CN115785129B - Spiropyrano copper complex and preparation method and application thereof - Google Patents
Spiropyrano copper complex and preparation method and application thereof Download PDFInfo
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Abstract
A spiropyran copper complex and a preparation method and application thereof belong to the technical field of preparation and application of environmental pollutant detection materialsThe field provides synthesis and application of a spiropyran copper ion complex probe for selectively detecting sulfide ions, wherein the probe is prepared by coordination of ring-opened pyridine spiropyran and copper ions, and recognition of the sulfide ions is realized through ultraviolet spectrum change caused by combination of the copper ion complex and the sulfide ions. The structural formula of the probe compound is as follows:
abbreviated as PY-SP+Cu 2+ 。
Description
Technical Field
The invention belongs to the technical field of preparation and application of environmental pollutant detection materials, and particularly relates to synthesis and application of a spiropyran copper ion complex probe for selectively detecting sulfide ions.
Background
Sulfide is one of important environmental pollutants discharged in the chemical production process, and can reduce the concentration of dissolved oxygen in water and inhibit the activities of aquatic organisms; irrigating farmlands with sulfide-containing water to cause root rot of crops; in an acidic aqueous environment, sulfur ions combine with hydrogen ions to produce toxic HS - And H 2 S, wherein H 2 The S can cause dizziness under extremely low concentration, and the higher concentration can cause loss of consciousness, permanent damage of brain tissues and even death caused by asphyxia. In organisms, high concentration of sulfur ions can stimulate mucous membrane, cause consciousness blurring, respiratory paralysis and the like, are also involved in physiological processes of anti-apoptosis, antioxidation, cardiovascular relaxation and the like, are closely related to a plurality of diseases (such as Alzheimer disease, hypertension, liver cirrhosis, down syndrome and the like), and the excessive and insufficient sulfur ions can cause various case disorders. Thus, S is fast and efficient 2- Has great significance in developing and establishing the analysis method.
Spiropyran (SP) and its derivatives are a typical class of organic photochromic compounds, the structure of which is formed by crosslinking two aromatic heterocycles through one spirocarbon atom, the two heterocyclic molecules do not form structural conjugation, and under the stimulation of ultraviolet light, the spirooxygen bond is broken and is converted into a conjugated ring-opening structure (MC structure), and the process is accompanied by obvious color change. Numerous studies have shown that MC structures are susceptible to complexing with metal ions and are therefore often used in studies of metal ion detection, while the literature on complexes of spiropyrans with metal ions is relatively small.
The detection of sulfide ions by using copper complexes has been long studied, and the mechanism is that sulfide ions abstract copper ions in the copper complexes to form copper sulfide precipitates, so that the complex structure is destroyed, and the ultraviolet absorption spectrum and fluorescence spectrum of the ligand are recovered in spectrum, thereby realizing the purpose of detecting sulfide ions. However, the selectivity of the existing copper complex for detecting sulfur ions is not high enough, other ions can be precipitated in a small amount, black copper sulfide precipitates are formed, the reaction time can be prolonged by the black precipitates, ultraviolet spectrum can be detected only by the precipitation, and the detection time can be prolonged. Therefore, a copper complex having a short detection time and a higher selectivity is required for detecting sulfur ions.
Disclosure of Invention
In order to solve the technical problem of precipitate formation, various novel ligands are tried, and the technical problem to be solved by the invention can be solved by unexpectedly finding out that the spiropyran can possibly.
The invention is realized by the following technical scheme: a spiropyran derivative probe has a structure shown in the following figure, and is abbreviated as PY-SP+Cu 2+ 。
The method for preparing the spiropyran copper complex probe for detecting the sulfide ions comprises the following steps of firstly utilizing half flowersThe method comprises the steps of generating reddish brown solid from cyanine and bromoethane in toluene, processing the reddish brown solid after filtration and drying by sodium hydroxide aqueous solution to obtain light yellow oily liquid, heating and refluxing the oily liquid and dihydroxybenzaldehyde in ethanol to obtain a hydroxyl substituted spiropyran structure, finally dropwise adding equimolar aqueous solution of cupric chloride into the alcoholic solution of the spiropyran structure, and obtaining PY-SP+Cu after the reaction is completed 2+ An aqueous solution.
The synthesis of the structure comprises two parts of preparation of pyridine spiropyran and copper ion complex thereof.
(1) Synthesis of pyridine spiropyrans
In the first step, 2, 3-trimethyl indoline and 2-bromoethane are taken as raw materials, reflux reaction is carried out for 24 hours in toluene, and the dark red solid, namely the bromosalt of the indoline, is obtained through cooling and filtering.
