CN107098890B - Colorimetric fluorescent probe for detecting copper ions with high selectivity and ultra-sensitivity - Google Patents
Colorimetric fluorescent probe for detecting copper ions with high selectivity and ultra-sensitivity Download PDFInfo
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- CN107098890B CN107098890B CN201710385411.0A CN201710385411A CN107098890B CN 107098890 B CN107098890 B CN 107098890B CN 201710385411 A CN201710385411 A CN 201710385411A CN 107098890 B CN107098890 B CN 107098890B
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- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention relates to a colorimetric fluorescent probe for detecting copper ions with high selectivity and ultrasensitiveness. Specifically, the probe is a rhodamine compound, and can be used as a copper ion colorimetric fluorescent probe for detecting copper ions. Such probes can achieve at least one of the following technical effects: copper ions are identified with high selectivity; the response to copper ions can be quickly realized; high-sensitivity analysis on copper ions can be realized; the quality is stable, and the product can be stored for a long time; and has stronger anti-interference capability.
Description
Technical Field
The invention relates to a rhodamine compound as a copper ion fluorescent probe, which can quickly and sensitively identify copper ions with high selectivity and can be used for measuring the concentration of the copper ions in a sample.
Background
Copper element is a trace heavy metal element and an essential nutrient which are necessary in organisms, has the content in cells which is second to zinc and iron, and plays an important role in basic physiological processes of various organisms. It plays a pivotal role as the third most abundant transition metal in the generation of cellular energy, oxygen transport and activation, and signal transduction in the human body. Copper ion is a specific metal cation, which can be used as a catalytic cofactor of various metalloenzymes, such as tyrosinase, superoxide dismutase, cytochrome oxidase, lysyl oxidase and the like, and plays a very key role in the metabolic process of the human body. Although the content of copper in human body is very low, the lack of copper element can cause the disturbance of metabolism and growth of the body, and the over-high content of copper can also produce great toxic effect on the human body. If the copper metabolism balance in human body is damaged, some serious neurodegenerative diseases can be caused, such as Wilson's syndrome, familial muscular atrophy, Burx's syndrome and Alzheimer's disease. In recent years, copper has been suspected to cause liver damage in infants. Short term exposure to high copper ion levels can cause gastrointestinal disturbances and long term exposure can cause liver and kidney damage.
On the other hand, with the development of industrial agriculture, various industrial (such as smelting, electroplating, mining, etc.) waste water and leachate of solid waste are directly discharged into water, so that the copper content in the water is higher and higher. Because copper has the characteristics of difficult degradation, easy accumulation, high toxicity and the like, copper can be enriched and absorbed by plants and enter a food chain, thereby endangering the health of various lives such as people, livestock, birds and the like. It is widely present in aqueous environments, and although not at high concentrations, it is of great interest to the environmental sciences due to its significant toxic effects. Therefore, it is important to find an efficient method for detecting copper ions in the environment.
The existing methods for detecting copper ions mainly comprise spectrophotometry, inductively coupled plasma-atomic emission spectrometry, atomic absorption spectrometry, cyclic voltammetry, inductively coupled plasma-mass spectrometry and the like, but the processes of the methods for detecting copper ions are particularly complicated, and the detection devices are generally expensive and are not suitable for large-batch detection and real-time detection.
Disclosure of Invention
The field urgently needs a colorimetric fluorescent probe for preparing simple, rapid and high-selectivity copper ions so as to effectively detect and detect the copper ions. Therefore, the invention synthesizes a novel colorimetric fluorescent probe for copper ions, which has the advantages of simple synthesis, high selectivity, high sensitivity and capability of quickly identifying the copper ions. Specifically, the invention provides a copper ion fluorescent probe which is a rhodamine compound and has the following structure:
preferably, the fluorescent probe of the present invention is:
the invention also provides a preparation method of the copper ion fluorescent probe, which comprises the following steps of mixing the corresponding rhodamine compound and 2-picolinic acid which correspond to the probe of the invention in a ratio of 1:3 to 1:4 in dichloromethane solution for one and a half hours under reflux.
The invention also provides a detection preparation or a kit for detecting the concentration of copper ions in a sample, which comprises the probe of the invention. Preferably, the detection formulation or kit of the invention further comprises instructions for use of the product. Also preferably, the kit of the present invention further comprises a buffer for determining the concentration of copper ions in the sample.
The invention also provides a method for detecting the concentration of copper ions in a sample, which comprises the step of contacting the probe with the sample to be detected.
The invention also provides the use of the probe of the invention in the preparation of a formulation for detecting the concentration of copper ions in a sample.
The invention also provides the use of the probe of the invention in the preparation of a kit for detecting the concentration of copper ions in a sample (e.g. a water sample).
The copper ion colorimetric fluorescent probe can act with copper ions to generate changes of a fluorescence spectrum and an ultraviolet absorption spectrum, so that the quantitative detection of the copper ions is realized.
