CN111205274B - Fluorescent probe capable of detecting copper ions and pyrophosphate and preparation method and application thereof - Google Patents
Fluorescent probe capable of detecting copper ions and pyrophosphate and preparation method and application thereof Download PDFInfo
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- CN111205274B CN111205274B CN202010130605.8A CN202010130605A CN111205274B CN 111205274 B CN111205274 B CN 111205274B CN 202010130605 A CN202010130605 A CN 202010130605A CN 111205274 B CN111205274 B CN 111205274B
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 123
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- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 62
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 title claims abstract description 47
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—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
- 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
- C07D405/06—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 linked by a carbon chain containing only aliphatic carbon atoms
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- 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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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- G01N21/64—Fluorescence; Phosphorescence
- 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 fluorescent probe capable of detecting copper ions and pyrophosphate, a preparation method and application thereof, and belongs to the technical field of analytical chemistry. The invention discloses and synthesizes a fluorescent probe (probe), the maximum excitation wavelength is 316nm, and the maximum emission wavelength is 445 nm. The fluorescent probe can efficiently and sensitively detect Cu by a fluorescence quenching method2+And Cu formed in the presence of copper ions2+Fluorescent probes (Cu)2+Probe) also enables efficient and sensitive detection of pyrophosphate (PPi) by fluorescence enhancement.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to a fluorescent probe capable of detecting copper ions and pyrophosphate as well as a preparation method and application thereof.
Background
Since many enzymes in organisms react with metal ions to various degrees, metal ions play a very important role in the metabolic processes of organisms, among which copper ions play a crucial role in human health. The copper ions in the drinking water are required to be less than 1.3 mg/L; copper poisoning can be caused by excessive copper ions ingested by a human body, and anemia, coronary heart disease and other diseases can be caused by lack of copper ions; disorders of copper ion metabolism can lead to disruption of cellular homeostasis, liver cirrhosis, Alzheimer's disease, Wilson's disease, neurological disorders, amyotrophic lateral sclerosis, hypoglycemia, and dyslexia.
On the other hand, pyrophosphate (PPi) is an important metabolite in various life reaction processes, and plays an important role in hydrolysis of citric acid and ATP, replication of DNA, production of cyclic adenosine monophosphate (c-AMP), and the like. Sufficient amounts of PPi can block calcification in synovial fluid, plasma and urine and can act as a natural inhibitor of hydroxyapatite formation in extracellular fluids. Many studies have shown that PPi plays a key role in arthritis and chondrococalcinosis.