And secondly, reacting indoline bromide obtained in the last step with a sodium hydroxide aqueous solution for 30min at normal temperature, extracting and drying by diethyl ether to obtain yellow liquid, then carrying out reflux reaction on the yellow liquid and 2-hydroxy salicylaldehyde in ethanol for 12h, and carrying out cold water crystallization to obtain a dark yellow solid, namely hydroxy spiropyran.
Thirdly, dissolving the hydroxyl spiropyran and chloromethyl pyridine in DMF, heating and reacting for 14h by taking potassium carbonate and potassium iodide as catalysts, and purifying by column chromatography (ethyl acetate/petroleum ether=10:1) after the reaction is finished to obtain yellow oily liquid, namely the pyridine spiropyran.
(2) Preparation of pyridine spiropyran copper ion probe detection solution
Respectively preparing pyridine spiropyran and copper chloride mother liquor with equal concentration, and mixing and dissolving the mother liquor in deionized water with equal volume to obtain a probe solution of pyridine copper ions.
The detection mechanism is based on spectral change caused by coordination of the sulfur ions, and can carry out high-sensitivity selective detection on the sulfur ions in water
3. The application of the spiropyran copper complex in the field of sulfur ion detection is not reported, and in addition, the complex has good water solubility, has a great application prospect for detecting sulfur ions in water environment, and simultaneously provides a new direction for the application of a spiropyran structure, such as the application of sulfur ions in wastewater generated in the production process of sulphide ores, textile, printing and dyeing, coke, paper pulp or tanning chemical raw materials and the like.
The invention discloses a selective detection method of spiropyran copper ion complex to sulfur ions: after sulfur ions are added into the spiropyran copper ion complex, the ultraviolet absorption spectrum of the spiropyran copper ion complex is obviously changed; based on the change of ultraviolet spectrum, the catalyst has excellent selectivity compared with other common response phenomena of anions; according to the titration curve, the detection limit is calculated to be 0.074uM, namely 0.0024mg/L, which is lower than the lowest detection concentration of methylene blue to sulfide of 0.02mg/L, and the method has good application prospect.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a hydroxy spiropyran;
FIG. 2 is a nuclear magnetic carbon spectrum of a hydroxyspiropyran;
FIG. 3 is a nuclear magnetic hydrogen spectrum of pyridine spiropyrans;
FIG. 4 is a nuclear magnetic carbon spectrum of pyridine spiropyrans;
FIG. 5 shows copper complex and S 2- Ultraviolet absorption spectra before and after ion action;
FIG. 6 is a titration curve of copper complex with sulfide ion;
FIG. 7 is a fitted curve of copper complex response to sulfide ions;
FIG. 8 is a bar graph of copper complex selectivity for sulfur ions;
Detailed Description
Example 1: a novel spiropyran copper ion complex probe has a structure shown in the following figure and abbreviated as PY-SP+Cu 2+ 。
The synthesis steps are as follows:
2, 3-trimethylindole (3.1732 g,0.02 mol) was mixed with 2-bromoethane (2.3745 g,0.022 mol) and heated under reflux in 40ml of acetonitrile for 24h with an oil bath at a reflux temperature of 85 ℃. After the reaction is finished, stopping heating, cooling to room temperature, and stopping stirringThe reaction was monitored by a dot plate, the reaction was essentially completed, acetonitrile was distilled off under reduced pressure, then a small amount of diethyl ether was added, at this time, a large amount of solids was precipitated, suction filtration was carried out to obtain a solid, and after vacuum drying, it was weighed to obtain 2.9851g of a compound, which was directly used in the next reaction, the product of the previous step (1.9851 g, 0.0075mol) and NaOH (1.51 g,0.038 mol) were added to 10ml of deionized water, stirred at room temperature for 30 minutes, and after completion of the reaction, extracted 3 times with 10ml of diethyl ether. The organic phases were combined and dried over anhydrous NaSO 4. The resulting liquid 1.0294g was concentrated by evaporation and used directly in the next step without further treatment, and the resulting liquid was oil-bath heated under reflux with 2, 3-dihydroxybenzaldehyde (0.7985 g,0.0058 mol) in 30ml of ethanol for 12h at a reflux temperature of 84 ℃. Stopping the reaction and cooling to room temperature, pouring the reaction solution into ice water for crystallization, placing the mixed solution in a refrigerator for 12 hours at low temperature, carrying out suction filtration, leaching by using an ethanol water solution (1:1), drying and weighing to obtain 1.7419g of yellow solid, wherein the total yield is 21.13%. 1 HNMR(600MHz,CDCl 3 )δ7.21-7.16(m,1H),7.10(d,J＝7.2Hz,1H),6.85(t,J＝8.7Hz,2H),6.81(d,J＝8.0Hz,1H),6.76(t,J＝7.6Hz,1H),6.66(d,J＝7.5Hz,1H),6.57(t,J＝8.3Hz,1H),5.71(d,J＝10.2Hz,1H),5.39(s,1H),3.39(dq,J＝14.6,7.3Hz,1H),3.23(dq,J＝14.2,6.9Hz,1H),1.32(s,3H),1.21-1.15(m,6H). 13 CNMR(151MHz,CDCl 3 )δ146.84,143.31,140.56,136.34,129.35,127.52,121.83,120.25119.91,118.69,117.88,115.44,106.37,105.58,52.13,37.76,26.17,19.78,14.30.
