solution, adding 10mol of lithium aluminum hydride, stirring at room temperature for 1-8 hours, quenching the reaction liquid with water, extracting with dichloromethane, taking an organic phase, adding anhydrous magnesium sulfate, drying, and purifying by column chromatography to obtain a target product RhB-CHO. HRMS: 427.2386.
2. preparation method of 2-aldehyde rhodamine 6G (Rh6G-CHO)
Adding 1mol of rhodamine 6G and 4mol of ethanolamine into dry 20mL of absolute ethyl alcohol in a round-bottom flask, carrying out oil bath reaction at 80 ℃ for 8-12h, cooling to room temperature, filtering, and washing the solid with ethanol for several times to obtain pink solid; and dissolving the pink solid in a tetrahydrofuran solution, adding 10mol of lithium tri-tert-butoxyaluminum hydride, stirring at room temperature for 1-8 hours, quenching the reaction liquid with water, extracting with dichloromethane, taking an organic phase, adding anhydrous magnesium sulfate, drying, and purifying by column chromatography to obtain a target product Rh 6G-CHO. HRMS: 398.1994.
3. preparation method of 2-aldehyde tetramethyl rhodamine TMR (TMR-CHO)
Adding 1mol of tetramethyl rhodamine TMR and 5mol of ethanolamine into dry 20mL of absolute ethyl alcohol in a round-bottom flask, carrying out oil bath reaction at 80 ℃ for 8-12h, cooling to room temperature, filtering, and washing the solid with ethanol for several times to obtain pink solid; and dissolving the pink solid in a tetrahydrofuran solution, adding 8mol of lithium triethoxy aluminum hydride, stirring at room temperature for 1-8 hours, quenching the reaction liquid with water, extracting with dichloromethane, taking an organic phase, adding anhydrous magnesium sulfate, drying, and purifying by column chromatography to obtain a target product TMR-CHO. HRMS: 371.1760.
4. preparation method of 2-aldehyde rhodamine 110 (Rh110-CHO)
Adding 1mol of rhodamine 110 and 6mol of ethanolamine into dry 20mL of absolute ethanol in a round-bottom flask, carrying out oil bath reaction at 80 ℃ for 8-12h, cooling to room temperature, filtering, and washing the solid with ethanol for several times to obtain pink solid; and dissolving the pink solid in a tetrahydrofuran solution, adding 5mol of diethoxy lithium aluminum hydride, stirring at room temperature for 1-8 hours, quenching the reaction liquid with water, extracting with dichloromethane, taking an organic phase, adding anhydrous magnesium sulfate, drying, and purifying by column chromatography to obtain a target product Rh 110-CHO. HRMS: 315.1134.
5. preparation method of 2-aldehyde rhodamine 101 (Rh101-CHO)
Adding 1mol of rhodamine 101 and 5mol of ethanolamine into dry 20mL of absolute ethanol in a round-bottom flask, carrying out oil bath reaction at 80 ℃ for 8-12h, cooling to room temperature, filtering, and washing the solid with ethanol for several times to obtain pink solid; and dissolving the pink solid in a tetrahydrofuran solution, adding 6mol of lithium aluminum hydride, stirring at room temperature for 1-8 hours, quenching the reaction liquid with water, extracting with dichloromethane, taking an organic phase, adding anhydrous magnesium sulfate, drying, and purifying by column chromatography to obtain a target product Rh 101-CHO. HRMS: 475.2386.
qualitative detection of cyanide ions by (di) 2-aldehyde rhodamine derivatives
1. Preparing a buffer solution of the 2-aldehyde rhodamine derivative, namely adding ethanol and disodium hydrogen phosphate-sodium dihydrogen phosphate (ethanol: disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution is 3:7 in volume ratio) into the 2-aldehyde rhodamine derivative in sequence, and uniformly mixing to obtain the 2-aldehyde rhodamine derivative with the concentration of 2 × 10-5And (3) 2-aldehyde rhodamine derivative buffer solution with mol/L and pH of 9.0.
2. The determination is that 2-aldehyde rhodamine derivative buffer solution obtained in the step 1) is respectively added with the concentration of 2 × 10-4mol/L of different anions F-，Cl-，Br-，I-，CO3 2-，NO2-，H2PO4 -，HPO4 2-，SO4 2-，S2-，ClO-，CN-Etc. found except CN-Other anions than ions have no effect. As shown in FIG. 1, RhB-CHO (a), Rh6G-CHO (b), TMR-CHO (c), Rh110-CHO (d) and Rh101-CHO (e), the color of the solution is changed from pink to colorless within 1 minute only when the 2-aldehyde rhodamine derivative meets cyanide ions, the color is changed rapidly and visually, and the color can be seen by naked eyes, which shows that the 2-aldehyde rhodamine derivative can be used for CN-Has excellent selectivity and can be used in a plurality of anionsAnd qualitatively distinguishing and detecting cyanide ions.
(III) quantitative detection of cyanide ions by RhB-CHO
1. Preparing a buffer solution of RhB-CHO, namely adding ethanol and disodium hydrogen phosphate-sodium dihydrogen phosphate (ethanol: disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution is 3:7 by volume ratio) into RhB-CHO in sequence, and mixing uniformly to obtain RhB-CHO with the concentration of 2 × 10-5RhB-CHO buffer solution at mol/L, pH 9.0.
2. Drawing a standard curve: dissolving sodium cyanide in deionized water at a concentration of 0.008M to obtain a mother liquor.
