CN110283213B - Colorimetric probe capable of detecting bisulfite and mercury ions, and synthesis method and application thereof - Google Patents
Colorimetric probe capable of detecting bisulfite and mercury ions, and synthesis method and application thereof Download PDFInfo
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- CN110283213B CN110283213B CN201910470897.7A CN201910470897A CN110283213B CN 110283213 B CN110283213 B CN 110283213B CN 201910470897 A CN201910470897 A CN 201910470897A CN 110283213 B CN110283213 B CN 110283213B
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- 239000000523 sample Substances 0.000 title claims abstract description 66
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- -1 mercury ions Chemical class 0.000 title claims abstract description 30
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- 238000001308 synthesis method Methods 0.000 title description 2
- 238000001514 detection method Methods 0.000 claims abstract description 17
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- 229910021135 KPF6 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
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- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
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Abstract
The invention discloses a colorimetric probe capable of continuously detecting bisulfite and mercury ions, a synthetic method and application thereof. The colorimetric probe is prepared by reacting 2-halopyridine, 5-aldehyde-2-thiopheneboronic acid and [ Ru (cycme) Cl2]22, 2' -bipyridine and 3-ethyl-2, 3-dihydro-1, 1, 2-trimethyl-1H-benzo [ e]And (3) sequentially reacting the indole hexafluorophosphate to obtain the indole hexafluorophosphate. Can detect HSO in aqueous solution respectively and continuously3 ‑And Hg2+Especially in conjunction with HSO3 ‑After action, in situ on Hg2+The detection effect is more obvious. The colorimetric probe has high sensitivity and good selectivity.
Description
Technical Field
The invention belongs to the technical field of analysis and detection, and particularly relates to a colorimetric probe capable of detecting bisulfite and mercury ions, a synthetic method and application thereof.
Background
Bisulfite has widespread use in human life, often as an additive in the production of food and pharmaceuticals, but excessive intake of bisulfite may also cause some physical harm, such as diarrhea, hypotension, asthma and allergic reactions, and is therefore important for the detection of bisulfite ions. At present, the detection method of bisulfite ion is commonly used in chromatography, capillary electrophoresis, chemiluminescence, enzyme analysis, spectroscopy, etc.
As a common environmental pollutant, mercury ions can cause irreversible damage to the central nervous system and the digestive system after entering a human body due to non-biodegradability and bioaccumulation. With the attention of people on body health and environmental protection, the chemical sensor with high selectivity and high sensitivity to the ions is designed and synthesized, and has important significance on aspects of environmental monitoring, disease prevention and treatment and the like. Currently, common mercury ion detection means include atomic absorption/emission spectrometry, gas chromatography, nuclear magnetic resonance, X-ray fluorescence spectrometry, inductively coupled plasma-mass spectrometry, electrochemical methods (such as anodic stripping voltammetry, oxidation-reduction potential method, and the like), colorimetric methods (such as traditional dithizone method), and the like.
Compared with a photochemical sensor constructed based on small organic molecules, the photochemical sensor constructed by the metal complex is rapidly developed in recent years due to the advantages of large Stokes displacement, low excitation energy, good stability, easy realization of colorimetric identification and the like. And its excellent performance as a sensor benefits from its well-tunable phosphorescence emission properties. Although the detection of small molecules and ions by means of changes in phosphorescence/fluorescence emission has certain advantages in terms of sensitivity, colorimetric sensors based on intuitive color changes are simpler to operate, even without the aid of instruments, and are quite convenient in practical applications. An excellent colorimetric sensor needs to have good absorption in a visible light region, wherein due to the formation of Ru-C, the MLCT state absorption of the ring metal ruthenium complex is located in the visible light region, and functional groups are easily introduced and act with specific ions through ligand adjustment, so that the spectrum change of the visible light region is caused, and the change visible to naked eyes is realized. Therefore, attention has been drawn to work on the use of cyclometalated ruthenium complexes for detecting ions. However, these complexes can only singly recognize a specific ion in a specific solvent or aqueous solution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a colorimetric probe capable of detecting bisulfite and mercury ions, wherein the colorimetric probe can simultaneously identify metal ions Hg2+And anionic HSO3 -Capacity to Hg in water2+And HSO3 -All have better selectivityAnd adding HSO to the complex3 -Thereafter, a macroscopic color change can be formed for the mercury ions, thereby simplifying the test method.
