CN115073338A - High-selectivity mercury ion recognition fluorescent probe, preparation method and application - Google Patents
High-selectivity mercury ion recognition fluorescent probe, preparation method and application Download PDFInfo
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- CN115073338A CN115073338A CN202210826218.7A CN202210826218A CN115073338A CN 115073338 A CN115073338 A CN 115073338A CN 202210826218 A CN202210826218 A CN 202210826218A CN 115073338 A CN115073338 A CN 115073338A
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 7
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title description 17
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 52
- -1 mercury ions Chemical class 0.000 claims abstract description 51
- 239000000523 sample Substances 0.000 claims abstract description 50
- 238000012216 screening Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000007853 buffer solution Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 39
- 238000001514 detection method Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000010206 sensitivity analysis Methods 0.000 abstract 1
- 230000008859 change Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- NOYXYBQRVOLZFQ-UHFFFAOYSA-N 2-benzylidene-5-hydroxy-3H-inden-1-one Chemical compound C1C2=C(C=CC(=C2)O)C(=O)C1=CC3=CC=CC=C3 NOYXYBQRVOLZFQ-UHFFFAOYSA-N 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 239000007995 HEPES buffer Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- YYPUSXWRDIQUQE-UHFFFAOYSA-N phenoxymethanethioic s-acid Chemical compound OC(=S)OC1=CC=CC=C1 YYPUSXWRDIQUQE-UHFFFAOYSA-N 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- DBLXOVFQHHSKRC-UHFFFAOYSA-N ethanesulfonic acid;2-piperazin-1-ylethanol Chemical compound CCS(O)(=O)=O.OCCN1CCNCC1 DBLXOVFQHHSKRC-UHFFFAOYSA-N 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZRKQOVXGDIZYDS-UHFFFAOYSA-N 5-hydroxy-2,3-dihydroinden-1-one Chemical compound OC1=CC=C2C(=O)CCC2=C1 ZRKQOVXGDIZYDS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 229910001987 mercury nitrate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 1
- VJZNUICECYWOFV-UHFFFAOYSA-N o-phenyl carbamothioate Chemical compound NC(=S)OC1=CC=CC=C1 VJZNUICECYWOFV-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/02—Monothiocarbonic acids; Derivatives thereof
- C07C329/04—Esters of monothiocarbonic acids
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
- G01N21/62—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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
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Abstract
The invention relates to a fluorescent probe for identifying mercury ions with high selectivity. Specifically, the probe provided by the invention can be used for measuring, detecting or screening mercury ions, can realize rapid and high-sensitivity analysis on the mercury ions, can realize detection on the mercury ions of a real water sample, and has the advantages of simplicity in synthesis, stable property and benefit for commercial application.
Description
Technical Field
The invention belongs to the field of fluorescent probes, and particularly relates to an indanone compound fluorescent probe and application thereof in measuring, screening or detecting mercury ions; the invention also provides a method for preparing the fluorescent probe.
Background
Mercury is a heavy metal element, commonly called mercury, and poisoning can be caused when people inhale mercury vapor, eat marine products polluted by mercury or inhale mercury compounds. The main sources of mercury pollution include industrial waste water from solid waste combustion, instrument factories, precious metal smelting and the like, and since more and more mercury is released into the environment, serious influences are caused to both human bodies and the environment, and thus more and more attention is paid. Even if mercury with very low concentration enters a human body, the mercury can cause serious harm to the brain, the liver, the nervous system and the like, and at present, the environmental protection standard of China is increasingly improved, and the requirement on the sensitivity of mercury ions is increasingly high. Therefore, a method for identifying mercury ions with high selectivity is urgently needed, and especially, the method has important significance for in-situ and ultrasensitive monitoring of mercury ions in the environment and protecting the ecological environment.
Currently, common methods for detecting mercury ions mainly include spectrophotometry, spectroscopy, electrochemistry, fluorescent probe analysis, and the like. Among the methods for detecting mercury ions, fluorescent probe analysis has been the focus of attention of many researchers because of its advantages such as simple operation, high selectivity and high sensitivity. Many fluorescent probes for detecting mercury ions have been reported, but most of the fluorescent probes still have some defects, such as complex synthesis, low sensitivity, poor selectivity, poor water solubility, and the like. Therefore, the development of mercury ion fluorescent probes with simple synthesis, good water solubility, and high sensitivity and selectivity is a problem to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide a high-sensitivity high-selectivity mercury ion fluorescent probe, and a preparation method and use thereof, which have the characteristics of good water solubility, high sensitivity, high selectivity and simple synthesis, and are particularly suitable for effectively measuring, screening or detecting mercury ions in a water environment.
