CN108822138B - Application of metal complex fluorescent probe in detection of hydrogen sulfide in gas - Google Patents
Application of metal complex fluorescent probe in detection of hydrogen sulfide in gas Download PDFInfo
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- CN108822138B CN108822138B CN201810293742.6A CN201810293742A CN108822138B CN 108822138 B CN108822138 B CN 108822138B CN 201810293742 A CN201810293742 A CN 201810293742A CN 108822138 B CN108822138 B CN 108822138B
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 30
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 17
- 239000007850 fluorescent dye Substances 0.000 title claims description 14
- 239000007789 gas Substances 0.000 title claims description 14
- 238000001514 detection method Methods 0.000 title description 13
- 239000000523 sample Substances 0.000 abstract description 24
- XPDXVDYUQZHFPV-UHFFFAOYSA-N Dansyl Chloride Chemical class C1=CC=C2C(N(C)C)=CC=CC2=C1S(Cl)(=O)=O XPDXVDYUQZHFPV-UHFFFAOYSA-N 0.000 abstract description 20
- 239000010949 copper Substances 0.000 abstract description 17
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- 229910001431 copper ion Inorganic materials 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 7
- 150000004699 copper complex Chemical class 0.000 abstract description 3
- 238000006862 quantum yield reaction Methods 0.000 abstract description 3
- 238000010206 sensitivity analysis Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- -1 sulfur ions Chemical class 0.000 description 8
- 239000012224 working solution Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- ONRREFWJTRBDRA-UHFFFAOYSA-N 2-chloroethanamine;hydron;chloride Chemical compound [Cl-].[NH3+]CCCl ONRREFWJTRBDRA-UHFFFAOYSA-N 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- BQAHELYRKADDGO-UHFFFAOYSA-N n-(furan-2-ylmethyl)-1-pyridin-2-ylmethanamine Chemical compound C=1C=COC=1CNCC1=CC=CC=N1 BQAHELYRKADDGO-UHFFFAOYSA-N 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 230000004224 protection Effects 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000011161 development Methods 0.000 description 4
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- 241000282414 Homo sapiens Species 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
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- 210000002345 respiratory system Anatomy 0.000 description 3
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
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- 238000012544 monitoring process Methods 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 210000000196 olfactory nerve Anatomy 0.000 description 1
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 230000024883 vasodilation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The dansyl chloride derivative has large Stokes shift, relatively high quantum yield, simple synthetic route and good light stability; and contains a polydentate ligand, and a stable dansyl chloride copper metal complex probe is generated after coordination with copper ions. The copper complex probe has good sensitivity analysis on hydrogen sulfide and good selectivity on hydrogen sulfide.
Description
Technical Field
The invention relates to the technical field of analytical chemistry, in particular to a preparation method of a metal complex fluorescent probe.
Background
Since the reform is opened, along with the rapid development of economy, the industrial level is rapidly advanced, the living standard of human beings is obviously improved, and meanwhile, a series of environmental problems are brought, wherein the problem of air pollution is particularly serious and comprises the pollution of gases such as sulfur oxides, nitrogen oxides, hydrocarbons, carbon monoxide and the like. For example, hydrogen sulfide H2S is a toxic pollutant gas, colorless, foul smell, extremely toxic and inflammable. Mainly comes from the manufacturing process of sulfur, sulfuric acid, dye and cosmetics, and the decomposition process of microorganism. Trace hydrogen sulfide can stimulate respiratory tract to cause dizziness and headachePain, throat discomfort, cough, and prolonged exposure to H2The S gas can cause olfactory nerve paralysis, seriously damage central nerves and respiratory systems and harm human health. On the other hand, H2S, a very important bioactive sulfur substance in vivo, is a third endogenous gas signaling molecule found after NO and CO, plays an important role in physiological processes such as myocardial protection, neuromodulation, vasodilation, anti-inflammation, central nervous system, respiratory tract, gastrointestinal tract, and endocrine system, and is closely related to Huntington ' S, parkinson ' S disease, alzheimer ' S disease, and even cancer. Therefore, the development of a method for detecting the sulfur ions with high selectivity and high sensitivity has great research significance for monitoring environmental pollution and human health.