The second technical problem to be solved by the present invention is to provide a method for preparing the colorimetric probe.
The third technical problem to be solved by the invention is to provide the application of the colorimetric probe.
In order to solve the first technical problem, the invention adopts the following technical scheme:
a colorimetric probe capable of detecting bisulfite and mercury ions, the colorimetric probe having the following chemical formula:
in order to solve the second technical problem, the synthesis route designed by the present invention comprises the following steps (only a specific substance is represented in the reaction structural formula, for example, 2-halopyridine is represented by 2-bromopyridine):
1) preparing 5- (2-pyridyl) thiophenecarboxaldehyde, namely a compound 1;
2-halopyridine, an organic solvent and carbonic acid are sequentially added into a reaction device. Stirring thoroughly under inert atmosphere, adding 5-aldehyde-2-thiopheneboronic acid and Pd (PPh)3)4And (3) refluxing for 20-24 h at 90-100 ℃, and stopping the reaction. Purifying to obtain light yellow 5- (2-pyridyl) thiophenecarboxaldehyde solid.
2) Preparing a metal ruthenium complex containing aldehyde groups, namely a compound 2;
adding 5- (2-pyridyl) thiophenecarboxaldehyde and KPF into a reaction device in sequence6And acetonitrile. Introducing argon or nitrogen to drive off oxygen in the reaction device, and adding [ Ru (cycme) Cl2]2And stirring and refluxing the mixed solution at 50-60 ℃ for 12-18 h, and cooling to room temperature. The solvent was removed to give an orange-red solid. Then adding 2, 2' -bipyridine and methanol, and carrying out reflux reaction for 8-14 h at 60-80 ℃ under an inert atmosphere. Purifying to obtain black metallic ruthenium complex solid containing aldehyde group.
3) Preparing a target colorimetric probe, namely a metal ruthenium complex I;
and sequentially adding 3-ethyl-2, 3-dihydro-1, 1, 2-trimethyl-1H-benzo [ e ] indole hexafluorophosphate, an aldehyde group-containing metal ruthenium complex and ethanol into a reaction device, reacting for 8-14 hours at 70-85 ℃ in the dark, changing the color of the solution from red to reddish brown, and purifying to obtain a reddish brown solid.
Preferably, in the step 1), the 2-halopyridine is 2-bromopyridine or 2-chloropyridine.
Preferably, in the step 1), the organic solvent is ethylene glycol dimethyl ether or tetrahydrofuran.
Preferably, in the step 1), 2-halopyridine, 5-aldehyde-2-thiopheneboronic acid and carbonate, Pd (PPh) and the like are added according to the mass ratio3)4Is (2.5-3.0): (2.5-3.0): 1: (0.05-0.1).
Preferably, in the step 2), according to the mass ratio, the [ Ru (cycme) Cl2]25- (2-pyridyl) thiophenecarboxaldehyde and 2, 2' -bipyridine are 1: (1.2-1.6): (2.5-4).
Preferably, in the step 3), the amount of the aldehyde group-containing metal ruthenium complex and 3-ethyl-2, 3-dihydro-1, 1, 2-trimethyl-1H-benzo [ e ] indole hexafluorophosphate is 1: 1 to 1.5.
In order to solve the third technical problem, the invention uses the colorimetric probe to detect bisulfite and mercury ions in an aqueous solution respectively.
In order to solve the third technical problem, the invention also uses the colorimetric probe for continuously detecting the bisulfite and mercury ions in the aqueous solution.
