CN111187275B - 4- (5-tetrazole sulfydryl hexyloxy) soil licorice A-type fluorescent probe and preparation method thereof - Google Patents
4- (5-tetrazole sulfydryl hexyloxy) soil licorice A-type fluorescent probe and preparation method thereof Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 title claims abstract description 14
- 235000001453 Glycyrrhiza echinata Nutrition 0.000 title claims abstract description 10
- 235000017382 Glycyrrhiza lepidota Nutrition 0.000 title claims abstract description 10
- 229940010454 licorice Drugs 0.000 title claims abstract description 10
- 239000002689 soil Substances 0.000 title abstract description 6
- 240000004670 Glycyrrhiza echinata Species 0.000 title abstract 2
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 title description 8
- YMRIDJQAEZFTSC-UHFFFAOYSA-N 2,3-dihydro-1h-tetrazole Chemical compound N1NC=NN1 YMRIDJQAEZFTSC-UHFFFAOYSA-N 0.000 title description 2
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- 239000000523 sample Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 235000003205 Smilax rotundifolia Nutrition 0.000 claims description 12
- 240000009022 Smilax rotundifolia Species 0.000 claims description 12
- 238000004809 thin layer chromatography Methods 0.000 claims description 12
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 241000202807 Glycyrrhiza Species 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- -1 phenyl ester Chemical class 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 244000303040 Glycyrrhiza glabra Species 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
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- 235000019441 ethanol Nutrition 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical class S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 15
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000000215 hyperchromic effect Effects 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 150000003536 tetrazoles Chemical class 0.000 abstract description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 3
- 150000004775 coumarins Chemical class 0.000 abstract description 3
- 235000001671 coumarin Nutrition 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 9
- 238000001514 detection method Methods 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 5
- NGGYSPUAKQMTNP-UHFFFAOYSA-N Glabrene Chemical compound C1=C(O)C=C2OCC(C3=C4OC(C=CC4=C(O)C=C3)(C)C)=CC2=C1 NGGYSPUAKQMTNP-UHFFFAOYSA-N 0.000 description 4
- KKLOCFOZPFGVBB-UHFFFAOYSA-N Glabrene Natural products C1=C(O)C=C2OCC(C3=CC=C4OC(C=CC4=C3O)(C)C)=CC2=C1 KKLOCFOZPFGVBB-UHFFFAOYSA-N 0.000 description 4
- 241001351508 Glycyrrhiza acanthocarpa Species 0.000 description 4
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- DVLFYONBTKHTER-UHFFFAOYSA-N 3-(N-morpholino)propanesulfonic acid Chemical compound OS(=O)(=O)CCCN1CCOCC1 DVLFYONBTKHTER-UHFFFAOYSA-N 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- ZGFASEKBKWVCGP-UHFFFAOYSA-N cyclocoumarol Chemical compound C12=CC=CC=C2OC(=O)C2=C1OC(OC)(C)CC2C1=CC=CC=C1 ZGFASEKBKWVCGP-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
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- QOLHWXNSCZGWHK-BWBORTOCSA-N (6r,7r)-1-[(4s,5r)-4-acetyloxy-5-methyl-3-methylidene-6-phenylhexyl]-4,7-dihydroxy-6-(11-phenoxyundecylcarbamoyloxy)-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylic acid Chemical compound C([C@@H](C)[C@H](OC(C)=O)C(=C)CCC12[C@@H]([C@@H](OC(=O)NCCCCCCCCCCCOC=3C=CC=CC=3)C(O1)(C(O)=O)C(O)(C(O2)C(O)=O)C(O)=O)O)C1=CC=CC=C1 QOLHWXNSCZGWHK-BWBORTOCSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- CFNMUZCFSDMZPQ-GHXNOFRVSA-N 7-[(z)-3-methyl-4-(4-methyl-5-oxo-2h-furan-2-yl)but-2-enoxy]chromen-2-one Chemical compound C=1C=C2C=CC(=O)OC2=CC=1OC/C=C(/C)CC1OC(=O)C(C)=C1 CFNMUZCFSDMZPQ-GHXNOFRVSA-N 0.000 description 1
- 229940126559 Compound 4e Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PHHAXWBLJNBVNS-UHFFFAOYSA-N Isoglycycoumarin Natural products C=1C=2C(OC)=C3CCC(C)(C)OC3=CC=2OC(=O)C=1C1=CC=C(O)C=C1O PHHAXWBLJNBVNS-UHFFFAOYSA-N 0.000 description 1
- 239000007993 MOPS buffer Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 208000037887 cell injury Diseases 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- LTINPJMVDKPJJI-UHFFFAOYSA-N iodinated glycerol Chemical compound CC(I)C1OCC(CO)O1 LTINPJMVDKPJJI-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- XGPBRZDOJDLKOT-UHFFFAOYSA-N praeruptorin A Natural products C1=CC(=O)OC2=C1C=CC1=C2C(OC(C)=O)C(OC(=O)C(C)=CC)C(C)(C)O1 XGPBRZDOJDLKOT-UHFFFAOYSA-N 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
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Abstract
The invention discloses six 4- (5-tetrazole mercapto-hexyloxy) soil licorice A-type fluorescent probes and a preparation method and application thereof, and the structural formula of the probes is shown in the specification
The 4- (5-tetrazole mercaptohexyloxy) glabrous A-type fluorescent probe combines the fluorescent characteristics of coumarins and tetrazole derivatives and is applied to DMSO/H2The O solution has high selectivity and sensitivity to lead ions, has obvious hyperchromic effect compared with other ions, has a change in the maximum absorption peak, and can be used as a lead ion fluorescent probe.
