CN115028578B - Fluorescent probe for identifying cobalt ions in soil and preparation method and application thereof - Google Patents
Fluorescent probe for identifying cobalt ions in soil and preparation method and application thereof Download PDFInfo
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- CN115028578B CN115028578B CN202210481806.1A CN202210481806A CN115028578B CN 115028578 B CN115028578 B CN 115028578B CN 202210481806 A CN202210481806 A CN 202210481806A CN 115028578 B CN115028578 B CN 115028578B
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- fluorescent probe
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- cobalt ions
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 93
- 229910001429 cobalt ion Inorganic materials 0.000 title claims abstract description 59
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002689 soil Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000523 sample Substances 0.000 claims abstract description 39
- 238000001514 detection method Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000002262 Schiff base Substances 0.000 claims abstract description 7
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
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- 239000000243 solution Substances 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
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- 238000001035 drying Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 229960003350 isoniazid Drugs 0.000 claims description 5
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011550 stock solution Substances 0.000 claims description 5
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- 238000007605 air drying Methods 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
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- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
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- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 22
- 150000002500 ions Chemical class 0.000 abstract description 20
- 230000008859 change Effects 0.000 abstract description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 10
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- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 6
- 125000006735 (C1-C20) heteroalkyl group Chemical group 0.000 description 6
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 6
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
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- 239000011521 glass Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
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- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
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- 239000012086 standard solution Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- 125000006538 C11 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
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- 125000004619 benzopyranyl group Chemical group O1C(C=CC2=C1C=CC=C2)* 0.000 description 1
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- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
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- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
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- 125000002541 furyl group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/86—Hydrazides; Thio or imino analogues thereof
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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"
-
- 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
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The application relates to the technical field of fluorescent probes, in particular to a fluorescent probe for identifying cobalt ions in soil, and a preparation method and application thereof. The provided fluorescent probe belongs to a Schiff base type fluorescent probe, the structural general formula is shown as a formula I, the structural formula I comprises a C=N bond and a C=O bond, and the fluorescent probe can realize the combination effect on single heavy metal ion cobalt ions and can not react with other heavy metal ions; when the fluorescent probe is combined with cobalt ions, the coordination effect of the cobalt ions and N and O atoms in a probe molecule, particularly the coordination effect of the cobalt ions and the nitrogen atoms inhibits the photoinduction electron transfer effect of a probe system, so that a fluorescence enhancement phenomenon is generated, the identification of the cobalt ions is realized through fluorescence change, the qualitative or quantitative identification of the cobalt ions can be realized, the interference of other heavy metal ions is avoided, and the fluorescent probe has the advantages of high sensitivity, convenience in use, low cost and the like; provides a new method and application prospect for realizing the rapid detection of cobalt metal.
Description
Technical Field
The application belongs to the technical field of fluorescent probes, and particularly relates to a fluorescent probe for identifying cobalt ions in soil, and a preparation method and application thereof.
Background
The identification and detection of metal cations are of great significance in the fields of biosensing, environmental detection and the like. Heavy metals in the soil cannot be biodegraded, and finally enter the human body through a food chain, and then enter the human body to have strong interaction with proteins, enzymes and the like, so that the heavy metals lose activity or accumulate in certain organs in the human body to cause chronic poisoning. For example, after serious contamination of soil with cobalt, crops can die; cobalt poisoning caused by exceeding cobalt content in human body is clinically manifested by inappetence, vomiting, diarrhea and the like; therefore, the detection of cobalt ions is of great importance.
The fluorescence detection technology converts molecular binding information into a fluorescence signal which is easy to detect through a corresponding fluorescence signal transmission mechanism, so that in-situ real-time detection on the molecular level is realized. The method has the advantages of high sensitivity, simple operation and the like, and is widely applied to various fields of chemistry, biology, environmental detection and the like.
At present, the most common domestic heavy metal detection means mainly comprise: an Atomic Absorption Spectrometer (AAS), an inductively coupled plasma mass spectrometer (ICP-MS), an inductively coupled plasma atomic emission spectrometer (ICP-AES), an Atomic Fluorescence Spectrometer (AFS), an X-ray fluorescence spectrometer (XRF), a Laser Induced Breakdown Spectrometer (LIBS) and the like, and the method has quantitative and qualitative detection functions on heavy metals, but the used instruments are expensive and have high detection cost. The fluorescent probe technology is a new method based on optical signal change and measurement technology, has the advantages of high detection sensitivity, good selectivity, convenient use, low cost, no need of pretreatment and the like, and has potential application prospect in the environment detection field of heavy metal ions and the like.