Compared with the prior art, the colorimetric probe provided by the invention has the following beneficial effects:
first, the colorimetric probes of the present invention utilize benzo [ e ]]Indole structure recognition of HSO3 -The object of (a); at the same time, thiophene groups and Hg can also be utilized2+The coordination of the Hg ions in the Hg-Hg complex is realized2+Especially in conjunction with HSO3 -After action, in situ on Hg2+The detection is more obvious, namely Hg can be continuously identified2+And HSO3 -。
Secondly, the colorimetric probe has good detection/chemical stability, high sensitivity and good selectivity.
Thirdly, the colorimetric probe of the present invention has a good solubility in water.
Drawings
FIG. 1 is a hydrogen spectrum of an intermediate product of the present invention.
FIG. 2 is a hydrogen spectrum of the colorimetric probe of the present invention.
FIG. 3 shows different equivalent weights of HSO of the colorimetric probe of the present invention3 -The change in absorbance was titrated.
FIG. 4 shows different equivalent amounts of HSO of the colorimetric probe of the present invention3 -The resulting detection line LOD was titrated.
FIG. 5 shows HSO of the colorimetric probes of the present invention under different anion interferences3 -Influence on its absorbance.
FIG. 6 is a graph of colorimetric probes of the present invention at different equivalents of Hg2+The change in absorbance was titrated.
FIG. 7 is a graph of colorimetric probes of the present invention at different equivalents of Hg2+The resulting detection line LOD was titrated.
FIG. 8 shows Hg under different cation interferences for the colorimetric probes of the present invention2+Influence on its absorbance.
FIG. 9 shows a colorimetric probe of the present invention with HSO added3 -Post in situ detection of different equivalent Hg2+Change in lower absorbance.
FIG. 10 shows a colorimetric probe of the present invention with HSO added3 -Post in situ detection of different equivalent Hg2+And obtaining the LOD of the detection line.
FIG. 11 shows the addition of HSO to a colorimetric probe of the present invention3 -And then detecting the change of the absorbance under different metal ions in situ.
FIG. 12 shows a colorimetric probe of the present invention in the presence of HSO3 -Post in situ detection of Hg2+A colorimetric image visible to the naked eye.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example one preparation of a colorimetric probe of the present invention:
(1) synthesis of 5- (2-pyridyl) thiophenecarboxaldehyde
To a 100mL three-necked flask were added 2-bromopyridine (0.51g, 3.2mmol), ethylene glycol dimethyl ether (15mL), and potassium carbonate (5mL, 0.8mmol) in that order. After stirring thoroughly under argon protection, 5-formyl-2-thiopheneboronic acid (0.52g, 3.3mmol) and Pd (PPh) were added3)4(0.19g, 0.16mmol) was refluxed at 100 ℃ for 24 hours, and then the reaction was stopped. Water (10mL) was added, extracted 3 times with dichloromethane and spin-dried to give a brown oil. Column chromatography using dichloromethane/petroleum ether (v/v, 1/1) as developing solvent gave 0.17g of pale yellow solid in 28% yield.
Nuclear magnetic resonance chemical shift:1H NMR(400MHz,CDCl3)δ:9.94(s,1H),8.66～8.63(m,1H),7.80～7.72(m,3H),7.70(d,J＝4.0Hz,1H),7.31～7.27(m,1H).
(2) synthesis of Compound 2
A100 mL three-necked flask was charged with 5- (2-pyridyl) thiophenecarboxaldehyde (0.15g, 0.78mmol), KPF6(0.2937g, 1.60mmol), and acetonitrile (12mL) in this order. After introducing argon for 10min, [ Ru (cycme) Cl2]2(0.3g, 0.5mmol) was added, and the mixture was stirred at 55 ℃ under reflux for 16h and then cooled to room temperature. And removing the solvent by rotary evaporation to obtain an orange-red solid. 2, 2' -bipyridine (0.25g,1.57 mmol) and methanol (12mL) were added to the above reaction flask, and then the mixture was refluxed at 70 ℃ for 12 hours under argon gas. The reaction was stopped and spin dried. Column chromatography of 0.27g of black solid with dichloromethane/acetonitrile (v/v,10/1) as developing solvent gave 58% yield.