Therefore, the detection of copper ions and PPi has extremely important significance. Various methods have been established for the Detection of Copper ions, n nanosensor (Liu, L.; Fan, Z.; Zheng, X.; Xi, D., Nanopore-Based Strategy for Sensing of cooper (II) Ion and Real-Time Monitoring of a Click reaction. ACS Sensors 2019,4(5), 1323-doping 1328), Fluorescence (Jo, J.; Lee, H.Y.; Liu, W.; Olasz, A.; Chen C. -H.; Lee, D., reaction-Based Detection of cooper (II) Ion in Water: oxidation cycling of azo as Fluorescence, Tu-On Signaling J., sea, J. C.; La, C.; Lee, D., reaction-detecting of Copper Ion, J. C.; photo-nano Sensing method, N.S. J.S.38, W.; photo-nano Sensing method, S.16000, J.; photo-acoustic-Sensing method, J. S.S.J.; light emission, S.S.16000, J.S.S.S.J.; light emission, S.S.S.S.S.16000, J. 3, light emission, S.2+ACS appl.mater.inter.2019,11(2), 1917-; wang, r.; yuan, w.; liu, q.; shi, m.; feng, w.; wu, z.; hu, k.; Easy-to-Use Colorimetric Cyanine Probe for the Detection of Cu2+in Wilson's disease. acs appl. mater. inter.2018,10(24), 20377-; kumar, p.; kumar, s.; singhal, d.; gupta, R., Turn-On Fluorescent Sensors for the Selective Detection of Al3+(and Ga3+) and PPi ions, incorg, chem.2019,58(15), 10364-; an, Y.; yao, z.; li, C.; shi, G., A Turn-on Fluorescent Sensor for pyropophosphonate Based on the analysis of Cu2+Fluorescence enhancement developed by means of medium characterized Perylene dioxide aggregates. ACS appl. mater. Inter.2012,4(2),614-618)A strong method; chen et al (Chen, C.; Zhao, D.; Sun, J.; Yang, X., Colorimetric Logic Gate for Pyrophosphosphosphonium and Pyrophosphonium view Regulating the Catalytic performance of Horseradish Peroxibase ACS Appl. Mat. Inter.2016 (8), 29529. Zosterase. 29535), Dey et al (Dey, S.; Sukul, P.K., Selective Detection of Pyrophonium equations in Aqueous Medium Using chromatography 2019,4 (14)), 91. Zosterase. 16200) developed Colorimetric method, Li et al (Li, Lifj., Y., Zo. H.; Zouh Zouhn. Zo H. (III.)/Zo J.; Zo N. (III, Z.) -H.; Zo H.; Zo Zosterase. Press et al (Y, Zo H.; Zosterase. Press)2+Electrochemical luminescence method developed by complex Bifunctional Gold Nanoparticles and Sensitive Sensing of pyrophoric ion. ACS applied. Mater. Inter.2014,6(20), 18104-. Among them, fluorescence analysis attracts attention in the field of analytical chemistry because of its advantages such as easy operation, high stability, sensitive signal, high selectivity, etc.
Therefore, to achieve the simultaneous detection of copper ions (Cu) by fluorescence analysis2+) And Pyrophosphate (PPi), a new fluorescent probe needs to be developed to achieve the above object.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a fluorescent probe capable of detecting copper ions and pyrophosphate; the second purpose of the invention is to provide a preparation method of a fluorescent probe capable of detecting copper ions and pyrophosphate; the invention also aims to provide the application of the fluorescent probe capable of detecting copper ions and pyrophosphate in the aspect of detecting the copper ions; the fourth purpose of the invention is to provide the application of the fluorescent probe capable of detecting copper ions and pyrophosphate in the aspect of detecting pyrophosphate.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a fluorescent probe capable of detecting copper ions and pyrophosphate, the structural formula of the fluorescent probe is as follows:
2. the preparation method of the fluorescent probe has the following general reaction formula:
preferably, the reaction is specifically:
and (3) mixing and dissolving 4-hydroxy umbelliferone, paraformaldehyde and proline in ethanol or methanol, heating and refluxing in an oil bath for 12-14 h, filtering a reaction product after the reaction is finished, and drying to obtain the fluorescent probe.
Preferably, the mass ratio of the 4-hydroxy umbelliferone, the paraformaldehyde and the proline is 0.8-1.0: 1-1.1: 0.8-1.0.
Preferably, the temperature of the heating reflux is 78 ℃ or higher.
3. The fluorescent probe is applied to the aspect of detecting copper ions.
4. The fluorescent probe is applied to detecting pyrophosphate.
Preferably, the fluorescent probe in the application is firstly coordinated with copper ions to form Cu2+-a fluorescent probe.