The hydroxy spiropyran (0.2032 g,0.66 mmol) of the last step was dissolved in 5ml DMF and added with stirring to dry K 2 CO 3 (0.1383 g,0.99 mmol), 2-chloromethylpyridine (0.1192, 0.73 mmol), KI (0.0564 g), and then gradually heating to 100℃to react for 14 hours; adding water (at least 5 times the volume of DMF added), extracting with ethyl acetate multiple times, and mixing the organic phases (upper layer); then dried over anhydrous magnesium sulfate, filtered, evaporated and concentrated, and purified by a silica gel column to give 0.0641g of a yellow oily liquid with a yield of 24.4% (eluent petroleum ether: ethyl acetate=4:1v/V). 1 HNMR(600MHz,CDCl 3 )δ8.47(t,J＝12.6Hz,1H),7.44–7.36(m,1H),7.24–7.14(m,1H),7.10(t,J＝9.4Hz,3H),6.92–6.82(m,3H),6.80–6.72(m,2H),6.55(t,J＝9.7Hz,1H),5.75(t,J＝12.5Hz,1H),5.08–4.99(m,2H),3.42–3.33(m,1H),3.26–3.15(m,1H),1.37–1.31(m,3H),1.24–1.11(m,6H). 13 CNMR(151MHz,CDCl 3 )δ157.70,148.46,147.29,146.07,144.72,136.73,129.11,127.34,122.23,121.58,120.48,119.89,119.60,118.48,117.60,106.32,104.79,72.93,52.00,37.96,25.66,19.99,14.56.
EXAMPLE 2 detection of copper ions by spiropyran copper ion Complex
(1) Probe mother liquor and related anion configuration
0.00398g of 7-pyridine spiropyran is weighed and dissolved in 10ml of absolute ethanol to prepare 1X 10 -3 The mol/L hydroxyl spiropyran mother liquor is reserved;
0.00170g of cupric chloride dihydrate is weighed and dissolved in 10ml of deionized water to prepare 1X 10 -3 The mol/L copper ion aqueous solution is reserved;
in addition, an aqueous solution of the relevant anions was prepared as a mother liquor (1X 10) -3 mol/L), including S 2- ，CO 3 2- ,SO 3 2- ,SO 4 2- ,H 2 PO 4 - ,HPO 4 2- ,F - ,Cl - ,Br - ,I - ,NO 3 2- ,SCN - And ClO 3 - 。
Mixing 0.5ml of pyridine spiropyran mother liquor and 0.5ml of copper ion mother liquor respectively, and adding deionized water to constant volume of 50ml to obtain 1×10 -5 The hydroxy spiropyran copper ion complex solution with mol/L is ready for use.
Application of probe in detection of sulfur ions
The method comprises the following specific steps:
(1) Probe mother liquor and related anion configuration
Dissolving pyridine spiropyran in absolute ethanol to obtain 1×10 extract -3 The mol/L hydroxyl spiropyran mother liquor is reserved;
weighing cupric chloride dihydrate, dissolving in deionized water, and preparing into 1×10 -3 The mol/L copper ion aqueous solution is reserved; in addition, an aqueous solution of the relevant anions was prepared as a mother liquor (1X 10) -3 mol/L), including S 2- ，CO 3 2- ,SO 3 2- ,SO 4 2- ,H 2 PO 4 - ,HPO 4 2- ,F - ,Cl - ,Br - ,I - ,NO 3 2- ,SCN - And ClO 3 - 。
Mixing 0.5ml of pyridine spiropyran mother liquor and 0.5ml of copper ion mother liquor respectively, fixing volume to 50ml with deionized water, standing for 1 hr, and reacting completely to obtain 1×10 -5 The hydroxy spiropyran copper ion complex solution with mol/L is ready for use.
(2) Ultraviolet spectrum method for detecting sulfur ions by probe molecules
Taking a solution of the probe molecule, i.e., a solution of the hydroxycospirane copper ion complex (1X 10) -5 mol/L), the ultraviolet absorption spectrum is detected, strong absorption peaks are formed at 384nm and 482nm, then sulfur ions are gradually added, the absorption peak at 384nm is enhanced, the absorption peak at 482nm is weakened, and the maximum absorption peak is red shifted to 424nm and 493nm to generate a new absorption peak.