Specifically, the invention provides a compound having a structure represented by formula (I):
in the formula (I), R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 ，R 12 ，R 13 ，R 14 And R 15 Is hydrogen atom, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, sulfonic group, ester group or carboxyl; r is 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 ，R 12 ，R 13 ，R 14 And R 15 May be the same or different.
In some embodiments of the invention, the compound of the invention is R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 ，R 12 ，R 13 ，R 14 And R 15 A compound of formula (ii) all hydrogen atoms, having the formula:
the invention also provides a process for the preparation of a compound of formula (I) comprising the steps of: reacting a compound of formula (III) with a compound of formula (IV) to produce a compound of formula (I), wherein the reaction formula is as follows:
in formulae (I), (III) and (IV): r 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 ，R 12 ，R 13 ，R 14 And R 15 Is hydrogen atom, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, sulfonic group, ester group, carboxyl; r 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 ，R 12 ，R 13 ，R 14 And R 15 May be the same or different.
In some specific embodiments of the invention, a compound of formula (iii) and a compound of formula (iv) in a certain molar ratio are dissolved in dichloromethane, stirred at room temperature for reaction, after the reaction is completed, the organic solvent is evaporated by rotation to obtain a crude product, and the crude product is separated and purified by column chromatography to obtain a pure compound of formula (I).
In some embodiments of the invention, the molar ratio of the compound of formula (III) to the compound of formula (IV) is from 1:1 to 1: 3.
In some embodiments of the invention, the reaction time at normal temperature is 1 to 6 hours.
In some embodiments of the invention, the reaction temperature is ambient temperature.
In some specific embodiments of the invention, 5-hydroxy-1-indanone and benzaldehyde with a molar ratio of 1:1 are dissolved in ethanol, the mixture is refluxed and stirred for 72 hours at 80 ℃ under the catalytic action of piperazine, after the reaction is finished, the organic solvent is evaporated by rotation to obtain a crude product, and the crude product is separated and purified by column chromatography to obtain a pure compound of formula (II I).
The invention also provides a fluorescent probe composition for measuring, screening or detecting mercury ions, which comprises the compound of formula (I) of the invention.
In some embodiments of the invention, the compound of formula (I) has the following structure:
in some embodiments of the invention, the fluorescent probe composition further comprises a solvent, an acid, a base, a buffer solution, or a combination thereof.
The invention also provides application of the compound shown in the formula (I) in preparing a reagent for measuring, screening or detecting mercury ions.
The invention also provides a method of detecting the presence of or determining the level of mercury ions in a sample, comprising:
a) contacting a compound of formula (I) or formula (ii) with a sample to form a fluorescent compound;
b) determining the fluorescent properties of the fluorescent compound.
In some embodiments of the invention, the sample is a chemical sample.
In some embodiments of the invention, the sample is an aquatic environment sample.
In some embodiments of the invention, the aquatic environment sample is a groundwater, river or lake aquatic environment sample.
The invention also provides a kit for detecting the existence of mercury ions in a sample or determining the content of mercury ions in the sample, which comprises the compound shown in the formula (I) or the formula (II).
Compared with the prior art, the invention has the following remarkable advantages and effects:
(1) good water solubility
The mercury ion fluorescent probe has good water solubility, can detect or measure mercury ions in a pure water system, and is very suitable for detecting or measuring mercury ions in water environments, particularly underground water, rivers or lake water samples.
(2) High sensitivity
The mercury ion fluorescent probe provided by the invention reacts very sensitively with mercury ions, so that the mercury ion fluorescent probe is favorable for detection of mercury ions, and is particularly suitable for detection or measurement of mercury ions in a water environment with the concentration of 0-2.5 mu M.
(3) High selectivity
The mercury ion fluorescent probe can selectively and specifically react with mercury ions to generate a product with fluorescence change, and compared with other substances commonly found in a common water environment, the mercury ion fluorescent probe provided by the invention comprises but not limited to chromium ions, copper ions, ferrous ions, calcium ions, potassium ions, magnesium ions, sodium ions, nickel ions, lead ions, tin ions, zinc ions, nitrate ions, sulfate ions and chloride ions, and shows higher selectivity for the mercury ions.