Disclosure of Invention
The invention aims to provide a fluorescent probe for identifying cobalt ions in soil, and a preparation method and application thereof, and aims to solve the problem that the cobalt ions in the soil cannot be detected independently and rapidly and efficiently in the prior art.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the application provides a fluorescent probe, which belongs to Schiff base type fluorescent probes, and has a structural general formula shown in formula I,
wherein R is 1 And R is 2 Any one of the same or different C1-C20 alkyl, C1-C20 heteroalkyl, C1-C20 substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl is selected.
In a second aspect, the present application provides a method for preparing a fluorescent probe, comprising the steps of:
providing a compound shown in a structural general formula II and a structural general formula III, wherein,
the structural general formula II is R 1 -CHO of the general structural formula III
Dissolving a compound with a structural formula II and a compound with a structural formula III in an organic solvent for condensation reaction to obtain a precursor;
dissolving the precursor in an organic solvent, and carrying out recrystallization treatment to obtain a fluorescent probe shown in a formula I, wherein the formula I isR 1 And R is 2 Any one of the same or different C1-C20 alkyl, C1-C20 heteroalkyl, C1-C20 substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl is selected.
In a third aspect, the present application provides the use of a fluorescent probe for qualitative or quantitative detection of cobalt ions in soil systems, water systems, organisms.
The fluorescent probe provided by the first aspect belongs to a Schiff base type fluorescent probe, the structural formula is shown as a formula I, the structural formula I comprises a C=N bond and a C=O bond, and the fluorescent probe can realize the combination effect on single heavy metal ion cobalt ions and can not react with other heavy metal ions; when the fluorescent probe is combined with cobalt ions, the cobalt ions are coordinated with N atoms of C=N bonds and O atoms of C=O bonds in probe molecules, especially the coordination of the cobalt ions and the nitrogen atoms inhibits photoinduction electron transfer of a probe system, so that fluorescence enhancement phenomenon is generated, identification of the cobalt ions is realized through fluorescence change, qualitative or quantitative identification of the cobalt ions can be realized, interference of other heavy metal ions is avoided, and the fluorescent probe has the advantages of high sensitivity, convenience in use, low cost and the like; provides a new method and application prospect for realizing the rapid detection of cobalt metal.
According to the preparation method of the fluorescent probe, the compound shown in the structural formula II and the compound shown in the structural formula III are subjected to condensation reaction and then subjected to recrystallization treatment, so that the fluorescent probe shown in the structural formula I is prepared, the preparation process is simple, large-scale instruments and equipment are not needed, the preparation yield is high, and the obtained fluorescent probe can realize qualitative or quantitative detection of single heavy metal ion cobalt ions and can be widely applied.
The fluorescent probe is used for qualitatively or quantitatively detecting cobalt ions in a soil system, a water system and an organism, and the provided fluorescent probe can realize qualitative or quantitative detection of single heavy metal ion cobalt ions, so that the fluorescent probe has high detection sensitivity and high speed, and is beneficial to providing a new method and application prospect for realizing rapid detection of cobalt metal.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic analysis diagram provided in an embodiment of the present application.
Fig. 2 is a nuclear magnetic resonance hydrogen spectrum of a fluorescent probe molecule provided in an embodiment of the present application.
FIG. 3 is a crystal structure diagram of a fluorescent probe molecule provided in an embodiment of the present application.
Fig. 4 is a schematic diagram of a standard equation of fluorescence emission wavelength intensity of the fluorescent probe molecule G1 for detecting cobalt ions according to the embodiment of the present application.
FIG. 5 shows the fluorescent probe molecules provided in the examples of the present application along with Co in 1,4 dioxane 2+ Is added to the fluorescence change map.
FIG. 6 shows the fluorescent probe molecules provided in the examples of the present application along with Co in 1,4 dioxane 2+ Is added to the ultraviolet change chart.