At a concentration of 2 × 10-5Adding known solutions containing cyanide ions and CN at different concentrations into RhB-CHO buffer solution at mol/L and pH 9.0-The concentration ratio of the CN to the RhB-CHO is 0 to 3.6, and CN is added at intervals of 0.1 time-Measuring the spectral change, as shown in FIG. 2(RhB-CHO), with the addition of cyanide ion, the absorbance of RhB-CHO at 575nm is continuously reduced, with the absorbance of the maximum absorption peak at 575nm as ordinate and the cyanide ion concentration as abscissa, drawing a standard curve as shown in FIG. 3, the linear range of cyanide ion corresponding to RhB-CHO standard curve is (0-1.8) × 10-5mol/L。
3. The determination is carried out by adding solution to be determined containing cyanide ions into solution with concentration of 2 × 10-5And (3) uniformly mixing the solution in mol/L of RhB-CHO buffer solution with the pH value of 9.0, measuring the absorbance at 575nm in a spectrophotometer after 2 minutes, and finally calculating the concentration of cyanide ions in the solution to be measured according to a standard curve shown in figure 3.
Quantitative detection of cyanide ions by (tetra) 2-aldehyde rhodamine derivatives
The method is the same as the method (III) and is different only in changing the 2-aldehyde rhodamine derivative.
FIGS. 4-7 show Rh6G-CHO, TMR-CHO, Rh110-CHO, Rh101-CHO concentrations 2 × 10-5And (3) a cyanide ion standard curve corresponding to mol/L and pH of 9.0.
As can be seen from FIGS. 4-7, the linear range of cyanide ion corresponding to Rh6G-CHO standard curve is (0-1) × 10-5mol/L. Cyanide ion line corresponding to TMR-CHO standard curveThe sex range is (0.3-1) × 10-5The linear range of cyanide ions corresponding to the mol/L.Rh110-CHO standard curve is (0.5-1.2) × 10-5The linear range of cyanide ions corresponding to the mol/L.Rh101-CHO standard curve is (0.2-1.2) × 10-5mol/L。
Claims (9)
1. The method for quantitatively detecting cyanide ions by spectrophotometry based on the 2-aldehyde rhodamine derivatives is characterized by comprising the following steps: adding a solution to be detected containing cyanide ions into a buffer solution of the 2-aldehyde rhodamine derivative, uniformly mixing, and measuring the absorbance at the maximum absorption peak under a spectrophotometer; the buffer solution of the 2-aldehyde rhodamine derivative is prepared by sequentially adding ethanol and disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution into the 2-aldehyde rhodamine derivative and uniformly mixing; the 2-aldehyde rhodamine derivative has a structural general formula shown as (I):
(Ⅰ)
wherein the content of the first and second substances,
R1=R2=R3=R4=H；
or R1=R4=H，R2=-CH2CH3，R3=-CH3；
Or R1=R2=-CH3，R3=R4=H；
Or R1=R2=-CH2CH3，R3=R4=H；
Or R1And R4Together form- (CH)2)3-，R2And R3Together form- (CH)2)3-。
2. The method for quantitatively detecting cyanide ions based on spectrophotometry of 2-aldehyde rhodamine derivative as claimed in claim 1, wherein the buffer solution of 2-aldehyde rhodamine derivative has a pH = 9.0.
3. The method for quantitatively detecting cyanide ions based on spectrophotometry of 2-aldehyde rhodamine derivatives as claimed in claim 1, wherein the concentration of the 2-aldehyde rhodamine derivatives in the buffer solution of the 2-aldehyde rhodamine derivatives is (1-5) × 10-5mol/L。
4. The method for quantitatively detecting cyanide ions based on spectrophotometry of 2-aldehyde rhodamine derivative as claimed in claim 1, wherein ethanol to disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution =3:7 by volume ratio.
5. The method for quantitatively detecting cyanide ions based on spectrophotometry of 2-aldehyde rhodamine derivatives as claimed in claim 1, wherein the preparation method of the 2-aldehyde rhodamine derivatives comprises the following steps: taking rhodamine compounds, ethanolamine and absolute ethyl alcohol, reacting for 8-12h at 75-85 ℃, cooling to room temperature, filtering, dissolving the obtained solid in tetrahydrofuran solution, adding a reducing agent, stirring for 1-8 h at room temperature, adding water for quenching, extracting by dichloromethane, and purifying by column chromatography to obtain the 2-aldehyde rhodamine derivatives.
6. The method for quantitatively detecting cyanide ions based on spectrophotometry of 2-aldehyde rhodamine derivatives as claimed in claim 5, wherein the rhodamine compound is rhodamine B, rhodamine 6G, tetramethyl rhodamine TMR, rhodamine 110 or rhodamine 101.
7. The method for quantitatively detecting cyanide ions based on spectrophotometry of 2-aldehyde rhodamine derivatives as claimed in claim 5, wherein the reducing agent is lithium aluminum hydride, lithium tri-tert-butoxyaluminum hydride, lithium triethoxyaluminum hydride, lithium diethoxyaluminum hydride or borane.
8. The method for quantitatively detecting cyanide ions based on spectrophotometry of 2-aldehyde rhodamine derivatives as claimed in claim 5, wherein the molar ratio of rhodamine compound ethanolamine =1 (3-6).
9. The method for quantitatively detecting cyanide ions based on spectrophotometry of 2-aldehyde rhodamine derivative as claimed in claim 5, wherein the molar ratio of rhodamine compound to reducing agent =1 (1-10).
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