The invention has the beneficial effects that: the invention synthesizes the method capable of detecting copper ions (Cu)2+) And pyrophosphate, wherein the fluorescent probe molecule contains N atom and O atom, and can react with Cu2+Coordination occurs to form the compound Cu2+Fluorescent probes (Cu)2+Probe), which reduces the conjugation property of the fluorescent probe itself and quenches the fluorescence of the fluorescent probe; at the same time because of Cu2+Since the coordination ability to pyrophosphate is stronger than that of the fluorescent probe (probe), copper ions (Cu) are generated in the presence of the fluorescent probe (probe) and pyrophosphate (PPi)2+) Preferentially coordinate with pyrophosphate, thereby leading to the restoration of the structure of the fluorescent probe and the enhancement of the fluorescence intensity; copper ion (Cu)2+) Can quench the fluorescence of the fluorescent probe instantly, and the fluorescenceThe quenching degree of the signal and the concentration of the copper ions are in good linear relation within the range of 0.01-0.8 mu M; pyrophosphate can instantaneously react Cu2+The quenched fluorescence is recovered, and the recovery degree of the fluorescence signal and the concentration of pyrophosphate are in a good linear relation within the range of 2-40 mu M. The fluorescent probe can be simultaneously applied to the high-selectivity sensitive detection of copper ions and pyrophosphate.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a hydrogen spectrum characterization result of the fluorescent probe (probe) prepared in example 1;
FIG. 2 is a carbon spectrum characterization result of the fluorescent probe (probe) prepared in example 1;
FIG. 3 is a photograph of a fluorescent probe (probe) solution prepared in example 1 under irradiation of visible light (a) and an ultraviolet lamp (b);
FIG. 4 is a UV fluorescence spectrum of a fluorescent probe (probe) solution prepared in example 1;
FIG. 5 shows copper ions (Cu)2+) And the influence of pyrophosphate (PPi) on the fluorescence intensity of the fluorescent probe (probe) prepared in example 1;
FIG. 6 shows copper ion (Cu) in solutions of different pH values2+) Influence on the fluorescence intensity of the fluorescent probe (probe) prepared in example 1;
FIG. 7 shows copper ion (Cu) at different reaction times2+) Influence on the fluorescence intensity of the fluorescent probe (probe) prepared in example 1;
FIG. 8 shows copper ion (Cu) at different reaction temperatures2+) Fluorescence of the fluorescent Probe (Probe) prepared in example 1The effect of light intensity;
FIG. 9 shows copper ion (Cu) concentrations2+) Influence (A) on the fluorescence intensity of the fluorescent probe (probe) prepared in example 1 and the linear relationship (B);
FIG. 10 is a graph showing the effect of different metal ions on the fluorescence intensity of a fluorescent probe (probe);
FIG. 11 Pyrophosphate (PPi) versus different concentrations of copper ion (Cu)2+) Formed Cu2+Fluorescent probes (Cu)2+-probe) influence of the fluorescence intensity;
FIG. 12 is a graph of pyrophosphate (PPi) vs. Cu for different reaction times2+Fluorescent probes (Cu)2+-probe) influence of the fluorescence intensity;
FIG. 13 is a graph of pyrophosphate (PPi) vs. Cu at different reaction temperatures2+Fluorescent probes (Cu)2+-probe) influence of the fluorescence intensity;
FIG. 14 is a graph of pyrophosphate (PPi) versus Cu concentrations2+Fluorescent probes (Cu)2+Probe) influence of fluorescence intensity (A) and linear relationship (B);
FIG. 15 shows different anion pairs for Cu2+Fluorescent probes (Cu)2+-probe) fluorescence intensity.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Example 1
Preparing a fluorescent probe (probe) capable of detecting copper ions and pyrophosphate, wherein the reaction formula is as follows:
the specific reaction steps are as follows: mixing and dissolving 1.50g of 4-hydroxy umbelliferone, 0.28g of paraformaldehyde and 1.08g of proline in ethanol, heating to over 78 ℃ in an oil bath, and carrying out reflux reaction overnight; and after the reaction is finished, filtering and drying a reaction product to obtain the fluorescent probe (probe) capable of detecting copper ions and pyrophosphate.
In the preparation process, the fluorescent probe (probe) capable of detecting copper ions and pyrophosphate can be obtained by carrying out corresponding reactions on the substances of 4-hydroxy umbelliferone, paraformaldehyde and proline in a mass ratio of 0.8-1.0: 1-1.1: 0.8-1.0, wherein an ethanol solvent adopted in the reactions can be replaced by a methanol solvent.
Example 2
The nuclear magnetic resonance and spectral characteristics of the fluorescent probe (probe) synthetically prepared in example 1 were tested:
the hydrogen spectrum and the carbon spectrum of the fluorescent probe (probe) are respectively shown in fig. 1 and fig. 2, and the data results of the hydrogen spectrum and the carbon spectrum are as follows:1H NMR(300MHz,D2O)δ＝7.60(d,J＝8.8Hz,1H),6.88(d,J＝8.8Hz,1H),6.11(s,1H),4.44(s,2H),3.92(m,1H),3.73(m,1H),3.27(m,1H),2.44(m,1H),2.32(s,3H),2.10(m,1H),1.96(m,2H)ppm；13C NMR(100MHz,D2o) δ 173.5,163.5,159.7,156.8,152.8,128.4,112.9,112.8,109.9,104.1,68.5,55.3,46.6,29.1,23.3,18.1ppm, which demonstrates that the structure of the fluorescent probe (probe) prepared in example 1 is indeed that
The fluorescent probe (probe) was dissolved in a 40mM PBS buffer solution at pH 7.4 to form a 0.05. mu.M solution, which was colorless and transparent under visible light irradiation, as indicated by cuvette a in FIG. 3, and a blue fluorescent solution under ultraviolet light irradiation, as indicated by cuvette b in FIG. 3.