(4) Good stability
The mercury ion fluorescent probe has good stability and can be stored and used for a long time.
(5) Simple synthesis
The mercury ion fluorescent probe is simple to synthesize and beneficial to commercial popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows the fluorescence spectrum change before and after the probe (5. mu.M) is added to mercury ions (20. mu.M);
FIG. 2 shows the change of absorption spectrum before and after the probe (20. mu.M) is added to mercury ions (20. mu.M);
FIG. 3 is a fluorescence spectrum of a probe (5. mu.M) after addition of mercury ions (0 to 4. mu.M);
FIG. 4 is a graph showing the operation of probe (5. mu.M) for quantitative analysis of various concentrations of mercury ions (0-2.5. mu.M).
FIG. 5 is a test of the ability of a probe (5. mu.M) to selectively recognize mercury ions. Wherein the numbers 1-16 are respectively: 1. blank; 2. chromium ion Cr 2+ (ii) a 3. Copper ion Cu 2+ (ii) a 4. Ferrous ion Fe 2+ (ii) a 5. Calcium ion Ca 2+ (ii) a 6. Potassium ion K + (ii) a 7. Magnesium ion Mg 2+ (ii) a 8. Sodium ion Na + (ii) a 9. Ni ion Ni 2+ (ii) a 10. Lead ion Pb 2+ (ii) a 11. Sn ion Sn 2+ (ii) a 12. Zinc ion Zn 2+ (ii) a 13. Nitrate ion NO 3 - (ii) a 14. Sulfate ion SO 4 2- (ii) a 15. Chloride ion Cl - (ii) a 16. Hg ion Hg 2+ (5. mu.M) (50. mu.M for all other analytes, except where indicated). The bar graph represents the fluorescence intensity values of the probes at 505nm in the presence of the different analytes;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and should not be used to limit the scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention. Example 1: synthesis of Compounds of formula (II)
The synthetic design route is as follows:
embodiment 1: 236mg (1mmol) of 2-benzylidene-5-hydroxy-1-indanone is dissolved in 15mL of dichloromethane, 173mg (1mmol) of phenyl thiocarbamate is added, then DIPEA129mg (1mmol) is added, stirring is carried out for 2h at normal temperature, then rotary evaporation is carried out by a rotary evaporator to obtain a crude product, and chromatographic column separation is carried out to obtain a pure product 275mg of pure product, wherein the yield is 73.9%.
Embodiment 2: 236mg (1mmol) of 2-benzylidene-5-hydroxy-1-indanone is dissolved in 15mL of dichloromethane, 260mg (1.5mmol) of phenyl thiocarbonate is added, then DIPEA194mg (1.5mmol) is added, stirring is carried out at normal temperature for 2h, and rotary evaporation is carried out by a rotary evaporator to obtain a crude product. If purer product is desired, the product is purified by column chromatography to obtain 290mg of pure product with 78% yield.
Embodiment 3: 236mg (1mmol) of 2-benzylidene-5-hydroxy-1-indanone is dissolved in 15mL of dichloromethane, 346mg (2mmol) of phenyl thiocarbonate is added, then DIPEA258mg (2mmol) is added, stirring is carried out at normal temperature for 4h, and rotary evaporation is carried out by a rotary evaporator to obtain a crude product. If a purer product is to be obtained, the pure product is obtained by chromatographic column separation, and 310mg of the pure product is obtained, wherein the yield is 83.3%.
Embodiment 4: 236mg (1mmol) of 2-benzylidene-5-hydroxy-1-indanone is dissolved in 15mL of dichloromethane, 519mg (3mmol) of phenyl thiocarbonate is added, DIPEA387mg (3mmol) is added, stirring is carried out at normal temperature for 4 hours, rotary evaporation is carried out by a rotary evaporator to obtain a crude product, and chromatographic column separation is carried out to obtain a pure product 330mg, wherein the yield is 88.7%.
Embodiment 5: 236mg (1mmol) of 2-benzylidene-5-hydroxy-1-indanone is dissolved in 15mL of dichloromethane, 519mg (3mmol) of phenyl thiocarbonate is added, DIPEA387mg (3mmol) is added, stirring is carried out at normal temperature for 6 hours, and rotary evaporation is carried out by a rotary evaporator to obtain a crude product. If purer product is desired, the product is purified by column chromatography to obtain 335mg of pure product with a yield of 90.1%.