(2) The probe of the invention can selectively detect the sulfur ions
The probe is reacted with different anions to detect the ultraviolet absorption spectrum without obvious change, and the ions in the control group comprise CO 3 2- ,SO 3 2- ,SO 4 2- ,H 2 PO 4 - ,HPO 4 2- ,F - ,Cl - ,Br - ,I - ,NO 3 2- ,SCN - And ClO 3 -. The ultraviolet spectrum change after the action of the sulfur ions and the probe is obvious.
(2) Ultraviolet spectroscopic analysis of probe molecule interactions with sulfide ions
Taking a solution of the probe molecule, i.e., a solution of the pyridine spiropyran copper ion complex (1X 10) -5 mol/L) 2ml are added into a cuvette dropwise in a gradually manner 10 -3 The reaction time of the sulfur ions was 1 minute in mol/L (2 uL each), and the ultraviolet spectrum changes before and after the reaction were detected. The result shows that the ultraviolet absorption peak shows continuous and obvious change, and from the graph, two larger absorption peaks at 384nm and 482nm are seen, and S is added 2- After ions, the absorption peak at 384nm was increased, the absorption peak at 482nm was decreased, and the maximum absorption peak was red shifted to 424nm,493nm to produce a new absorption peak.
(3) Probe pair sulfur ion selectivity assay
For other common anions (CO 3 2- ,SO 3 2- ,SO 4 2- ,H 2 PO 4 - ,HPO 4 2- ,F - ,Cl - ,Br - ,I - ,NO 3 2- ,SCN - And ClO 3 - ) Detection was performed. 2ml of mother solution of pyridine spiropyran copper ions is taken and added into a cuvette, then 10 times of corresponding ions are added, the change of characteristic peak of ultraviolet spectrum at 384nm is detected, and the selectivity is evaluated through the change of absorbance at the position. The experimental results show that the absorbance change of anions other than the sulfide ion is small at this position, so that the sulfide ion can be selectively detected.
(4) Detection limit detection
The change in absorption intensity at 384nm was very regular according to the titration curve in 2.2.5, with S 2- The increasing ion concentration, the enhancement of 384nm absorption peak, and the appearance of 494nm new absorption peak illustrate the probe molecule copper complex and S 2- Gradually complexing to form a complex. The detection limit can be calculated by a 3 sigma/k empirical formula. The ultraviolet absorbance spectra after interaction of the same set of probes with the sulfide ions were measured 10 times in succession. The absorbance at 384nm was calculated to be σ=8.35×10 -5 . The change of the absorption intensity at 384nm in the ultraviolet absorption spectrum in the first 8 titration changes is selected to be plotted and fitted into a straight line, and the linear equation is Y=0.00337X+0.16028, R 2 0.99258 based on the experience C of the limit of detection DL =3σ/k, substituting the corresponding parameters, resulting in a detection limit of 0.074uM. Namely 0.0024mg/L, which is lower than the lowest detection concentration of methylene blue to sulfide of 0.02mg/L, and has good application prospect.
Claims (3)
1. Spiropyran derivativeA biological probe, characterized in that: the structural formula of the compound is shown as the following formula, and is abbreviated as PY-SP+Cu 2 + ，
2. A method for preparing the spiropyran derivative probe of claim 1, characterized in that: the method comprises the following specific steps:
(1) Synthesis of pyridine spiropyrans
Firstly, taking 2, 3-trimethyl indoline and EtBr as raw materials, carrying out reflux reaction in toluene for 24 hours, and cooling and filtering to obtain a dark red solid, namely indoline bromide;
secondly, reacting indoline bromide obtained in the last step with a sodium hydroxide aqueous solution for 30min at normal temperature, extracting and drying by diethyl ether to obtain yellow liquid, then carrying out reflux reaction on the yellow liquid and 2, 3-dihydroxybenzaldehyde in ethanol for 12h, and carrying out cold water crystallization to obtain a dark yellow solid, namely hydroxyl spiropyran;
thirdly, dissolving the hydroxyl spiropyran and chloromethyl pyridine in DMF, heating and reacting for 14h by taking potassium carbonate and potassium iodide as catalysts, and purifying by column chromatography after the reaction is finished to obtain yellow oily liquid, namely pyridine spiropyran;
(2) Preparation of spiropyran derivative probe detection solution
Respectively preparing pyridine spiropyran and copper chloride mother liquor with equal concentration, and mixing and dissolving the pyridine spiropyran and copper chloride mother liquor in deionized water with equal volume to obtain a spiropyran derivative probe detection solution;
the structural formulas of the 2, 3-trimethyl indoline, the bromine salt of the indoline, the hydroxyl spiropyran or the pyridine spiropyran are respectively shown as the following formulas:
3. the use of the spiropyran derivative probe according to claim 1 for detecting sulfide ions in wastewater produced in the production process of sulfide ores, textiles, printing and dyeing, cokes, paper pulp or leather-making chemical materials.
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