Description
Technical Field
The invention relates to the technical field of fluorescent probes, in particular to six 4- (5-tetrazole mercaptohexyloxy) glabrous-earth A-type fluorescent probes with different substituents, and a preparation method and application thereof.
Background
With the increasingly serious environmental pollution caused by the development of industry and agriculture, the objects for environmental analysis and monitoring become more and more complex, so that the requirements on the sensitivity, the detection limit and the accuracy of the environmental analysis technology are higher and higher. At present, analysis and test methods of volatile substances related to air pollution, surfactants related to water pollution, metals such as copper, mercury, tin and the like and pH are important research objects of environmental analysis. Lead is a common environmental pollutant. The main source of the method is waste water discharge of automobile exhaust, storage batteries, smelting, hardware, electroplating and other industries. Lead has long biological half-life period, is easy to accumulate in human body, and has great damage to the blood system, the digestive system, the reproductive system and the urinary system of the human body. High concentrations of lead can also cause spinal cord motor cell damage in children, leading to reduced motor function. Therefore, establishing a trace lead ion analysis technology is very important for environmental protection. The fluorescence analysis method has the advantages of simple and convenient operation, low cost, good selectivity, rapid response, in-situ real-time and the like, is a simple and practical analysis technology, and plays an increasingly important role in the aspect of cation detection in environment and life systems.
The coumarin derivative has excellent fluorescent characteristics, has the advantages of large Stokes shift, high fluorescence quantum yield, good light stability and the like, and a small molecular fluorescent probe taking coumarin as a fluorophore gradually becomes a new research hotspot in recent years, thereby showing good application prospects in the fields of ion detection, biomolecular probes and the like. Tetrazole, as a carboxyl-based electron mediator such as a living organism, has low toxicity and biocompatibility, and is widely used in the fields of chemistry, biology and the like.
Therefore, it is necessary to design a fluorescent probe for trace lead ion concentration detection to achieve the purpose of trace lead ion detection.
Disclosure of Invention
It is an object of the present invention to address at least the above-mentioned deficiencies and to provide at least the advantages which will be described hereinafter.
Another purpose of the invention is to provide a 4- (5-tetrazole mercaptohexyloxy) glabrous A type fluorescent probe which has simple structure, easy synthesis and good fluorescence performance.
The invention also aims to provide a preparation method of the 4- (5-tetrazole mercaptohexyloxy) glabrous A-type fluorescent probe.
The invention also aims to provide the application of the 4- (5-tetrazole mercaptohexyloxy) glabrous-earth A-type fluorescent probe as the lead ion detection.
To achieve these objects and other advantages and in accordance with the purpose of the invention, as embodied and broadly described herein, there is provided a fluorescent probe of 4- (5-tetrazole mercaptohexyloxy) native licorice type a, wherein the structural formula is as follows:
wherein R is1Is composed of
Correspondingly, the chemical names are respectively:
4- [6 '- (1-methyl-5' -tetrazolylthio) hexyloxy ] terra-glycyrrhiza a derivative;
4- [ 6' - (1-phenyl-5-tetrazolylthio) hexyloxy ] glabrene A derivative;
4- [6 '- (1-p-methoxyphenyl-5' -tetrazolylthio) hexyloxy ] glabrene A derivative;
4- [6 '- (1-p-ethylphenyl-5' -tetrazolylthio) hexyloxy ] glabrene A derivative;
4- [6 '- (1-p-chlorophenyl-5' -tetrazolylthio) hexyloxy ] terra-glycyrrhiza a derivative;
4- [6 '- (1-m-nitrophenyl-5' -tetrazolylthio) hexyloxy ] glabrene A derivative.