FIG. 7 is a graph showing fluorescence spectra of fluorescent probe molecules according to the examples of the present application after the fluorescent probe molecules react with different metal ions.
FIG. 8 is a graph of the fluorescent probe molecules provided in the examples of the present application under 365nm ultraviolet light after adding different metal ions.
Fig. 9 is a schematic diagram illustrating the effect of the probe G1 and metal ions according to the embodiment of the present application.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application in the examples and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass in the specification of the embodiment of the present application may be a mass unit well known in the chemical industry field such as μ g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
The first aspect of the embodiment of the application provides a fluorescent probe, which belongs to Schiff base type fluorescent probes, the structural general formula is shown as formula I,
wherein R is 1 And R is 2 Any one of the same or different C1-C20 alkyl, C1-C20 heteroalkyl, C1-C20 substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl is selected.
The fluorescent probe provided in the first aspect of the embodiment of the present application belongs to a schiff base type fluorescent probe, the structural formula is shown in formula I, the structural formula I includes a c=n bond and a c=o bond, and the fluorescent probe can realize a binding effect on a single heavy metal ion cobalt ion and cannot react with other heavy metal ions; when the fluorescent probe is combined with cobalt ions, the cobalt ions are coordinated with N atoms of C=N bonds and O atoms of C=O bonds in probe molecules, especially the coordination of the cobalt ions and the nitrogen atoms inhibits photoinduction electron transfer of a probe system, so that fluorescence enhancement phenomenon is generated, identification of the cobalt ions is realized through fluorescence change, qualitative or quantitative identification of the cobalt ions can be realized, interference of other heavy metal ions is avoided, and the fluorescent probe has the advantages of high sensitivity, convenience in use, low cost and the like; provides a new method and application prospect for realizing the rapid detection of cobalt metal.
In some embodiments, the C1-C20 alkyl is selected from any of C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl, C20 alkyl.
In some embodiments, the C1-C20 heteroalkyl is selected from any of C1 heteroalkyl, C2 heteroalkyl, C3 heteroalkyl, C4 heteroalkyl, C5 heteroalkyl, C6 heteroalkyl, C7 heteroalkyl, C8 heteroalkyl, C9 heteroalkyl, C10 heteroalkyl, C11 heteroalkyl, C12 heteroalkyl, C13 heteroalkyl, C14 heteroalkyl, C15 heteroalkyl, C16 heteroalkyl, C17 heteroalkyl, C18 heteroalkyl, C19 heteroalkyl, C20 heteroalkyl.
In some embodiments, the substituted alkyl of C1-C20 is selected from any one of C1 substituted alkyl, C2 substituted alkyl, C3 substituted alkyl, C4 substituted alkyl, C5 substituted alkyl, C6 substituted alkyl, C7 substituted alkyl, C8 substituted alkyl, C9 substituted alkyl, C10 substituted alkyl, C11 substituted alkyl, C12 substituted alkyl, C13 substituted alkyl, C14 substituted alkyl, C15 substituted alkyl, C16 substituted alkyl, C17 substituted alkyl, C18 substituted alkyl, C19 substituted alkyl, C20 substituted alkyl. In some embodiments, the substituents are selected from at least one of chlorine atoms, bromine atoms, iodine atoms, hydroxyl groups.
In some embodiments, the aryl group is selected from any one of phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, and fluorenyl.
In some embodiments, the substituted aryl is selected from any one of substituted phenyl, substituted naphthyl, substituted anthracenyl, substituted phenanthrenyl, substituted pyrenyl, and substituted fluorenyl. In some embodiments, the substituents are selected from at least one of chlorine atoms, bromine atoms, iodine atoms, hydroxyl groups.
In some embodiments, the heteroaryl is selected from any one of a monocyclic heteroaryl and a fused ring heteroaryl.
In some embodiments, the monocyclic heteroaryl is selected from any one of furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, pyridyl, pyranyl, pyrimidinyl, and pyrazinyl.
In some embodiments, the fused ring heteroaryl is selected from any one of benzofuranyl, benzothienyl, benzopyrrolyl, benzimidazolyl, benzoxazolyl, benzopyrazolyl, benzothiazolyl, benzopyranyl, quinoline, and acridine.