The analysis of hydrogen sulfide was originally limited to chemical analysis and electrochemical analysis, and the detection method had low sensitivity. Since the 60 s of the 20 th century, with the wide application of spectroscopic and chromatographic techniques, the development of hydrogen sulfide analysis, such as inductively coupled plasma atomic emission spectroscopy, high performance liquid chromatography and gas chromatography, was promoted. With the development and application of the technology, the hydrogen sulfide analysis technology has updated progress, including modern spectral analysis, modern chromatographic analysis, spectrum-chromatography combination, biosensing, immunoassay and the like, and most of the methods can meet the requirements of trace analysis of hydrogen sulfide and have high precision and sensitivity. However, they all have the disadvantages of complex operation, time and labor waste, high cost and the like to different degrees, and the used monitoring instrument has large volume and high price, thus failing to meet the purpose of rapidly detecting hydrogen sulfide on site.
In recent years, fluorescence analysis techniques have attracted increasing research and development because fluorescence analysis methods have the greatest advantages of short response time, high sensitivity, wide detection range, and simpler operation techniques. The Nagano subject group synthesizes and prepares a macrocyclic copper ion complex fluorescent probe for detecting hydrogen sulfide based on a fluorescence method, and the identification can be completed in only a few seconds, thereby realizing the on-off detection of the hydrogen sulfide. However, most current fluorescent probes for detecting hydrogen sulfide are based on a fluorescence quenching turn-off process, and the detection method is easily influenced by a plurality of environmental conditions. However, there are few reports of fluorescence-enhanced turn-on based detection. The dansyl chloride derivative has large Stoke shift, relatively high quantum yield, simple synthetic route, good light stability and good water solubility. Based on the excellent spectral performance of dansyl chloride, a turn-on fluorescence enhanced dansyl chloride metal complex fluorescent probe is designed and prepared, and the analysis and detection of hydrogen sulfide are realized.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of a metal complex fluorescent probe, which is a novel method for designing and synthesizing a water-soluble fluorescent functionalized dansyl chloride metal complex. And the problem of the relation between the fluorescent signal output and the hydrogen sulfide concentration in the reaction process is solved through a fluorescent switch mechanism.
A preparation method of a metal complex fluorescent probe comprises the following steps:
s1: adding dansyl chloride and triethylamine into a round-bottom flask containing dichloromethane, then adding chloroethyl amine hydrochloride, reacting and stirring at room temperature for 0.5-1.5h under the protection of nitrogen, and removing a dichloromethane solvent by using a rotary evaporator to obtain a yellow oily substance;
s2: then separating and purifying the obtained substance by using a silica gel column to obtain a product Ds-1;
s3: weighing Ds-1 products, placing the Ds-1 products into DMF for dissolving, adding furan-2-ylmethyl-pyridine-2-ylmethyl-amine and anhydrous potassium carbonate, stirring at room temperature for 22-26h, adding ice water into reaction mixed liquid to generate a large amount of precipitate, filtering to obtain precipitate solids, and separating and purifying the obtained substances by using a silica gel column to obtain yellow oily products Ds-2:
s4: the solid product Ds-2 was dissolved in ethanol solution to give a solution with a concentration of 100 mM. Then mixing and stirring the solution and copper chloride aqueous solution with the same volume and the same concentration for 5-15min to obtain 50mM copper ion complex Ds-Cu working solution of dansyl chloride, and placing the working solution in a refrigerator for later use.
Preferably, the mass volume addition ratio of dansyl chloride, triethylamine, dichloromethane and chloroethyl amine hydrochloride in the S1 is as follows: (0.1-0.2) g: (80-160) μ L: (8-12) mL: (0.0043-0.0086) g.
Preferably, the developing agent of the silica gel column in S2 is petroleum ether: ethyl acetate 4:1, Rf 0.42.
Preferably, the mass volume addition ratio of Ds-1, DMF, furan-2-ylmethyl-pyridin-2-ylmethyl-amine, anhydrous potassium carbonate and ice water in S3 is as follows: (0.06-0.07) g: (2-4) mL: (0.03-0.04) g: (0.02-0.03) g: (12-18) mL.
Preferably, the developing agent of the silica gel column in S3 is petroleum ether: ethyl acetate 4:1-1: 1.
The dansyl chloride copper metal complex probe provided by the invention is applied to detecting hydrogen sulfide.