Carrying out ultraviolet detection on a fluorescent probe (probe) solution, wherein the excitation wavelength is 300-340 nm, and obtaining an excitation spectrogram, so that the maximum excitation wavelength of the fluorescent probe (probe) is 316 nm; fluorescence detection was performed at the maximum excitation wavelength to obtain a fluorescence spectrum, as shown in FIG. 4. From FIG. 4, it can be seen that the maximum excitation wavelength of the fluorescent probe (probe) is 316nm and the maximum emission wavelength is 445 nm.
Example 3
Copper ion (Cu)2+) And effect of pyrophosphate (PPi) on fluorescence of fluorescent probe (probe):
the fluorescent probe (probe) was dissolved in PBS buffer solution at pH 7.4 to obtain a fluorescent probe solution (probe) with a concentration of 0.05 μ M, and then copper ion (Cu) was added thereto2+) Make Cu2+The concentration was 0.5. mu.M (probe + Cu)2+) Then, pyrophosphate (PPi) was further added to make the concentration of PPi 180. mu.M (probe + Cu)2++ PPi). The fluorescence intensities of the three solutions were measured with 316nm as the excitation wavelength and 445nm as the emission wavelength, respectively, and the results are shown in fig. 5. As can be seen from the change in fluorescence intensity in FIG. 5, Cu was added2+Then, the fluorescence intensity of the probe at 445nm is reduced from about 450 to about 100, the quenching effect is obvious, the quenching efficiency is about 78 percent, and the fluorescent probe can detect Cu by a fluorescence quenching method2+(ii) a With the addition of 180. mu.M pyrophosphate (PPi) again, the fluorescence of the system increased. The reason for this is that Cu2+The probe (probe) and N and O atoms contained in the probe (probe) are connected through coordination to form a compound Cu2+Probe, whereby the conjugation effect of the probe molecule itself is destroyed and its fluorescence is quenched, and the probe molecule contains the compound Cu2+The addition of pyrophosphate (PPi) was continued during the dissolution of the probe, since PPi and Cu2+Has a stronger coordination than Cu2+With probe, thus Cu in solution2+Preferentially coordinate to PPi, destroying the compound Cu2+Probe, so that the fluorescence of the solution continues to increase. Thus, it was demonstrated that the fluorescent probe (probe) can be used for detecting Cu by fluorescence quenching2+And detecting PPi by a fluorescence enhancement method.
Example 4
Detection of copper ions (Cu) by fluorescence quenching method of fluorescent probe (probe) under different conditions2+) Influence of (2)：
1. Effect of pH in solution on quenching efficiency
The fluorescent probes (probes) were dissolved in PBS buffer solutions of pH 5.8, 6.2, 6.6, 7.0, 7.4, and 8.5, respectively, to obtain fluorescent probe solutions of 40mM concentration at different pH values, and Cu of 0.3. mu.M concentration was added2+The reaction was carried out for 10min, and the fluorescence intensities at 316nm as the excitation wavelength and 445nm as the emission wavelength were measured at 25 ℃ respectively, and the results are shown in FIG. 6. As can be seen from the results in FIG. 6, Cu is present in the solution having a pH of 5.8 to 8.52+The fluorescence intensity of the fluorescent probe (probe) can be reduced to a certain extent, and the quenching effect is gradually enhanced along with the increase of the pH value in the solution, and the quenching efficiency of copper ions on the fluorescent probe reaches the maximum of about 70% at the pH value of 8.5 and the pH value of 7.4.