In some embodiments, the substituted heteroaryl is selected from any one of a substituted monocyclic heteroaryl and a substituted fused ring heteroaryl. In some embodiments, the substituents are selected from at least one of chlorine atoms, bromine atoms, iodine atoms, hydroxyl groups.
In some embodiments, in formula I, R 1 Selected from pyrenyl, R 2 Selected from pyridyl, resulting fluorescent probe of formulaIs C 23 H 15 N 3 O has a structural formula shown as a formula G1,
the fluorescent probe molecule of the formula G1 is used for detecting cobalt ions, the action principle is shown in the figure 1, the fluorescent probe molecule G1 comprises a C=N bond and a C=O bond, when the fluorescent probe molecule G1 is combined with cobalt ions, the cobalt ions are coordinated with N atoms of the C=N bond and O atoms of the C=O bond in the probe molecule, especially the coordination of the cobalt ions and the nitrogen atoms inhibits the photoinduction electron transfer of a probe system, so that a fluorescence enhancement phenomenon is generated, the identification of the cobalt ions is realized through fluorescence change, and the cobalt ions are not interfered by other heavy metal ions.
A second aspect of the embodiments of the present application provides a method for preparing a fluorescent probe, including the following steps:
s01, providing a compound shown in a structural general formula II and a structural general formula III, wherein,
the structural general formula II is R 1 -CHO of the general structural formula III
S02, dissolving a compound with a structural general formula II and a compound with a structural general formula III in an organic solvent for condensation reaction to obtain a precursor;
s03, dissolving the precursor in an organic solvent, and carrying out recrystallization treatment to obtain the fluorescent probe shown in the formula I, wherein the formula I isR 1 And R is 2 Any one of the same or different C1-C20 alkyl, C1-C20 heteroalkyl, C1-C20 substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl is selected.
According to the preparation method of the fluorescent probe provided by the second aspect of the embodiment of the application, the compound shown in the structural formula II and the compound shown in the structural formula III are subjected to condensation reaction and then are subjected to recrystallization treatment, so that the fluorescent probe shown in the structural formula I is prepared, the preparation process is simple, large-scale instruments and equipment are not needed, the preparation yield is high, and the obtained fluorescent probe can realize qualitative or quantitative detection of single heavy metal ion cobalt ions and can be widely applied.
In step S01, compounds of the general structural formula II and the general structural formula III are provided, wherein,
the structural general formula II is R 1 -CHO of the general structural formula IIIR 1 And R is 2 Any one of the same or different C1-C20 alkyl, C1-C20 heteroalkyl, C1-C20 substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl is selected.
In some embodiments, to obtain a fluorescent probe represented by structural formula G1, a compound of structural formula II is selected from 1-pyrene formaldehyde, and a compound of structural formula III is selected from isoniazid.
In step S02, the compound with the structural formula II and the compound with the structural formula III are dissolved in an organic solvent and then subjected to condensation reaction, so that a precursor is obtained.
In some embodiments, the molar ratio of the compound of structural formula II to the compound of structural formula III is 1:1.5 to 1.7. In some embodiments, the molar ratio of the compound of structural formula II to the compound of structural formula III is 1:1.5. for control of-CHO in Compound II and NH in Compound III 2 Is favorable for the reaction of the two.
In some embodiments, the condensation reaction is at a temperature of 72 to 78 ℃ for a time of 24 to 25 hours. The temperature and time of the condensation reaction are controlled, and the product obtained by the final reaction is ensured to be a fluorescent probe provided by the structural formula I. If the reaction temperature is too low or the reaction time is too short, the reaction is incomplete, and the fluorescent probe provided by the structural formula I cannot be obtained. In some embodiments, the condensation reaction is at a temperature of 75 ℃ for a period of 24 hours.
In some embodiments, the organic solvent comprises at least one of methanol, ethanol.
In some specific embodiments, the compound of the structural formula II and the compound of the structural formula III are dissolved in sewage ethanol, and then placed in a constant-temperature oil bath pot to react for 24 hours at 75 ℃, cooled, filtered and washed with absolute ethanol to obtain a precursor.
In step S03, the precursor is dissolved in an organic solvent, and recrystallization treatment is performed to obtain the fluorescent probe shown in the formula I.
In some embodiments, the organic solvent comprises at least one of methanol, ethanol.