The action principle is as follows:
the probe quenches a fluorophore by utilizing an electronic effect or an electron transfer mechanism of a heavy metal ion, particularly a stable metal complex is formed by an organic fluorescent ligand and Cu (II), and the generation reason mainly depends on that an excited state electron in a chromophore can be received by a d track in a central hollow of paramagnetic Cu (II), so that the process of ligand fluorescence generation is blocked. Thus, once the copper ions in the complex are removed to release the free ligand, the fluorescence of the ligand is restored. According to the theory of soft and hard acids and bases, S2-And Cu2+Has strong affinity with each other, the formed copper sulfide precipitate is very stable, and the Ksp of the copper sulfide precipitate is 1.27 × 10-36. Adding H to the solution2After S, Cu (II) can be separated from the complex, free fluorescent ligand is released, and fluorescence is recovered. Therefore, a theoretical basis is provided for the application of the metal complex fluorescent probe in the field of hydrogen sulfide detection through a fluorescence switching mechanism.
The invention has the following beneficial effects:
the dansyl chloride derivative has large Stokes shift, relatively high quantum yield, simple synthetic route and good light stability; and contains a polydentate ligand, and a stable dansyl chloride copper metal complex probe is generated after coordination with copper ions. The copper complex probe has good sensitivity analysis on hydrogen sulfide and good selectivity on hydrogen sulfide.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a scheme for the synthesis of dansyl chloride copper metal complex;
FIG. 2 shows the structure and fluorescence spectrum of a dansyl chloride copper metal complex fluorescent probe;
FIG. 3 is a diagram of the fluorescence switch process when a probe detects hydrogen sulfide small molecules;
FIG. 4 is a graph of the linear relationship between hydrogen sulfide concentration and probe fluorescence recovery intensity;
FIG. 5 is a fluorescence spectrum diagram of the probe for selective detection of other six kinds of small molecule gases.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
A preparation method of a metal complex fluorescent probe comprises the following steps:
s1: adding 0.1g of dansyl chloride and 80 mu L of triethylamine into a round-bottom flask containing 8mL of dichloromethane, then adding 0.0043g of chloroethylamine hydrochloride, reacting and stirring at room temperature for 0.5h under the protection of nitrogen, and removing dichloromethane solvent by using a rotary evaporator to obtain yellow oil;
s2: the resulting material was then purified by silica gel column chromatography on petroleum ether: ethyl acetate 4:1, RfSeparating and purifying under the condition of 0.42 to obtain a product Ds-1;
s3: 0.06g of Ds-1 product was weighed and dissolved in 2mL of DMF, and then 0.03g of furan-2-ylmethyl-pyridin-2-ylmethyl-amine and 0.02g of anhydrous potassium carbonate were added, and after stirring at room temperature for 22 hours, 12mL of ice water was added to the reaction mixture, and a large amount of precipitate was generated, and the precipitate was filtered to obtain a solid, and then the obtained substance was purified by silica gel column petroleum ether/: separation and purification are carried out under the condition of ethyl acetate being 4:1, and a yellow oily product Ds-2 is obtained:
s4: the solid product Ds-2 was dissolved in ethanol solution to give a solution with a concentration of 100 mM. Then mixing and stirring the solution with copper chloride aqueous solution with the same volume and the same concentration for 5min to obtain 50mM copper ion complex Ds-Cu working solution of dansyl chloride, and placing the working solution in a refrigerator for later use.
Example 2
S1: adding 0.1500g of dansyl chloride and 117 mu L of triethylamine into a round-bottom flask containing 10mL of dichloromethane, then adding 0.0065g of chloroethylamine hydrochloride, reacting and stirring at room temperature for 1h under the protection of nitrogen, and removing dichloromethane solvent by using a rotary evaporator to obtain yellow oily matter;
s2: the resulting material was then purified by silica gel column chromatography on petroleum ether: ethyl acetate 4:1, RfSeparating and purifying under the condition of 0.42 to obtain a product Ds-1;
s3: 0.0625g of Ds-1 was weighed and dissolved in 3mL of DMF, 0.0376g of furan-2-ylmethyl-pyridin-2-ylmethyl-amine and 0.0276g of anhydrous potassium carbonate were added, and after stirring at room temperature for 24 hours, 15mL of ice water was added to the reaction mixture to cause a large amount of precipitate to be formed, and the precipitate was filtered to give a solid, and then the obtained material was purified by silica gel column petroleum ether: separation and purification are carried out under the condition of ethyl acetate being 3:1, and a yellow oily product Ds-2 is obtained:
s4: the solid product Ds-2 was dissolved in ethanol solution to give a solution with a concentration of 100 mM. Then mixing and stirring the solution with copper chloride aqueous solution with the same volume and the same concentration for 10min to obtain 50mM copper ion complex Ds-Cu working solution of dansyl chloride, and placing the working solution in a refrigerator for later use.