2. Copper ion (Cu)2+) Effect of reaction time with fluorescent Probe on quenching efficiency
Under otherwise identical conditions (PBS buffer as solvent, pH 7.4, fluorescent probe concentration 0.05. mu. M, Cu2+At a concentration of 0.3. mu.M and a detection temperature of 25 ℃ and a test in which copper ions (Cu) were added to a solution of a fluorescent probe (probe)2 +) The results of the changes in fluorescence intensity after 0min, 5min, 10min, 20min and 30min of reaction are shown in FIG. 7. From the comparison of fluorescence intensities shown in FIG. 7, it can be seen that the fluorescent probe (probe) and Cu added2+The fluorescence intensity of the fluorescent material is basically consistent and is not influenced by reaction time, and copper ions (Cu)2+) The reaction time with the fluorescent probe (probe) had little effect on the quenching efficiency, indicating that copper ions (Cu)2+) The complex is formed rapidly by the reaction with the fluorescent probe (probe), and the fluorescent probe (probe) or the compound Cu2+The probe has better stability.
3. Copper ion (Cu)2+) Effect of reaction temperature with fluorescent Probe on quenching efficiency
Under otherwise identical conditions (PBS buffer as solvent, pH 7.4, fluorescent probe concentration 0.05. mu. M, Cu2+Concentration of 0.3. mu.M), the test was carried out at different temperatures (25 ℃, 37 ℃ and 50 ℃)Adding copper ions (Cu) into a fluorescent probe (probe) solution2+) The fluorescence intensity after the post-reaction was changed, and the result is shown in FIG. 8. From the comparison of fluorescence intensities shown in FIG. 8, it can be seen that the fluorescent probe (probe) and Cu added at different temperatures2+The fluorescence intensity is basically consistent, and is not influenced by the reaction temperature, and the copper ions (Cu)2+) The effect of the change in the reaction temperature with the fluorescent probe (probe) on the quenching efficiency was small, indicating that copper ions (Cu)2+) The complex is formed rapidly by the reaction with the fluorescent probe (probe), and the fluorescent probe (probe) or the compound Cu2+The probe has better stability.
4. Copper ion (Cu)2+) Effect of concentration on fluorescence intensity of fluorescent Probe (sensitivity detection)
Under otherwise identical conditions (PBS buffer as solvent, pH 7.4, fluorescent probe concentration 0.05. mu.M, reaction temperature 25 ℃, reaction time 5min, excitation wavelength 316nm, emission wavelength 445nm), different Cu were tested2+Effect of concentration (0nM, 10nM, 20nM, 40nM, 60nM, 80nM, 100nM, 200nM, 400nM, 600nM, 800nM) on quenching efficiency of fluorescence intensity of the fluorescent probe (probe), and change of fluorescence intensity is shown in A in FIG. 9. As can be seen from the change in fluorescence intensity, with Cu2+The concentration is gradually increased from 0.01 to 0.8 mu M, and the fluorescence intensity of the fluorescent probe is correspondingly gradually reduced, which indicates that the concentration is in Cu2+The concentration can influence the efficiency in fluorescence quenching to a large extent and there is a corresponding linear relationship. According to Cu2+The linear calibration plot fitted to the change in concentration and fluorescence intensity is shown as B in fig. 9, and has the linear equation of I-88.93-129.66 lnc (μ M) (where I is the fluorescence intensity and c is Cu2+Concentration (. mu.M)), the correlation coefficient (r) was 0.993. As can be seen from FIG. 9, the probe of the present invention has high sensitivity for detecting copper ions, and can coordinate with the concentration of 0.01-0.8. mu.M.
5. Fluorescent probe (probe) for copper ion (Cu)2+) Study of the selectivity
Under the same conditions (PBS buffer as solvent, pH 7.4, fluorescent probe concentration)0.05 μ M, 0.3 μ M metal ion concentration, 25 deg.C reaction temperature, 5min reaction time, and 316nm excitation wavelength; emission wavelength of 445nm), different metal ions (Cu) were tested2+、Na+、K+、Ca2+、Zn2+、Mg2+、Pb2+、Hg2+、Fe3+、Al3+、Ni2+、Co2+) The results of the influence on the fluorescence intensity of the fluorescent probe (probe) are shown in FIG. 10. As can be seen from FIG. 10, the difference in metal ion (Cu)2+、Na+、K+、Ca2+、Zn2+、Mg2+、Pb2+、Hg2+、Fe3+、Al3+、Ni2+、Co2+) Only adding copper ions (Cu)2+) The obvious quenching effect appears only when the fluorescence intensity of the fluorescent probe (probe) shows that the fluorescent probe (probe) has a quenching effect on copper ions (Cu)2 +) Has good selectivity.