In some specific embodiments, the precursor is added into 150mL of methanol for dissolution, the mixture is sealed by tinfoil paper at room temperature, the mixture is completely dissolved by ultrasound until the mixture is clear, the mixture is volatilized and recrystallized at room temperature, and the fluorescent probe shown in the formula I is obtained after filtration and drying.
In some specific embodiments, the fluorescent probe is prepared from 1-pyrene formaldehyde and isoniazid as raw materials, and the preparation process is as follows:
230mg (1.0 mmol) of 1-pyrene formaldehyde, 206mg (1.5 mmol) of isoniazid and 60mL of absolute ethyl alcohol are added to obtain a mixed solution A;
placing the mixed solution A in a constant-temperature oil bath pot to react at 75 ℃ for 24 hours, cooling, filtering, and washing with absolute ethyl alcohol to obtain a product B;
and (3) adding 150mL of methanol into the product B to dissolve, sealing the product B at room temperature by using tinfoil paper, completely dissolving the product B by using ultrasonic until the product B is clear, volatilizing the product B at room temperature for recrystallization, filtering and drying the product B to obtain the probe shown as the chemical formula G1.
The synthetic route pattern is as follows:
in a third aspect, the embodiment of the application provides an application of the fluorescent probe, wherein the application is to qualitatively or quantitatively detect cobalt ions in soil systems, water systems and organisms.
The application of the fluorescent probe provided by the third aspect of the embodiment of the application is that the fluorescent probe is used for qualitatively or quantitatively detecting cobalt ions in a soil system, a water system and an organism, and the provided fluorescent probe can realize the qualitative or quantitative detection of single heavy metal ion cobalt ions, so that the detection sensitivity is high, the speed is high, and the fluorescent probe is favorable for providing a new method and application prospect for realizing the rapid detection of cobalt metal.
In some embodiments, provided fluorescent probes are used in a method for detecting cobalt ions in soil, comprising the steps of:
dissolving a fluorescent probe with a structural formula I in dimethyl sulfone, diluting with 1,4 dioxane to obtain a fluorescent reagent, then dripping a sample to be identified into the fluorescent reagent, performing fluorescence excitation, and testing the fluorescence wavelength of fluorescence excitation.
In some embodiments, the concentration of probe in the fluorescent reagent is 1 to 1.2X10 -3 mol·L -1 。
In some embodiments, at an excitation wavelength of 371nm, when Co is added 2+ When the sample is taken, the intensity of the fluorescent reagent is obviously enhanced, and the fluorescent color is light purple under the irradiation of a portable ultraviolet lamp (365 nm).
The following description is made with reference to specific embodiments.
Example A1
A preparation method of a fluorescent probe for identifying cobalt ions in soil comprises the following steps:
(1) Dissolving 230mg of 1-pyrene formaldehyde and 206mg of isoniazid in absolute ethyl alcohol to obtain a mixed solution A; the concentration of ethanol was 95%.
(2) Placing the mixed solution A into a constant-temperature oil bath pot at 75 ℃ for reaction for 24 hours, cooling and filtering; washing with absolute ethanol for three times to obtain product B;
(3) Dissolving the B product in 150mL of methanol, completely dissolving with ultrasound to clarify, sealing with tinfoil at room temperature, recrystallizing, filtering and oven drying to obtain probe G1
Example B1
Method for identifying cobalt ions in soil using probe G1 obtained in example A1
Providing a sample: weighing 75g of cobalt oxide (CoO) and kaolin, mixing into a slurry, stirring, air-drying, grinding, adding an organic solvent DMSO, performing vibration extraction, and drying the obtained supernatant into solid powder. Then preparing cobalt ion to-be-detected liquid with different concentration gradients, detecting the concentration of cobalt metal in the to-be-detected liquid by ICP-MS, and finally dissolving the cobalt metal into secondary water to prepare 1X 10 -1 Co of mol.L-1 2+ Stock solution.
