CN115073338B - Fluorescent probe for high-selectivity recognition of mercury ions, preparation method and application - Google Patents
Fluorescent probe for high-selectivity recognition of mercury ions, preparation method and application Download PDFInfo
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- CN115073338B CN115073338B CN202210826218.7A CN202210826218A CN115073338B CN 115073338 B CN115073338 B CN 115073338B CN 202210826218 A CN202210826218 A CN 202210826218A CN 115073338 B CN115073338 B CN 115073338B
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- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 49
- -1 mercury ions Chemical class 0.000 title claims abstract description 47
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000000523 sample Substances 0.000 claims abstract description 55
- 238000012216 screening Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 25
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 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 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- HBEFYGYBMKPNSZ-UHFFFAOYSA-N s-phenyl chloromethanethioate Chemical compound ClC(=O)SC1=CC=CC=C1 HBEFYGYBMKPNSZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 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
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 38
- 238000001514 detection method Methods 0.000 abstract description 12
- 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
- 238000012360 testing method Methods 0.000 description 13
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 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 4
- 239000007995 HEPES buffer Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- DBLXOVFQHHSKRC-UHFFFAOYSA-N ethanesulfonic acid;2-piperazin-1-ylethanol Chemical compound CCS(O)(=O)=O.OCCN1CCNCC1 DBLXOVFQHHSKRC-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 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
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 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
- 239000012491 analyte Substances 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
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 239000003673 groundwater Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 229910001453 nickel 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
- 229910001432 tin ion Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 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
- 238000004364 calculation method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001987 mercury nitrate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- GOYSNRKWKPRHEA-UHFFFAOYSA-N 5-hydroxyinden-1-one Chemical compound OC1=CC=C2C(=O)C=CC2=C1 GOYSNRKWKPRHEA-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- 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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
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Abstract
The invention relates to a fluorescent probe for high-selectivity recognition of mercury ions. Specifically, the probe can be used for measuring, detecting or screening mercury ions, can realize rapid high-sensitivity analysis of mercury ions, can realize detection of mercury ions of a real water sample, and has the advantages of simple synthesis, stable property and contribution to commercial application.
Description
Technical Field
The invention belongs to the field of fluorescent probes, and particularly relates to a fluorescent probe of an indenone compound 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 known as mercury, and can cause poisoning when people inhale mercury vapor or eat marine products polluted by mercury or inhale mercury compounds. Major sources of mercury pollution include waste water from industries such as combustion of solid waste, instrumentation factories, and smelting noble metals, and as more and more mercury is released into the environment, serious effects are caused on the human body and the environment, and thus, more and more attention is paid. Even if mercury with very low concentration enters human body, serious harm is generated to brain, liver, nervous system and the like, and at present, the environmental protection standard of China is increasingly improved, and the requirement on mercury ion sensitivity is higher. Therefore, a method for identifying mercury ions with high selectivity is urgently needed, and the method has important significance for protecting ecological environment, especially for in-situ and ultrasensitive monitoring of mercury ions in the environment.
Currently, the common mercury ion detection methods mainly comprise spectrophotometry, spectrometry, electrochemical method, fluorescent probe analysis and the like. Among the detection methods of numerous mercury ions, fluorescent probe analysis has been the focus of attention of many researchers because of its advantages of simple operation, high selectivity, high sensitivity, and the like. The fluorescent probes for detecting mercury ions are reported to a large extent, 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, development of a mercury ion fluorescent probe with simple synthesis, good water solubility, high sensitivity and high selectivity is a problem which needs to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the invention aims to provide a high-sensitivity high-selectivity mercury ion fluorescent probe, and a preparation method and application 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 water environment.
Specifically, the invention provides a compound, which has a structure shown in a formula (I):
,R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14 and R 15 in the formula (I) are hydrogen atoms, linear or branched alkyl groups, linear or branched alkoxy groups, sulfonic acid groups, ester groups, carboxyl groups ;R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14 and R 15 may be the same or different.
In some embodiments of the invention, the compounds of the invention are compounds of formula (II) wherein R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14 and R 15 are both hydrogen atoms, having the formula:
the invention also provides a preparation method of the compound shown in the formula (I), which comprises the following steps: reacting a compound of formula (III) with a compound of formula (IV) to produce a compound of formula (I) having the following reaction formula:
：R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14 and R 15 in the formulae (I), (III) and (IV) are hydrogen atoms, linear or branched alkyl groups, linear or branched alkoxy groups, sulfonic acid groups, ester groups, carboxyl groups ;R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14 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 normal temperature for reaction, and after the reaction is finished, the organic solvent is evaporated to dryness in a spinning manner to obtain a crude product, and the crude product is separated and purified by column chromatography to obtain the 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 ambient reaction time is 1 to 6 hours.