Nuclear magnetic resonance chemical shift: 1H NMR (400MHz, CD3 CN). delta. (ppm):9.80(s,1H),8.48(d, J ═ 8.2Hz,1H),8.41(d,J＝8.2Hz,1H),8.35(t,J＝7.7Hz,2H),8.07～7.97(m,2H),7.93～7.77(m,7H),7.71(t,J＝7.8Hz,1H),7.55(d,J＝5.7Hz,1H),7.45(t,J＝7.4Hz,1H),7.28(m,J＝6.5Hz,3H),7.12(s,1H),6.94(t,J＝6.5Hz,1H)；13C NMR(101MHz,CD3CN),δ(ppm):184.12,162.22,157.66,157.17,156.87,155.54,154.71,151.06,150.98,150.61,149.42,146.21,143.84,136.62,136.32,135.34,134.49,134.30,127.08,126.53,126.51,126.39,126.26,123.44,123.29,123.05,122.93,122.17,119.69,117.27；MS(Maldi-TOF,CHCA)m/z:Calculated for602.06([M-PF6]+),Found:601.98.
(3) synthesis of target product Compound I
Benzoindoxyl hexafluorophosphate (0.06g, 0.15mmol), a metal ruthenium complex containing an aldehyde group (0.09g, 0.12mmol) and ethanol (10mL) were sequentially added to a 50mL three-necked flask, and reacted at 80 ℃ for 12 hours while the reaction apparatus was protected from light, whereby the color of the solution changed from red to reddish brown. Column chromatography with acetonitrile/methanol/saturated KPF6 and water as developing agent to obtain 0.053g of reddish brown solid with 40% yield.
Nuclear magnetic resonance chemical shift: 1H NMR (400MHz, Methanol-d4) δ 8.74-8.49 (m,5H),8.36(d, J ═ 8.5Hz,1H), 8.25-8.17 (m,2H), 8.17-8.06 (m,2H), 8.02-7.84 (m,8H),7.78(q, J ═ 7.9Hz,2H), 7.72-7.60 (m,2H),7.54(dd, J ═ 7.4,5.7Hz,1H),7.38(dp, J ═ 5.6,1.6Hz,4H),7.16(d, J ═ 15.6Hz,1H),7.03(dd, J ═ 7.4,5.7, 1H),4.70(d, J ═ 7.4, 2H),2.02(dd, 2H), 19.3.3H, 3H), 3.3.3H (d, J ═ 2H).
Example two applications of the colorimetric probes of the present invention:
(1) preparation of colorimetric Probe solution
0.0022g (0.002mmol) of target metal ruthenium complex is weighed and is made to be 100mL by HEPES buffer solution to obtain 2X 10-5M colorimetric probe solution.
(2) HSO of different equivalent3 -Absorbance test of the Probe of the present invention
(3) Under interference of different anions, HSO3 -Influence on its absorbance
Adding different anion Cl with the concentration of 1mM into the prepared colorimetric probe solution-、Br-、I-、ClO4 -、SO4 2-、NO3 -、H2PO4 -、CO3 2-、HCO3 -、Ac-、HS-And continuing to add 40 μ M HSO on the basis3 -After equilibration, the change in absorbance at a wavelength of 500nm was measured with an ultraviolet spectrophotometer. The test results are shown in FIG. 5. As can be seen from FIG. 5, the colorimetric probe is better selective for bisulfite ions.
(4) Different equivalent Hg2+Absorbance test of the Probe of the present invention
(5) Hg under different cation interferences2+Influence on its absorbance
Adding different cationic Cu with the concentration of 2mM into the prepared colorimetric probe solution2+、Pb2+、Cr2+、Co2 +、Ni2+、Sr2+、Ag+、Mn2+、Ca2+、Mg2+、Ba2+、Na+And continuing to add 0.5mM Hg based thereon2+After equilibration, the change in absorbance at a wavelength of 500nm was measured with an ultraviolet spectrophotometer. The test results are shown in FIG. 8. As can be seen from FIG. 8, the colorimetric probe has better selectivity for mercury ions, and only a large amount of Ag+Some interference will occur.