Probe G1 was dissolved in DMSO to a concentration of 1X 10 -1 mol·L -1 Is a liquid to be measured; then diluted with 1,4 dioxane to give a concentration of 1×10 -3 mol·L -1 Then 1X 10 is gradually added dropwise to the fluorescent reagent - 3 mol·L -1 The metal liquid to be tested is then excited with 371nm excitation wavelength, and the fluorescence excitation wavelength is tested, and after cobalt ions are added, the maximum fluorescence wavelength excited by the reagent is 410nm, and the fluorescence intensity is obviously enhanced, so that the identification of the cobalt ions in the soil is proved.
Performance testing
1. The product obtained in example A1 was subjected to a property analysis.
Performing nuclear magnetic resonance hydrogen spectrum analysis on the fluorescent probe molecules and measuring the crystal structure of the fluorescent probe molecules by a single crystal X diffractometer; wherein, the single crystal cultivation method is as follows: 20mg of probe G1 was weighed into a beaker, 100ml of methanol was added and the solution was completely dissolved to clarity by sonication. The conical bottle mouth is sealed by tinfoil paper at room temperature, a plurality of small holes are reserved at the sealing film, and the bottle mouth is placed in a ventilation kitchen, so that the solution is naturally volatilized at room temperature, and yellow single crystals suitable for measurement are generated after about 7 days. The crystals were measured with a Bruker Smart Apex II CCD diffractometer (Bruker Germany). Mo-K alpha rays monochromatized by graphite monochromator μ=0.828 mm-1), single crystal diffraction data were collected in ω scan mode; intensity data were LP corrected using SAINT (Bruker AXS, madison, WI, USA); the crystal structure is obtained through direct method analysis, the full matrix least square method correction is carried out on the crystal structure, the anisotropic thermal parameters of all non-hydrogen atoms are corrected, and all the calculation is completed by using the SHELXL-2016 program.
2. Qualitative analytical testing
At a concentration of 1X 10 -3 mol L -1 When Co is added to the fluorescent probe aqueous solution of (a) at an excitation wavelength of 371nm 2+ The fluorescence intensity and color were analyzed at the time of the sample.
3. Quantitative analysis test
(1) Fluorescent probe solution configuration: 34.9mg of probe G1 is weighed, 1mL of dimethyl sulfoxide (DMSO) is added, and the probe G1 is fully dissolved in 10mL of glass cuvette to finally prepare 1 multiplied by 10 -1 mol L -1 Probe stock solution of (2).
Preparation of metal ion stock solution: weighing 75g of cobalt oxide (CoO) and kaolin, mixing to obtain slurry, stirring, air drying, grinding, adding organic solvent DMSO, shake extracting, oven drying the obtained supernatant to obtain solid powder, dissolving in secondary water to obtain 1×10 solution -1 mol L -1 Co of (C) 2+ For the stock solution, other metal ion preparation methods can be referred to.
(2) 5mL of 1X 10 -3 mol L -1 Fluorescent reagent standard solution, 3ml of fluorescent reagent is added dropwise into a cuvette, 40-60ul of fluorescent reagent with concentration of 1X 10 is added -3 mol L -1 Co 2+ The solution was mixed with it and subjected to fluorescence spectrometry with excitation wavelength of 371nm.
(3) By Co 2+ The concentration is on the abscissa and the fluorescence intensity is on the ordinate, thus obtaining the working curve.
(4) Sample measurement: taking a fluorescent reagent standard solution, adding Co 2+ Diluting the solution to scale, standing at room temperature for 5 min, dripping into a 3.0cm quartz cuvette for fluorescence measurement, and applying the fluorescence intensity on a working curveThe sample concentration was found.
4. Anti-interference experiment
At a probe concentration of 1X 10 -3 mol L -1 Co is added into the reagent of (2) 2+ The fluorescence at the rear 410nm is enhanced, and other metal ions (Pd) are respectively added into the fluorescent reagent 2+ 、Fe 2+ 、Ni 2+ 、Al 3+ 、Ag + 、Hg 2+ 、Li + 、Cd 2+ 、Cu 2+ 、Pb 2+ 、Ca 2+ 、Mn 2+ 、Fe 3+ 、Cr 3+ 、Zn 2+ 、Ba 2+ 、Mg 2+ 、Ru 3+ 、K + 、Na + 、Cs + ) Analysis was performed.
Analysis of results
1. The product obtained in example A1 was subjected to a property analysis.
The nuclear magnetic resonance hydrogen spectrum of the fluorescent probe molecule obtained in example A1 is shown in FIG. 2, and it can be confirmed that the structure of the fluorescent probe molecule obtained is shown in G1.