Example 2: the detection method aims at the change of the fluorescence spectrum before and after the mercury ion identification
5mL of distilled water was added to a colorimetric tube, 0.5mL of 4-hydroxyethylpiperazineethanesulfonic acid (HEPES, 100mM) was added, the volume was made to 10mL with distilled water, 50. mu.L of a stock solution of a probe (1mM) was taken out and put into the colorimetric tube, and then a stock solution of mercury ions was added so that the concentration of mercury ions was 20. mu.M, and after shaking uniformly, it was left to stand for 50 minutes, and the change in the fluorescence spectrum was measured by a fluorescence spectrometer, the above measurement was performed in a pure water system, the probe used was the probe prepared in example 1, and all the spectrum measurements were measured at 25 ℃. The results are shown in FIG. 1.
As is clear from FIG. 1, when mercury ions were added, the change in fluorescence intensity at 505nm was very significant.
Example 3: the detection method aims at the change of absorption spectrum before and after the mercury ion identification
5mL of distilled water was added to a colorimetric tube, 0.5mL of 4-hydroxyethylpiperazine ethanesulfonic acid (HEPES, 100mM) was added thereto, the volume was made to 10mL with distilled water, 200. mu.L of a stock solution of the probe (1mM) was removed and placed in the colorimetric tube, and then a stock solution of mercury ions was added so that the concentration of mercury ions was 20. mu.M, and after shaking uniformly, the tube was left to stand for 50 minutes, and the change in absorption spectrum was measured with an ultraviolet absorption spectrometer, the measurement being performed in a pure water system, the probe used was the probe prepared in example 1, and all the spectral measurements were performed at 25 ℃. The results are shown in FIG. 2.
As can be seen from FIG. 2, the absorption intensity at 325nm is significantly reduced.
Example 4: testing the concentration gradient of fluorescent probes for mercury ions
5mL of distilled water was added to a colorimetric tube, 0.5mL of 4-hydroxyethylpiperazine ethanesulfonic acid (HEPES, 100mM) was added, then distilled water was added to make a constant volume of 10mL, and finally 50. mu.L of a probe stock solution (1mM) was transferred and put into the colorimetric tube, and then mercury ion stock solutions of different concentrations (concentration: 0.05. mu.M, 0.1. mu.M, 0.2. mu.M, 0.3. mu.M, 0.5. mu.M, 0.7. mu.M, 1. mu.M, 1.5. mu.M, 2. mu.M, 2.5. mu.M, 3. mu.M, 3.5. mu.M, 4. mu.M, respectively) were added according to the preparation to be prepared, and after shaking uniformly, the mixture was left to stand for 50 minutes, and then the change in fluorescence intensity was measured by a fluorescence spectrometer. The above measurements were carried out in a pure water system, the probe used was the probe prepared in example 1, and all the spectroscopic measurements were carried out at 25 ℃. The results are shown in FIG. 3.
As is clear from FIG. 3, the fluorescence intensity at 505nm gradually increased with the increase in the concentration of added mercury ions; and, as can be seen from fig. 4, at 505nm, the fluorescence intensity of the mercury ion fluorescent probe (5 μ M) after adding mercury ions (0-2.5 μ M) shows a good linear relationship, which proves that the mercury ions can be quantitatively analyzed by the fluorescent probe.
Example 5: testing the selectivity of fluorescent probes for mercury ions
The analytes were: 1. blank; 2. chromium ion Cr 2+ (ii) a 3. Copper ion Cu 2+ (ii) a 4. Ferrous iron ion Fe 2+ (ii) a 5. Calcium ion Ca 2+ (ii) a 6. Potassium ion K + (ii) a 7. Magnesium ion Mg 2+ (ii) a 8. Sodium ion Na + (ii) a 9. Ni ion Ni 2+ (ii) a 10. Lead ion Pb 2+ (ii) a 11. Sn ion Sn 2 + (ii) a 12. Zinc ion Zn 2+ (ii) a 13. Nitrate ion NO 3 - (ii) a 14. Sulfate ion SO 4 2- (ii) a 15. Chloride ion Cl-; 16. hg ion Hg 2+ (5. mu.M) (50. mu.M for all other analytes, except where indicated). The bar graph represents the fluorescence intensity values of the probes at 505nm in the presence of different analytes. The above measurements were carried out in a pure water system, the probe used was the probe prepared in example 1, and all the spectroscopic measurements were carried out at 25 ℃. Specifically, 5mL of distilled water was added to a colorimetric tube, 0.5mL of 4-hydroxyethylpiperazineethanesulfonic acid (HEPES, 100mM) was added, the volume was adjusted to 10mL with distilled water, and finally 50 μ L of a stock solution of the probe (1mM) was transferred to the colorimetric tube, and a predetermined amount of the above-mentioned analyte was added thereto, shaken well, and allowed to stand for 50 minutes, and then the fluorescence intensity value was measured. The results are shown in FIG. 5.