The compound takes pyranocoumarin earth glycyrrhiza A as a fluorescent group, combines the fluorescent characteristics of coumarin derivatives, and is applied to DMSO/H2The O solution has high selectivity and sensitivity to lead ions, has obvious hyperchromic effect on the lead ions compared with other ions, has a change in the maximum absorption peak, and can be used as a lead ion fluorescent probe.
A preparation method of a 4- (5-tetrazole mercaptohexyloxy) glabrous greenbrier A type fluorescent probe comprises the following steps:
step one, taking the glabrous greenbrier rhizome A, 1, 6-dibromopropane and potassium carbonate as catalysts, carrying out reflux reaction in a solvent, filtering while the reaction is hot after the reaction is finished, and recrystallizing residues obtained by reduced pressure distillation to obtain an intermediate product 4- (6-bromopropoxy) glabrous greenbrier rhizome A;
and step two, under the condition that a reaction solvent and a catalyst exist, respectively carrying out reflux reaction on the intermediate product 4- (6-bromopropoxy) earth licorice A and mercaptotetrazole derivatives with different substituents, spin-drying the filtrate, and separating by column chromatography silica gel and thin layer chromatography silica gel to respectively obtain corresponding target products.
The specific synthetic route is as follows:
the method has the advantages of easily obtained raw materials, simple synthesis and convenient mass production.
Preferably, in the method for preparing the 4- (5-tetrazole mercaptohexyloxy) glabrous greenbrier rhizome A type fluorescent probe, the method for preparing the mercaptotetrazole derivatives with different substituents comprises the following steps:
dissolving the phenyl isothiocyanate derivative in pure water, adding sodium azide, refluxing, tracking the reaction by using Thin Layer Chromatography (TLC), and reacting the mixture by using a solvent with a volume ratio of 2: 1 or 4: 1, taking petroleum ether and ethyl acetate as developing agents, stopping reaction when a phenyl ester layer disappears, cooling to room temperature, dropwise adding concentrated hydrochloric acid, stirring until the pH is 3, separating out a large amount of white precipitate, performing suction filtration, taking a filter cake, adding pure water to the pH of 4-5, performing suction filtration, and recrystallizing the filter cake with absolute ethyl alcohol to obtain a corresponding mercaptotetrazole derivative;
the synthetic route is as follows:
wherein R1 is-CH2，C6H5-，-OCH3，-C2H5，-Cl，-NO2One kind of (1).
Preferably, in the method for preparing the 4- (5-tetrazole mercaptohexyloxy) glabrous A-type fluorescent probe, the solvent in the first step is acetonitrile, and 95% ethanol is used for recrystallization.
Preferably, in the preparation method of the 4- (5-tetrazole mercaptohexyloxy) glabrous-earth licorice A-type fluorescent probe, in the second step, tetrahydrofuran is used as a reaction solvent, and triethylamine is used as a catalyst.
An application of 4- (5-tetrazole mercaptohexyloxy) glabrous greenbrier rhizome A type fluorescent probe for detecting lead ions. The compound selectively combines metal lead ions in solvents such as water, DMSO, buffer solution and the like, and the ultraviolet-visible light of the compound has a large hyperchromic effect or the maximum absorption peak of the compound changes.
Tetrazole, as a carboxyl-based electron mediator such as a living organism, has low toxicity and biocompatibility, and is widely used in the fields of chemistry, biology and the like.
The invention at least comprises the following beneficial effects:
the 4- (5-tetrazole mercaptohexyloxy) soil licorice A-type fluorescent probe disclosed by the invention combines the advantages of excellent fluorescent property, large Stokes shift, high fluorescence quantum yield, good light stability and the like of coumarin derivatives and the advantages of lower toxicity and biocompatibility of tetrazole, and can achieve the purpose of trace detection of lead ions.
The preparation method has the advantages of easily obtained raw materials, simple synthesis and convenient mass production.