Example 5
Different conditions for Cu2+Fluorescent probes (Cu)2+Probe) fluorescence enhancement method for detecting the effect of pyrophosphate (PPi):
1. different copper ion (Cu)2+) Concentration to Cu2+Fluorescent probes (Cu)2+-probe) influence of fluorescence intensity
First, different copper ions (Cu)2+) Cu was formed at a concentration (0. mu.M, 0.1. mu.M, 0.3. mu.M, 0.5. mu.M, 0.7. mu.M, 0.9. mu.M) and a fluorescent probe (probe) at a concentration of 0.05. mu.M2+Fluorescent probes (Cu)2+-probe), and then fluorescence intensity changes before and after the measurement under the same conditions (solvent of 40mM PBS buffer solution with pH 7.4, temperature 25 ℃, excitation wavelength 316nm, emission wavelength 445nm) with addition of 20 μ M pyrophosphate (PPi), the results of which are shown in fig. 11. From FIG. 11, it can be seen that Cu2+PPi vs Cu when the concentration increased from 0.1. mu.M to 0.5. mu.M2+The fluorescence recovery effect of the probe is gradually increased, and the recovery effect is gradually decreased at 0.5. mu.M to 0.9. mu.M, wherein Cu2+PPi vs Cu at a concentration of 0.5. mu.M2+The fluorescence enhancement effect of the probe is most remarkable.
2. Pyrophosphate (PPi) and Cu2+Fluorescent probes (Cu)2+-probe) effect of reaction temperature on efficiency enhancement
To a 40mM PBS buffer solution at pH 7.4 were added a fluorescent probe (probe) (concentration 0.05. mu.M) and Cu2+(0.5. mu.M) formation of Cu2+Fluorescent probes (Cu)2+Probe), pyrophosphate (PPi) (20. mu.M) was added thereto, and the reaction was carried out at 25 ℃, 37 ℃ and 50 ℃ for 10min, respectively, and the change in fluorescence intensity was measured at an excitation wavelength of 316nm and an emission wavelength of 445nm, as shown in FIG. 12. PPi and Cu can be seen2+The reaction temperature of the probe had substantially no effect on the fluorescence intensity, indicating that PPi, probe and Cu2+The strength of the coordination capacity is basically independent of the reaction temperature.
To a 40mM PBS buffer solution at pH 7.4 were added a fluorescent probe (probe) (concentration 0.05. mu.M) and Cu2+(0.5. mu.M) formation of Cu2+Fluorescent probes (Cu)2+Probe), pyrophosphate (PPi) (20. mu.M concentration) was added at 25 ℃, and changes in fluorescence intensity at 0min, 2min, 5min, 10min, 15min, 25min, and 30min of the reaction were measured at an excitation wavelength of 316nm and an emission wavelength of 445nm, and the results are shown in FIG. 13. PPi and Cu can be seen2+The reaction time of the probe had substantially no effect on the fluorescence intensity, indicating that PPi and Cu2+The coordination capacity between the two is stronger, and the reaction speed is high.
3. Pyrophosphate (PPi) concentration vs. Cu2+Fluorescent probes (Cu)2+Probe) influence of fluorescence intensity (sensitivity detection)
Under the same conditions (40 mM PBS buffer, pH 7.4, fluorescent probe concentration 0.05. mu.M, copper ion concentration 0.5. mu.M, reaction temperature 25 ℃, reaction time 5min, excitation wavelength 316nm, emission wavelength 445nm), PPi to Cu were added at different concentrations (0. mu.M, 2. mu.M, 5. mu.M, 8. mu.M, 15. mu.M, 20. mu.M, 25. mu.M, 30. mu.M, 35. mu.M, 40. mu.M) for testing2+Fluorescent probes (Cu)2+Probe) the effect of the fluorescence intensity enhancement efficiency, the change in fluorescence intensity of which is shown as A in FIG. 14. As can be seen from the change of fluorescence intensity, the concentration of the PPi gradually increases from 0 to 40 mu M, and the Cu concentration gradually increases2+-fluorescent probesThe corresponding gradual increase in the fluorescence intensity of the needle indicates that the efficiency in fluorescence enhancement can be greatly affected at PPi concentration, and a corresponding linear relationship exists. A linear calibration graph obtained by fitting from changes in PPi concentration and fluorescence intensity is shown as B in fig. 14, where I is 4.20c +147.18 (where I is fluorescence intensity, c is PPi concentration (μ M)), and the correlation coefficient (r) is 0.991. From FIG. 14, it can be seen that the probe of the present invention and Cu2+Coordinated Cu formation2+The fluorescent probe has a higher sensitivity for the detection of PPi, a lower concentration of PPi in solution being equally as capable of Cu2+Cu in fluorescent probes2+Coordination is preferred.