As can be seen from FIG. 5, the probe of the present invention has high selectivity for mercury ions, can specifically react with mercury ions, and the fluorescence spectrum changes significantly before and after the reaction, while the fluorescence intensity does not change significantly after the reaction between other common analytes in the water environment and the probe
Example 6: detection limit test and calculation of probes
The detection limit was calculated by fluorescence titration. The detection limit calculation formula is as follows:
detection limit of 3 sigma/k
σ is the standard deviation of the fluorescence intensity of the blank probe, and k is the slope of the linear plot of FIG. 4.
From this, the detection limit of the probe of formula (II) for mercury ions was calculated to be 16 nM.
Example 7: probe Hg in three real water samples 2+ Analysis of (2)
Three real water samples are respectively collected, a water sample A is collected from the water of the first lake of the university of Jinan, a water sample B is collected from the underground water of the Jinyunchuan river of Jinan, a water sample C is collected from the river water of the Jinyangchuan river of Jinan, the water samples are all detected, no mercury ion is found, then, two groups of test systems are configured for each water sample, a probe of 5 mu M is added into each group of test systems, the used probe is the probe prepared in the embodiment 1, then, mercury nitrate of 1 mu M and 2 mu M is respectively added into each group of test systems of each water sample, the samples are uniformly shaken and are kept stand for 50 minutes, and then the fluorescence intensity change of each group of test systems is tested, so that the mercury ion content of each group of test systems is calculated.
The above procedure was repeated three times.
The test results are shown in the following table, and the test results show that the recovery rates of the three water samples are 84.07-109.20%, so that the fluorescent probe can be further proved to be capable of effectively detecting Hg in real water samples 2+ 。
Although the present invention has been described in the above-mentioned embodiments, it is to be understood that the present invention may be further modified and changed without departing from the spirit of the present invention, and that such modifications and changes are within the scope of the present invention.
Claims (10)
1. A compound having the structure:
wherein R is 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 ，R 12 ，R 13 ，R 14 And R 15 Is hydrogen atom, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, sulfonic group, ester group, carboxyl; r 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 ，R 12 ，R 13 ，R 14 And R 15 May be the same or different.
2. The compound of claim 1, wherein R is 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 ，R 12 ，R 13 ，R 14 And R 15 Are all hydrogen atoms.
3. A process for the preparation of a compound according to claim 1 or 2, comprising the steps of: reacting a compound of formula (III) with a compound of formula (IV) to produce a compound of formula (I), wherein the reaction formula is as follows:
4. the method of claim 3, comprising the steps of: dissolving a compound shown in a formula (III) and a compound shown in a formula (IV) in a certain molar ratio in dichloromethane, stirring at normal temperature for reaction, after the reaction is finished, evaporating an organic solvent to obtain a crude product by rotary evaporation, and performing column chromatography separation and purification to obtain a pure product.
5. The method according to claim 4, wherein the compound of formula (III) and the compound of formula (IV) are reacted at room temperature for 1 to 6 hours at a molar ratio of 1:1 to 1: 3.
6. A fluorescent probe composition for measuring, screening or detecting mercury ions comprising the compound of claim 1.
7. The fluorescent probe composition of claim 6, wherein the fluorescent probe composition further comprises a solvent, an acid, a base, a buffer solution, or a combination thereof.
8. Use of a compound according to claim 1 for the preparation of a reagent for measuring, screening or detecting mercury ions.
9. A method for detecting the presence of or determining the level of mercury ions in a sample, comprising:
a) contacting a compound of any one of claims 1-2 with a sample to form a fluorescent compound;
b) determining the fluorescent properties of the fluorescent compound.
10. The method of claim 9, wherein the sample is a chemical sample or an aqueous environment sample.
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| CN115745899A (en) * | 2022-10-31 | 2023-03-07 | 郑州师范学院 | Mercury (II) fluorescent probe, preparation method and application thereof |
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