(6) After addition of a defined amount of HSO3 -In the probe solution, the invention detects different equivalent Hg in situ2+Change in lower absorbance.
3mL of this colorimetric probe solution and 20uL of 2X 10 were taken-3M bisulfite ion in a test tube, then 0-20. mu.M Hg is added2+After equilibration, the change in absorbance at a wavelength of 500nm was measured with an ultraviolet spectrophotometer. The test results are shown in FIGS. 9 and 10. As can be seen from FIGS. 9 and 10, the colorimetric probe can continuously detect bisulfite ions and mercury ions.
(7) After addition of a defined amount of HSO3 -In the probe solution, the invention detects the influence of different metal ions on the absorbance thereof in situ.
3mL of this colorimetric probe solution and 20. mu.L of 2X 10-3M bisulfite ion solution in test tube with various cation concentrations of 2.5 × 10-2M, then respectively adding 20 equivalents of metal ions, and after balancing, testing the change of absorbance at the wavelength of 500nm by using an ultraviolet spectrophotometer. The test results are shown in FIG. 11. As can be seen from FIG. 11, the colorimetric probe is selective for mercury ion metal ions after the addition of the anion bisulfite ion, and only a large amount of silver ions will have a certain effect.
(8) In the presence of HSO3 -Post in situ detection of Hg2+A colorimetric image visible to the naked eye.
Group one: 2mL of this colorimetric probe solution and 20. mu.L of 2X 10-3M bisulfite ion in a test tube, then 1-30 equivalent concentration of 1 × 10-2M mercury ion solution (i.e. adding 1 equivalent first, carrying out detection analysis, then adding 1 equivalent in the system, and detectingAnalysis was carried out until a 30-normal concentration of 1X 10 was added to the system-2M in mercury ion), and mixing. And a second group: 2mL of the colorimetric probe solution was taken in a test tube, and then 30 equivalents of the colorimetric probe solution was directly added thereto at a concentration of 1X 10-2And (4) mixing the mercury ion solution of M uniformly. Both groups were left for 1 hour (1X 10 for each 1-equivalent increase in concentration for group one)-2The mercury ion solution of M was left for 1 hour). The results are shown in FIG. 12 (only 1 equivalent of the concentration is shown in the figure as 1X 10-2M mercury ion solution and 30 equivalent concentration of 1X 10-2Colorimetric plot of mercury ion solution of M).
After a proper amount of bisulfite ions are added into the colorimetric probe HEPES buffer solution system, the whole system is changed from orange to light pink, and then mercury ions with different concentrations can be detected, the mercury ion concentration in the first group is up to 1 equivalent of mercury ion solution each time, the system color is gradually darkened, the color change can be checked by naked eyes, when the mercury ion concentration is up to 30 equivalents, the color can be found to be changed from light pink when only bisulfite ions are added and mercury ions are not added into the system, while the color of the second group is changed from original orange to reddish brown when 30 equivalents of mercury ions are directly added into the colorimetric probe HEPES buffer solution system, the reddish brown is basically the same as the reddish brown of the first group and is closer to the original orange, but the difference between the reddish brown and the original orange can be checked by naked eyes.
In addition, the inventors also added 1 equivalent of HEPES buffer solution of the colorimetric probe of the present invention at a concentration of 1X 10 per time according to the method of group I-2Experiments are carried out on the mercury ion solution of M, and the result shows that the color of the system is not obviously changed and can not be checked by naked eyes when the mercury ion solution is added every time, and the color is changed to reddish brown close to orange color only when the color is changed to 30 equivalents cumulatively.