Example 3
S1: adding 0.2g of dansyl chloride and 160 mu L of triethylamine into a round-bottom flask containing 12mL of dichloromethane, then adding 0.0086g of chloroethylamine hydrochloride, reacting and stirring at room temperature for 1.5h under the protection of nitrogen, and removing dichloromethane solvent by using a rotary evaporator to obtain yellow oily matter;
s2: the resulting material was then purified by silica gel column chromatography on petroleum ether: ethyl acetate 4:1, RfSeparating and purifying under the condition of 0.42 to obtain a product Ds-1;
s3: 0.07g of Ds-1 product was weighed and dissolved in 4mL of DMF, and then 0.04g of furan-2-ylmethyl-pyridin-2-ylmethyl-amine and 0.04g of anhydrous potassium carbonate were added, and after stirring at room temperature for 26 hours, 18mL of ice water was added to the reaction mixture, and a large amount of precipitate was generated, and the precipitate solid was obtained by filtration, and then the obtained substance was purified by silica gel column petroleum ether: separation and purification are carried out under the condition of ethyl acetate 1:1, and a yellow oily product Ds-2 is obtained:
s4: the solid product Ds-2 was dissolved in ethanol solution to give a solution with a concentration of 100 mM. Then mixing and stirring the solution with copper chloride aqueous solution with the same volume and the same concentration for 15min to obtain 50mM copper ion complex Ds-Cu working solution of dansyl chloride, and placing the working solution in a refrigerator for later use.
Example 4 analysis of the sensitivity of dansyl chloride copper metal complex probe to hydrogen sulfide
The fluorescence spectrum of the copper complex probe prepared in example 2 is shown in FIG. 2, and then H at different concentrations of 1. mu.M complex probe solution is recorded2Change in fluorescence spectrum in the presence of S, H2S concentrations ranged from 0-1.0. mu.M, as shown in FIG. 3, with H2The fluorescence intensity of the probe at 538nm is gradually enhanced by increasing the concentration of S, so that the fluorescent probe for detecting the sulfur ions in an 'off-on' mode is formed.
FIG. 4 shows fluorescence intensity and H of the complex probe Ds-Cu2The linear relationship between the S concentrations, and the ordinate of the graph shows the ratio of the fluorescence intensity of the probe before and after addition of the sulfur ion (F/F)0) In which F is0The fluorescence intensity of the probe Ds-Cu without hydrogen sulfide added is represented, and F the fluorescence intensity of the probe Ds-Cu after hydrogen sulfide is added is represented. F/F is evident from the figure0Intensity of ratio with H2The S concentration is increased, and the intensity ratio F/F is increased in the concentration range of 0 to 1 mu M of the sulfur ion concentration0Has a good linear relation with the sulfur ion, and the obtained linear correlation coefficient R20.998, linear equation F/F0＝0.929+14.143[H2S]Based on the linear relationship, H can be realized2Quantitative analysis of S, calculating to obtain H in the detection solution according to the definition of the detection limit2The detection limit of S was 0.014. mu.M.
Example 5 analysis of the selectivity of the dansyl chloride copper metal complex probe for hydrogen sulfide
In order to study and discuss the selectivity of the complex probe system to hydrogen sulfide, common stable gases such as NH are selected3，NO2，N2，SO2，CO2And CO as the selective gas. These gases were injected into the solutions containing the probes, respectively, and changes in fluorescence spectra of the probes were observed, as shown in FIG. 5, with only H2The S gas obviously enhances the fluorescence intensity of the probe, other gases basically do not interfere the probe, and the results fully indicate that the probe can be used for the gas H2The selectivity of S is good.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (1)
1. The application of the metal complex fluorescent probe in detecting hydrogen sulfide in gas is characterized in that the structural formula of the metal complex fluorescent probe is as follows:
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| "Highly sensitive and selective fluorescence detection of copper(II) ion based on multi-ligand metal chelation";Shan Zhang et al.,;《Talanta》;20140405;第126卷;第185-190页 * |
| "一种基于铜配合物的高灵敏硫化氢荧光探针";黄彬等;《无机化学学报》;20131110;第29卷(第11期);第2283-2288页 * |
| Shan Zhang et al.,."Highly sensitive and selective fluorescence detection of copper(II) ion based on multi-ligand metal chelation".《Talanta》.2014,第126卷第185-190页. * |
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