The 4- (5-tetrazole mercapto-hexyloxy) soil licorice A-type fluorescent probe disclosed by the invention is relatively simple in structure and easy to synthesize, shows high selectivity and sensitivity to lead ions in a DMSO/H2O solution, has an obvious hyperchromic effect compared with other ions on the lead ions, has a change in the maximum absorption peak, and can be used as a lead ion fluorescent probe.
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.
Drawings
FIG. 1 shows the selectivity of 4- (5-tetrazole mercaptohexyloxy) Glycyrrhiza glabra A type fluorescent probes 4a-4f to lead ions.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1
The preparation method of the 4- (5-tetrazole mercaptohexyloxy) glabrous-earth A-type fluorescent probe 4 comprises the following steps:
preparation of intermediate 4- (6-bromopropoxy) native licorice A (2)
A100 mL three-necked round-bottomed flask was charged with 2.5060g (6.58mmol) of Glycyrrhiza glabra and 100.0mL of acetonitrile solvent, dissolved at a certain temperature, added with 10.0mL (65.80mmol) of 1, 6-dibromohexane, added with 1.8197g (13.16mmol) of anhydrous potassium carbonate, refluxed at 80 ℃ for 4 hours, followed by Thin Layer Chromatography (TLC), filtered while hot after the reaction was completed, and the residue obtained by distillation under reduced pressure was recrystallized from 95% ethanol to obtain 22.003 g of an intermediate, which was found to be 56.06% in yield.
Preparation of bis, mercaptotetrazole derivatives (3a-3f)
Dissolving 3.0mmol of phenyl isothiocyanate derivatives in pure water, adding 4.5mmol of sodium azide, refluxing for 2.5-9h, tracking the reaction by Thin Layer Chromatography (TLC), and reacting by using a volume ratio of 2: 1 or 4: 1, taking petroleum ether and ethyl acetate as developing agents, stopping reaction when a phenyl ester layer disappears, dropwise adding concentrated hydrochloric acid when the reaction solution is cooled to room temperature, stirring until the pH value is 3, separating out a large amount of white precipitate, performing suction filtration, taking a filter cake, adding pure water to the pH value of 4-5, performing suction filtration, and recrystallizing the filter cake with absolute ethyl alcohol to obtain the corresponding mercaptotetrazole derivative.
The synthesis was as follows:
wherein R1 are each-CH2，-C6H5，-OCH3，-C2H5，-Cl，-NO2(ii) a The corresponding mercaptotetrazole derivatives are labeled 3a, 3b, 3c, 3d, 3e, 3f, respectively.
Preparation of tris, 4- (5-tetrazole mercaptohexyloxy) glabrous greenbrier A type fluorescent probe (4a-4f)
Adding 0.1360g (0.25mmol) of 4- (6-bromohexyloxy) native licorice A and 5.0mL of tetrahydrofuran into a 50mL three-neck round-bottom flask, heating in an oil bath, dissolving at a certain temperature, adding 0.375mmol of corresponding mercaptotetrazole derivative (3a-3f) and 0.052mL (0.375mmol) of triethylamine, reacting at 62 ℃, tracking the reaction by thin-layer chromatography (TLC), after the reaction is finished, spin-drying the filtrate, and separating by column chromatography silica gel and thin-layer chromatography silica gel to obtain the target product 4- (5-tetrazolylmercaptohexyloxy) native licorice A type fluorescent probe (4a-4 f).
The physical property characterization of the target product 4- (5-tetrazole sulfydryl hexyl oxy) soil licorice A type fluorescent probe (4a-4f) is shown in the following table 1: wherein (4a-4f) of the compound corresponds to the structural formula:
TABLE 1 spectral physical Property data of Compounds (4a-4f)
Example 2
S1, the 4- (5-tetrazole mercaptohexyloxy) Glycyrrhiza glabra type A fluorescent probe 4a-4f prepared in example 1 was accurately weighed, and the 4a-4f was dissolved in DMSO and a 3-morpholinopropanesulfonic acid buffer solution (MOPS,10mM, pH 7.0) (8:2, v/v) to prepare 100mL of a probe stock solution (0.6667X 10)-4mol/L)；
S2, deionized water is used as solvent to prepare 0.01mol/L Cu2+、Fe3+、Zn2+、Na+、Cd2+、Ca2+、Mg2+、Mn2+、Pb2+、Ni2+、Co2+、Ag+And (3) placing the perchlorate metal cation stock solutions in 10mL volumetric flasks respectively.