4、Cu2+Fluorescent probes (Cu)2+Probe) Selective study of pyrophosphate (PPi)
Different anions (Cl) were tested under the same conditions (40 mM PBS buffer, pH 7.4 as solvent, 0.05. mu.M as fluorescent probe, 0.5. mu.M as copper ion, 25 ℃ as reaction temperature, 5min as reaction time, 40. mu.M as anion concentration, 316nm as excitation wavelength, 445nm as emission wavelength)-、NO3 -、CO3 2-、PO4 3-、HPO4 2-、H2PO4 -、HCO3 -、SO4 2-And pyrophosphate) on Cu2+Fluorescent probes (Cu)2+Probe), the results are shown in FIG. 15. As can be seen from FIG. 15, in the presence of different anions (Cl)-、NO3 -、CO3 2-、PO4 3-、HPO4 2-、H2PO4 -、HCO3 -、SO4 2-And pyrophosphate) only pyrophosphate (PPi), Cu was added2+Fluorescent probes (Cu)2+Probe) shows a significant enhancement effect, indicating that Cu is present2+Fluorescent probes (Cu)2+-probe) for copper ions (Cu)2+) Has good selectivity.
In conclusion, the invention synthesizes the fluorescent probe (probe), which can not only be efficiently synthesized by the fluorescence quenching methodSensitive detection of Cu2+And Cu formed in the presence of copper ions2+Fluorescent probes (Cu)2+Probe), and pyrophosphate (PPi) can be detected efficiently and sensitively by fluorescence enhancement. The principle of the detection is as follows: carboxyl group-containing fluorescent probe and Cu2+The coordination occurs, so that the conjugation of the fluorescent probe is weaker, and the fluorescence is quenched; due to PPi and Cu2+The binding coordination capacity is stronger, and Cu is in the case of simultaneously existing fluorescent probe (probe) and pyrophosphate (PPi)2+Preferentially coordinate with PPi, resulting in the reversion of the conjugated structure of the probe itself, resulting in an increase in fluorescence intensity. Therefore, the fluorescent probe can be used as a good detection probe and can be simultaneously used for Cu2+And detection of PPi.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (8)
1. A fluorescent probe capable of detecting copper ions and pyrophosphate is characterized in that the structural formula of the fluorescent probe is as follows:
2. the method for preparing the fluorescent probe according to claim 1, wherein the method has a general reaction formula:
3. the method for preparing the fluorescent probe according to claim 2, wherein the reaction is specifically:
and (3) mixing and dissolving 4-hydroxy umbelliferone, paraformaldehyde and proline in ethanol or methanol, heating and refluxing in an oil bath for 12-14 h, filtering a reaction product after the reaction is finished, and drying to obtain the fluorescent probe.
4. The method for producing a fluorescent probe according to claim 3, wherein the mass ratio of the 4-hydroxyumbelliferone, paraformaldehyde, and proline is 0.8 to 1.0:1 to 1.1:0.8 to 1.0.
5. The method of producing a fluorescent probe according to claim 3, wherein the temperature of the heating reflux is 78 ℃ or higher.
6. Use of the fluorescent probe according to claim 1 for detecting copper ions.
7. Use of the fluorescent probe of claim 1 for detecting pyrophosphate.
8. The use of claim 7, wherein the fluorescent probe is first coordinated with copper ions to form Cu2+-a fluorescent probe.
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