Claims (8)
1. A colorimetric probe for detecting bisulfite and mercury ions, the colorimetric probe having the chemical formula:
2. a method of preparing a colorimetric probe as defined in claim 1, wherein: the method comprises the following steps:
1) preparing 5- (2-pyridyl) thiophenecarboxaldehyde;
sequentially adding 2-halopyridine, an organic solvent and carbonate into a reaction device; stirring thoroughly under inert atmosphere, adding 5-aldehyde-2-thiopheneboronic acid and Pd (PPh)3)4Refluxing for 20-24 h at 90-100 ℃, and stopping the reaction; purifying to obtain light yellow 5- (2-pyridyl) thiophenecarboxaldehyde solid;
2) preparing a metal ruthenium complex containing aldehyde groups;
adding 5- (2-pyridyl) thiophenecarboxaldehyde and KPF into a reaction device in sequence6Acetonitrile; introducing argon or nitrogen to drive off oxygen in the reaction device, and adding [ Ru (cycme) Cl2]2Stirring and refluxing the mixed solution at 50-60 ℃ for 12-18 h, cooling to room temperature, and removing the solvent to obtain an orange-red solid; then adding 2, 2' -bipyridine and methanol, and carrying out reflux reaction for 8-14 h at 60-80 ℃ in an inert atmosphere; purifying to obtain black metal ruthenium complex solid containing aldehyde group;
3) preparing a target colorimetric probe, namely a metal ruthenium complex;
and sequentially adding 3-ethyl-1, 1, 2-trimethyl-1H-benzo [ e ] indole hexafluorophosphate, an aldehyde group-containing metal ruthenium complex and ethanol into a reaction device, reacting for 8-14 hours at 70-85 ℃ in a dark condition, changing the color of the solution from red to reddish brown, and purifying to obtain a reddish brown solid.
3. The method of preparing a colorimetric probe according to claim 2, wherein:
in the step 1), the 2-halopyridine is 2-bromopyridine or 2-chloropyridine.
4. The method for preparing a colorimetric probe according to claim 2 or 3, characterized in that:
in the step 1), the organic solvent is ethylene glycol dimethyl ether or tetrahydrofuran.
5. The method for preparing a colorimetric probe according to claim 2 or 3, characterized in that:
in the step 1), according to the mass ratio, 2-halopyridine, 5-aldehyde-2-thiopheneboronic acid and carbonate, Pd (PPh)3)4Is (2.5-3.0): (2.5-3.0): 1: (0.05-0.1).
6. The method for preparing a colorimetric probe according to claim 2 or 3, characterized in that:
in the step 2), according to the mass ratio, Ru (cycme) Cl2]25- (2-pyridyl) thiophenecarboxaldehyde and 2, 2' -bipyridine are 1: (1.2-1.6): (2.5-4).
7. The method for preparing a colorimetric probe according to claim 2 or 3, characterized in that: in the step 3), according to the amount of the substance, the metal ruthenium complex containing aldehyde group and 3-ethyl-1, 1, 2-trimethyl-1H-benzo [ e ] indole hexafluorophosphate are 1: 1 to 1.5.
8. Use of a colorimetric probe according to claim 1 for the preparation of a probe for continuous detection of bisulfite and mercury ions.
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| CN103145764A (en) * | 2013-03-05 | 2013-06-12 | 苏州太湖电工新材料股份有限公司 | Ruthenium comlex and mercury ion sensor as well as preparation methods thereof |
| CN103275698A (en) * | 2013-05-31 | 2013-09-04 | 太原理工大学 | Ratio-dependent bisulfite ion fluorescent probes and preparation method thereof |
| CN106496197A (en) * | 2016-10-27 | 2017-03-15 | 湖南师范大学 | A kind of Fluorescence Increasing type quick detection sulfurous acid hydrogen radical ion or the synthesis and application of sulfite ion fluorescent molecular probe |
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| CN103145764A (en) * | 2013-03-05 | 2013-06-12 | 苏州太湖电工新材料股份有限公司 | Ruthenium comlex and mercury ion sensor as well as preparation methods thereof |
| CN103275698A (en) * | 2013-05-31 | 2013-09-04 | 太原理工大学 | Ratio-dependent bisulfite ion fluorescent probes and preparation method thereof |
| CN106496197A (en) * | 2016-10-27 | 2017-03-15 | 湖南师范大学 | A kind of Fluorescence Increasing type quick detection sulfurous acid hydrogen radical ion or the synthesis and application of sulfite ion fluorescent molecular probe |
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