S3, taking a plurality of sample bottles, and operating as follows:
control group: adding (2mL +20uL) of the probe stock solution into one of the sample bottles;
experimental groups: adding 2mL of the probe stock solution and 20uL of the metal cation stock solution into each of the rest sample bottles, mixing uniformly,
after the control group and the experimental group are stabilized for 10min, the samples are respectively transferred to a cuvette, and the ultraviolet-visible light spectrum is sequentially measured, which is shown in figure 1.
As can be seen from FIG. 1, six kinds of fluorescent probes are directed to Pb2+Having a selective recognition effect, each compound and Pb2+After combination, the compound has obvious hyperchromic effect, the absorbance of other ions is not greatly changed, particularly the compound 4e has obvious increase of absorbance, and the characteristic absorption peaks of the compound appear in 352, 268, 259 and 235cm-1Adding Pb2+Rear maximum absorption Peak 259cm-1The absorbance increased from 0.5583 to 0.8906.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the uses set forth in the specification and examples. It can be applied to all kinds of fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art.
Claims (6)
1. 4- (5-tetrazole mercaptohexyloxy) glycyrrhiza glabra type A fluorescent probe with different substituents is disclosed, wherein the structural formula is as follows:
wherein R1 is
2. The method for preparing 4- (5-tetrazole mercaptohexyloxy) glabrous greenbrier A type fluorescent probe according to claim 1, comprising:
taking the glabrous greenbrier rhizome A and the 1, 6-dibromopropane as raw materials and potassium carbonate as a catalyst, carrying out reflux reaction in a solvent, filtering while the reaction is hot after the reaction is finished, and recrystallizing residues obtained by reduced pressure distillation to obtain an intermediate product 4- (6-bromopropoxy) glabrous greenbrier rhizome A;
step two, respectively carrying out reflux reaction on the intermediate product 4- (6-bromopropoxy) earth licorice A and mercaptotetrazole derivatives with different substituents under the condition of existence of a reaction solvent and a catalyst, spin-drying the filtrate, and separating by column chromatography silica gel and thin layer chromatography silica gel to respectively obtain corresponding 4- (5-tetrazole mercaptohexyloxy) earth licorice A type fluorescent probes;
the mercaptotetrazole derivatives with different substituents are as follows:
wherein R1 is-CH3Or
3. The method for preparing 4- (5-tetrazole mercaptohexyloxy) glabrous greenbrier A type fluorescent probe of claim 2, wherein when R1 of mercaptotetrazole derivatives of different substituents is:
the preparation method comprises the following steps:
dissolving a phenyl isothiocyanate derivative in pure water, adding sodium azide, carrying out reflux reaction, tracking the reaction by using a thin layer chromatography, and reacting the mixture by using a reaction solution prepared from the following components in a volume ratio of 2: 1 and 4: 1, taking petroleum ether and ethyl acetate as developing agents, stopping reaction when a phenyl ester layer disappears, cooling to room temperature, dropwise adding concentrated hydrochloric acid, stirring until the pH is 3, separating out a large amount of white precipitate, performing suction filtration, taking a filter cake, adding pure water to the pH of 4-5, performing suction filtration, and recrystallizing the filter cake with absolute ethyl alcohol to obtain a corresponding mercaptotetrazole derivative;
the synthetic route is as follows:
wherein, R2 is-OCH3，-C2H5，-Cl，-NO2One kind of (1).
4. The method for preparing 4- (5-tetrazole mercaptohexyloxy) glabrous greenbrier A type fluorescent probe according to claim 3, wherein the solvent in the first step is acetonitrile, and 95% ethanol is used for recrystallization.
5. The method for preparing 4- (5-tetrazole mercaptohexyloxy) glabrous greenbrier A type fluorescent probe according to claim 4, wherein in the second step, tetrahydrofuran is used as a reaction solvent, and triethylamine is used as a catalyst.
6. The application of the 4- (5-tetrazole mercaptohexyloxy) glabrous-earth A-type fluorescent probe as defined in claim 1 or obtained by the preparation method of any one of claims 2 to 5 in preparation of a probe for detecting lead ions.
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| CN109438462A (en) * | 2018-10-08 | 2019-03-08 | 广西中医药大学 | O- p-nitrophenyl formoxyl soil Radix Glycyrrhizae A with anti-tumor activity and its preparation method and application |
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