Specifically, the copper ion colorimetric fluorescent probe respectively acts with other ions such as sodium ions, aluminum ions, potassium ions, calcium ions, magnesium ions, zinc ions, cobalt ions, lead ions, mercury ions and the like, and the fluorescence spectrum and the ultraviolet absorption spectrum cannot be obviously changed, so that the selective identification of the copper ions is realized, and the copper colorimetric fluorescent probe can be optionally used for eliminating the interference of the existence of other ions such as sodium ions, aluminum ions, potassium ions, calcium ions, magnesium ions, zinc ions, cobalt ions, lead ions, mercury ions and the like on the quantitative determination of the copper ions.
Optionally, the copper ion fluorescent probe has good stability, and can be stored and used for a long time.
Furthermore, the copper ion colorimetric fluorescent probe is a rapid and high-selectivity copper ion colorimetric fluorescent probe, is simple to synthesize, and is beneficial to commercial popularization and application.
Drawings
FIG. 1 shows probe (5. mu.M) added with Cu2+Fluorescence spectra before and after (5 μ M);
FIG. 2 shows Cu concentrations2+(0-2. mu.M) effect on fluorescence spectra of probes (5. mu.M);
FIG. 3 is the effect of copper ions (5. mu.M) and different ionic analytes (50. mu.M) on the fluorescence intensity of the probe (5. mu.M);
FIG. 4 is the interference of different ion analytes (50. mu.M) on the response of copper ions (5. mu.M) and probes (5. mu.M).
The specific implementation mode is as follows:
the invention provides a synthetic route and a method of the rapid high-selectivity copper ion fluorescent probe and spectral performance of the rapid high-selectivity copper ion fluorescent probe.
The copper ion colorimetric fluorescent probe is a rhodamine compound and has the following structural general formula
In the above formula: r1,R2,R3,R4,R5,R6,R7,R8,R9And R10Is hydrogen atom, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, sulfonic group, ester group, carboxyl; r1,R2,R3,R4,R5,R6,R7,R8,R9And R10May be the same or different.
The synthetic route and the method of the copper ion colorimetric fluorescent probe are as follows:
specifically, the colorimetric fluorescent probe can be prepared by dissolving rhodamine compound and 2-picolinic acid in a certain molar ratio (example 1:3-1:4) in dichloromethane, stirring and refluxing, wherein the molar ratio of the rhodamine compound to the 2-picolinic acid is (1:3), refluxing for a period of time (for example 1.5h), then performing suction filtration by using a high-pressure pump to obtain a filtrate, and directly passing the filtrate through a chromatographic column to obtain a pure product.
Therefore, the invention also provides the application of the 2-picolinic acid in preparing the colorimetric fluorescent probe for detecting the copper ions.
The invention also provides application of the rhodamine compound in preparing a colorimetric fluorescent probe for detecting copper ions.
The colorimetric fluorescent probe for rapidly, highly selectively and sensitively identifying the copper ions has the remarkable characteristics of being capable of rapidly, highly selectively and sensitively identifying the copper ions and accurately and quantitatively analyzing the copper ions in the presence of other ions in a human body.
The invention will be explained in more detail below by means of the following examples. The following examples are illustrative only, and it should be understood that the present invention is not limited by the following examples.
Example 1
(scheme 1) 300mg (0.685mmol) of rhodamine compound is dissolved in 15m L dichloromethane, 253mg (2.055mmol) of 2-picolinic acid is added for refluxing for 1.5h, and then suction filtration is carried out by using a high-pressure pump to obtain a filtrate, and the filtrate is directly subjected to a chromatographic column to obtain a pure product, namely 163mg of pink pure product is obtained, and the yield is 44%.
(scheme 2) 300mg (0.685mmol) of rhodamine compound is dissolved in 15m L dichloromethane, 295mg (2.40mmol) of 2-picolinic acid is added for refluxing for 1.5h, then suction filtration is carried out by using a high-pressure pump to obtain filtrate, and the filtrate is directly passed through a chromatographic column to obtain a pure product, namely 194mg of pink pure product, wherein the yield is 52%.
(scheme 3) 300mg (0.685mmol) of rhodamine compound is dissolved in 15m L dichloromethane, 337mg (2.74mmol) of 2-picolinic acid is added for refluxing for 1.5h, and then suction filtration is carried out by using a high-pressure pump to obtain a filtrate, and the filtrate is directly passed through a chromatographic column to obtain a pure product, namely 227mg of pink pure product with the yield of 61%.
(scheme 4) 300mg (0.685mmol) of rhodamine compound is dissolved in 20m L dichloromethane, 337mg (2.74mmol) of 2-picolinic acid is added for refluxing for 1.5h, and then suction filtration is carried out by using a high-pressure pump to obtain a filtrate, and the filtrate is directly passed through a chromatographic column to obtain a pure product, namely 235mg of pink pure product with the yield of 63%.