In some embodiments of the invention, the reaction temperature is ambient.
In some specific embodiments of the invention, 5-hydroxy-1-indenone and benzaldehyde with the molar ratio of 1:1 are dissolved in ethanol, reflux and stirring are carried out for 72 hours at 80 ℃ under the catalysis of piperazine, after the reaction is finished, the organic solvent is distilled off in a rotary manner 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, comprising the compound of formula (I) according to 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 mercury ions in a sample or determining the amount 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 aqueous environment sample.
In some embodiments of the invention, the aqueous environment sample is a groundwater, river or lake aqueous environment sample.
The invention also provides a kit for detecting the presence of mercury ions in a sample or determining the content of mercury ions in a sample, comprising the compound of formula (I) or 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 provided by the invention 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 environment, especially groundwater, river or lake water samples.
(2) High sensitivity
The mercury ion fluorescent probe reacts with mercury ions very sensitively, thereby being beneficial to detection of mercury ions and being particularly suitable for detection or measurement of mercury ions in water environment with the concentration of 0-2.5 mu M.
(3) High selectivity
The mercury ion fluorescent probe can selectively react with mercury ions specifically to generate products with fluorescence change, and compared with other common substances in common water environment, the mercury ion fluorescent probe has higher selectivity to mercury ions, including 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.
(4) Good stability
The mercury ion fluorescent probe has good stability, and can be stored for a long time.
(5) Simple synthesis
The mercury ion fluorescent probe is simple to synthesize and is favorable for commercialization popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the change in fluorescence spectra of a probe (5. Mu.M) before and after addition of mercury ions (20. Mu.M);
FIG. 2 shows the change in absorption spectra of a probe (20. Mu.M) before and after addition of mercury ions (20. Mu.M);
FIG. 3 is a fluorescence spectrum of a probe (5. Mu.M) after addition of mercury ions (0-4. Mu.M);
FIG. 4 is a working curve of probe (5. Mu.M) for quantitative analysis of different 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 to 16 are respectively: 1. blank; 2. chromium ion Cr 2+; 3. copper ion Cu 2+; 4. ferrous ion Fe 2+; 5. calcium ions Ca 2+; 6. potassium ion K +; 7. magnesium ion Mg 2+; 8. sodium ions Na +; 9. nickel ion Ni 2+; 10. lead ions Pb 2+; 11. tin ions Sn 2+; 12. zinc ion Zn 2+; 13. nitrate ions NO 3 -; 14. sulfate ion SO 4 2-; 15. chloride Cl -; 16. mercury ion Hg 2+ (5 μm) (other analyte concentrations were 50 μm except for the specific designation). The bar graph represents fluorescence intensity values of the probe at 505nm in the presence of different analytes;
Detailed Description
The technical solutions of 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 apparent that the described embodiments are only some of the embodiments of the present invention and should not be used to limit the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention. Example 1: synthesis of Compound of formula (II)
The synthetic design route is as follows:
Embodiment 1: 236mg (1 mmol) of 2-benzylidene-5-hydroxy-1-indenone is dissolved in 15mL of dichloromethane, 173mg (1 mmol) of phenyl thiochloroformate is added, 129mg (1 mmol) of DIPEA is added, stirring is carried out for 2h at normal temperature, 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 the pure product is obtained, and the yield is 73.9%.
Embodiment 2: 236mg (1 mmol) of 2-benzylidene-5-hydroxy-1-indenone are dissolved in 15mL of methylene chloride, 260mg (1.5 mmol) of phenyl thiochloroformate are added, 194mg (1.5 mmol) of DIPEA are then 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 a purer product is to be obtained, the pure product is obtained by chromatographic column separation, and 290mg of the pure product is obtained, and the yield is 78%.
Embodiment 3: 236mg (1 mmol) of 2-benzylidene-5-hydroxy-1-indenone are dissolved in 15mL of methylene chloride, 346mg (2 mmol) of phenyl thiochloroformate are added, 258mg (2 mmol) of DIPEA are added, stirring is carried out for 4h at normal temperature, and rotary evaporation is carried out by using 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, 310mg of the pure product is obtained, and the yield is 83.3%.
Embodiment 4: 236mg (1 mmol) of 2-benzylidene-5-hydroxy-1-indenone are dissolved in 15mL of dichloromethane, 519mg (3 mmol) of phenyl thiochloroformate are added, 387mg (3 mmol) of DIPEA are added, stirring is carried out for 4h at normal temperature, rotary evaporation is carried out by using a rotary evaporator to obtain a crude product, and chromatographic column separation is carried out to obtain a pure product, 330mg, and the yield is 88.7%.