(scheme 5) 300mg (0.685mmol) of rhodamine compound is dissolved in 15m L dichloromethane, 337mg (2.74mmol) of 2-picolinic acid is added for refluxing for 3h, and then suction filtration is carried out by using a high-pressure pump to obtain a filtrate, and the filtrate is directly subjected to a chromatographic column to obtain a pure product, namely 246mg of pink pure product is obtained, and the yield is 66%.
Example 2
Firstly preparing 1mM probe stock solution and 10mM copper ion stock solution, firstly adding 5M L distilled water into a cleaned colorimetric tube, then sucking 50 mu L probe stock solution by using a liquid transfer gun, adding the probe stock solution into the tube, adding 0.5M L phosphate buffer solution (pH7.0), fixing the volume to 10M L, uniformly mixing, dividing the volume into two parts, adding 5 mu M copper ions into one tube, respectively measuring the fluorescence intensity values by using a fluorescence spectrometer after responding for 15min, wherein the excitation wavelength is 515nm, the emission wavelength is 630nm, and the test temperature is 25 ℃, and the result is shown in figure 1.
FIG. 1 shows probe (5. mu.M) added with Cu2+The fluorescence spectra before and after (5 μ M) show that the fluorescence change is very obvious by interpolation, which indicates that the probe has good response to copper ions.
Example 3
150M L of 5 μ M probe solution was prepared from a beaker on the basis of the stock solution and transferred to 12 clean cuvettes for accurate calibration, the stock solution of copper ions was added to the cuvettes to give final concentrations of 0,0.1,0.2,0.4,0.6,0.8,1.0,1.2,1.4,1.6,1.8,2.0 μ M and shaken well, the test system was pure water, 5mM phosphate buffer solution (pH7.0) was left to react for 15 minutes, and the emission spectrum was measured with a fluorescence spectrometer and recorded and stored, wherein the excitation wavelength was 515nm, the emission wavelength was 630nm, the test temperature was 25 ℃ and the results are shown in FIG. 2.
FIG. 2 shows Cu concentrations2+(0-2. mu.M) effect on fluorescence spectra of probes (5. mu.M);
it can be seen that Cu in the probe solution accompanies2+The concentration is increased, the fluorescence intensity is gradually enhanced, and the suitable concentration of the copper ions in the drinking water is 0.5-1.0 mg/L.
Example 4
Preparing 5 mu M probe solution of 200M L by using a beaker on the basis of a stock solution, respectively moving the probe solution into 16 colorimetric tubes for constant volume, placing the colorimetric tubes on a test tube rack in sequence, wherein the leftmost colorimetric tube is a blank probe, then adding the colorimetric tubes into the test tubes in sequence from left to right to ensure that the final copper ion concentration is 5 mu M and the concentrations of other ions are 50 mu M, reacting for 15 minutes, then putting all the solutions into a fluorescence spectrometer in sequence from left to right, recording a spectrogram and storing, and the result is shown in figure 3.
The above procedure was repeated, and after 50. mu.M of other ions were added, 5. mu.M of copper ions were rapidly added to the other tubes in the cuvette from which copper ions were removed. After 15 minutes of reaction, all solutions were placed in a fluorescence spectrometer in order from left to right for detection, and a spectrogram was recorded and stored, with the results shown in FIG. 4.
FIG. 3 is a graph showing the effect of copper ions (5. mu.M) and different ionic analytes (50. mu.M) on the fluorescence intensity of probes (5. mu.M).
FIG. 4 shows the interference of different ion analytes (50. mu.M) with the response of copper ions (5. mu.M) and probes (5. mu.M). a, blank; b is sodium ion; c, aluminum ions; d is potassium ion; e, calcium ions; f is magnesium ion; g, zinc ions; h is cobalt ion; i is lead ion; j is mercury ion; k is carbonate ion; l is nitrate radical ion; m is chloride ion; n is iodide ion; and o is sulfate ion.
All assays were performed after 15 min. The analytes include: copper ions, sodium ions, aluminum ions, potassium ions, calcium ions, magnesium ions, zinc ions, cobalt ions, lead ions, mercury ions, carbonate ions, nitrate ions, chloride ions, iodide ions, and sulfate ions. Their concentration was 5. mu.M for copper ions, and 50. mu.M for the other ions. All test conditions were done in pure water, the probe used was the probe prepared in example 1, and all spectra were measured after 15min of analyte addition at 25 ℃.
As can be seen from fig. 3 and 4, the fluorescence intensity of the probe for copper ions is not significantly interfered by common ions existing in the environment, so that the probe has good selectivity.
Although the present invention has been described in the above-mentioned embodiments, it is to be understood that the present invention may be further modified and changed without departing from the spirit of the present invention, and that such modifications and changes are within the scope of the present invention.
Claims (7)
3. the formulation of claim 2, wherein the sample is an aqueous sample.
5. the kit of claim 4, wherein the sample is an aqueous sample.
6. The kit of any one of claims 4-5, further comprising instructions for use.
7. The kit of any one of claims 4-5, further comprising a buffer for detecting the amount of copper ions in the sample.
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