Embodiment 5: 236mg (1 mmol) of 2-benzylidene-5-hydroxy-1-indenone are dissolved in 15mL of methylene chloride, 519mg (3 mmol) of phenyl thiochloroformate are added, 387mg (3 mmol) of DIPEA are then added, stirring is carried out at normal temperature for 6h, and rotary evaporation is carried out by using a rotary evaporator to obtain a crude product. If a purer product is to be obtained, the pure product is obtained by column chromatography, 335mg of the pure product is obtained, and the yield is 90.1%.
Example 2: variation of fluorescence spectrum of detection probe before and after mercury ion identification
5ML of distilled water was added to the cuvette, 0.5mL of 4-hydroxyethyl piperazine ethane sulfonic acid (HEPES, 100 mM) was added thereto, the volume was fixed to 10mL with distilled water, 50. Mu.L of a probe stock solution (1 mM) was removed and placed into the cuvette, and then a mercury ion stock solution was added so that the mercury ion concentration was 20. Mu.M, and after shaking uniformly, it was allowed to stand for 50 minutes, and the change in fluorescence spectrum thereof was measured with a fluorescence spectrometer, the above-mentioned measurement was performed in a pure water system, the probe used was the probe prepared in example 1, and all the spectral tests were measured at 25 ℃. The results are shown in FIG. 1.
As is clear from FIG. 1, the change in fluorescence intensity at 505nm is very pronounced when mercury ions are added.
Example 3: variation of absorption spectrum of detection probe before and after mercury ion identification
5ML of distilled water was added to the cuvette, 0.5mL of 4-hydroxyethyl piperazine ethane sulfonic acid (HEPES, 100 mM) was added thereto, the volume was fixed to 10mL with distilled water, 200. Mu.L of a probe stock solution (1 mM) was removed and placed into the cuvette, and then a mercury ion stock solution was added so that the mercury ion concentration was 20. Mu.M, and after shaking uniformly, it was allowed to stand for 50 minutes, and the change in absorption spectrum thereof was measured with an ultraviolet absorption spectrometer, the above-mentioned measurement was 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 value at 325nm is significantly reduced.
Example 4: testing concentration gradient of fluorescent probe to Mercury ion
5ML of distilled water, 0.5mL of 4-hydroxyethyl piperazine ethane sulfonic acid (HEPES, 100 mM) and distilled water are added to 10mL, 50 mu L of probe stock solution (1 mM) is finally removed and placed into a cuvette, and then different volumes of mercury ion stock solutions are added according to the intended preparation of different concentrations of mercury ions (the concentrations are 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 and 4 mu M respectively), and after uniform shaking, the sample is allowed to stand for 50 minutes, and then the fluorescence intensity change of the sample is tested by a fluorescence spectrometer. The above-mentioned measurement was performed in a pure water system using the probe prepared in example 1, and all spectroscopic tests were performed at 25 ℃. The results are shown in FIG. 3.
As is clear from fig. 3, the fluorescence intensity at 505nm gradually increases as the concentration of the added mercury ions increases; also, as can be seen from FIG. 4, at 505nm, the fluorescence intensity exhibited a good linear relationship after the addition of mercury ions (0-2.5. Mu.M) to the mercury ion fluorescent probe (5. Mu.M), which demonstrates that quantitative analysis of mercury ions can be performed by means of the fluorescent probe.
Example 5: testing the selectivity of fluorescent probes for mercury ions
The analytes were respectively: 1. blank; 2. chromium ion Cr 2+; 3. copper ion Cu 2+; 4. ferrous ion Fe 2+; 5. calcium ions Ca 2+; 6. potassium ion K +; 7. magnesium ion Mg 2+; 8. sodium ions Na +; 9. nickel ion Ni 2+; 10. lead ions Pb 2+; 11. tin ions Sn 2 +; 12. zinc ion Zn 2+; 13. nitrate ions NO 3 -; 14. sulfate ion SO 4 2-; 15. chloride ion Cl-;16. mercury ion Hg 2+ (5 μm) (other analyte concentrations were 50 μm except for the specific designation). The bar graph represents the fluorescence intensity values of the probe at 505nm in the presence of different analytes. The above-mentioned measurement was performed in a pure water system using the probe prepared in example 1, and all spectroscopic tests were performed at 25 ℃. Specifically, 5mL of distilled water was added to the cuvette, 0.5mL of 4-hydroxyethyl piperazine ethane sulfonic acid (HEPES, 100 mM) was added thereto, the volume was fixed to 10mL with distilled water, and finally 50. Mu.L of a probe stock solution (1 mM) was removed and placed in the cuvette, and then a certain amount of the above analyte was added thereto, and the mixture was shaken well and allowed to stand for 50 minutes to determine the fluorescence intensity value. 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 react with mercury ions specifically, and has significantly changed fluorescence spectra before and after reaction, while other analytes common in water environment do not significantly change fluorescence intensity after the probe is acted
Example 6: detection limit test and calculation of probe
The detection limit was calculated by fluorescence titration. The detection limit calculation formula is as follows:
Detection limit=3σ/k
Σ is the standard deviation of fluorescence intensity of the blank probe, and k is the slope of the linear graph of FIG. 4.
The detection limit of mercury ions by the probe of formula (II) was 16nM.
Example 7: analytical test of Hg 2+ in three real water samples by probe
Three real water samples are respectively collected, water sample A is collected from Jiazi lake water of Jinan university, water sample B is collected from Ji Nanshi jin Yun Chuan groundwater, water sample C is collected from Ji Nanshi jin Yang Chuan river water, all the water samples are detected, mercury ions are not found, then two groups of test systems are configured for each water sample, 5 mu M probes are added to each group of test systems, the probes are prepared in the embodiment 1, then 1 mu M mercury nitrate and 2 mu M mercury nitrate are respectively added to each group of test systems of each water sample, shaking is uniform, standing is carried out for 50 minutes, and then the change of fluorescence intensity of each water sample 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 rate of the three water samples is 84.07% -109.20%, and further prove that the fluorescent probe can effectively detect Hg 2+ in the real water sample.
While the invention has been described with reference to the above embodiments, it will be understood that the invention is capable of further modifications and variations without departing from the spirit of the invention, and these modifications and variations are within the scope of the invention.
Claims (9)
1. A compound having the structure:
。
2. A process for preparing the compound of claim 1, comprising the steps of: reacting 2-benzylidene-5-hydroxy-1-indenone with phenyl thiochloroformate to obtain a compound of formula (II), wherein the reaction formula is as follows:
。
3. The method of manufacturing as claimed in claim 2, comprising the steps of: dissolving 2-benzylidene-5-hydroxy-1-indenone and phenyl thiochloroformate in a certain molar ratio in dichloromethane, stirring at normal temperature for reaction, and evaporating the organic solvent by spin to obtain a crude product after the reaction is finished, and separating and purifying by column chromatography to obtain a pure product.
4. The method according to claim 3, wherein the molar ratio of the 2-benzylidene-5-hydroxy-1-indenone to the phenyl thiochloroformate is 1:1-1:3, and the reaction time is 1-6 hours.
5. A fluorescent probe composition for measuring, screening or detecting mercury ions comprising a compound of claim 1.
6. The fluorescent probe composition of claim 5, further comprising a solvent, an acid, a base, a buffer solution, or a combination thereof.
7. Use of a compound according to claim 1 for the preparation of a reagent for measuring, screening or detecting mercury ions.
8. A method for detecting the presence of mercury ions in a sample or determining the mercury ion content in a sample, comprising:
a) Contacting the compound of claim 1 with a sample to form a fluorescent compound;
b) Determining the fluorescent properties of the fluorescent compound.
9. The method of claim 8, wherein the sample is a chemical sample or an aqueous environment sample.
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| CN107298664A (en) * | 2017-07-11 | 2017-10-27 | 济南大学 | A kind of colorimetric fluorescence probe for analyzing mercury ion, preparation method and application |
| CN109776369A (en) * | 2019-03-14 | 2019-05-21 | 济南大学 | A kind of hypersensitive is highly selective to analyze hypochlorous fluorescence probe in real time |
| CN111171809A (en) * | 2020-01-02 | 2020-05-19 | 广州大学 | Hydroxyl indenone derivative fluorescent probe and preparation method and application thereof |
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| CN107298664A (en) * | 2017-07-11 | 2017-10-27 | 济南大学 | A kind of colorimetric fluorescence probe for analyzing mercury ion, preparation method and application |
| CN109776369A (en) * | 2019-03-14 | 2019-05-21 | 济南大学 | A kind of hypersensitive is highly selective to analyze hypochlorous fluorescence probe in real time |
| CN111171809A (en) * | 2020-01-02 | 2020-05-19 | 广州大学 | Hydroxyl indenone derivative fluorescent probe and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| A water-soluble and highly specificfluorescent probe with large Stokes shiftfor imaging basal HOCl in living cells and zebrafish;Yanfeng, Shi，等;Sensors & Actuators: B. Chemical;20190415;第291卷;243-249 * |
| Novel Carbonothioate-Based Colorimetric and Fluorescent Probe for Selective Detection of Mercury Ions;Wei Shu et al;Industrial & Engineering Chemistry Research;第55卷;8713-8718 * |
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