The fluorescent probe molecule obtained in example A1 was subjected to crystal growth, and crystals of probe G1 were successfully obtained, the crystal structure of which was measured by a single crystal X-ray diffractometer, the crystal structure diagram was shown in FIG. 3, the detailed crystallographic data was shown in Table 1,
TABLE 1
2. Qualitative analytical testing
An important index "detection limit" of the fluorescent probe can be obtained by Origin linear fitting.
The preparation method of the calculation formula of the detection limit is as follows:
mu.L of probe G1 test solution (1X 10) was pipetted with a 100. Mu.L pipette -3 mol·L -1 ) In a 10mL glass cuvette, 1X 10 is prepared by using 1,4 dioxane to fix the volume to 5mL -5 mol·L -1 Blank control. Sequentially preparing 15 bottles of blank control to-be-detected liquid with the same concentration at room temperature and electricityMeasuring the intensity of fluorescence emission wavelength of the probe G1 under the conditions of 500V pressure, 371nm excitation wavelength and 10 narrow peaks, calculating the value of sigma by a standard deviation formula, and obtaining a linear equation of y=37.70x+69.97 (R) by a detection limit formula (3 sigma/K) 2 = 0.9966), as shown in fig. 4.
At a concentration of 1X 10 -3 mol L -1 When Co is added to the fluorescent probe aqueous solution of (a) at an excitation wavelength of 371nm 2+ When a sample is obtained, the fluorescence intensity of the fluorescent reagent is obviously enhanced, and the fluorescence color is changed into light purple; co (Co) 2+ The detection limit is as low as 5.196×10 -7 mol L -1 。
3. Quantitative analysis test
Fluorescent probe molecules with Co in 1,4 dioxane 2+ The fluorescence change pattern of (2) is shown in FIG. 5, the fluorescence probe molecule is shown as Co in 1,4 dioxane 2+ The graph of the added ultraviolet change of (2) is shown in FIG. 6. The sample concentration was found on the working curve based on the fluorescence intensity.
4. Anti-interference experiment
As shown in FIG. 7, the fluorescence spectrum of the fluorescent probe molecules after the fluorescent probe molecules react with different metal ions shows that the fluorescent probe molecules have stronger fluorescence after the fluorescent probe molecules react with cobalt ions, and other ions have little fluorescence.
The graph of the fluorescent probe molecules under the 365nm ultraviolet lamp after adding different metal ions is shown in fig. 8, and as can be seen from fig. 8, the fluorescent probe molecules have stronger fluorescence after reacting with cobalt ions, and other ions have little fluorescence.
As shown in FIG. 9, only Co 2+ The fluorescence of the probe molecule at 410nm is enhanced, and the fluorescent reagent only detects cobalt ions and is not influenced by other metal ions.
In summary, the fluorescent probe provided by the application belongs to a Schiff base type fluorescent probe, the structural formula is shown as a formula I, the structural formula I comprises a C=N bond and a C=O bond, and the fluorescent probe can realize the combination effect on single heavy metal ion cobalt ions and can not react with other heavy metal ions; when the fluorescent probe is combined with cobalt ions, the cobalt ions are coordinated with N atoms of C=N bonds and O atoms of C=O bonds in probe molecules, especially the coordination of the cobalt ions and the nitrogen atoms inhibits photoinduction electron transfer of a probe system, so that fluorescence enhancement phenomenon is generated, identification of the cobalt ions is realized through fluorescence change, qualitative or quantitative identification of the cobalt ions can be realized, interference of other heavy metal ions is avoided, and the fluorescent probe has the advantages of high sensitivity, convenience in use, low cost and the like; provides a new method and application prospect for realizing the rapid detection of cobalt metal.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (3)
1. The application of the fluorescent probe in qualitative or quantitative detection of cobalt ions in soil systems, water systems and organisms is characterized in that the fluorescent probe belongs to Schiff base type fluorescent probes, the structural general formula of the fluorescent probe is shown as a probe G1,
2. the use according to claim 1, wherein the method of preparing the fluorescent probe comprises the steps of:
dissolving 230mg of 1-pyrene formaldehyde and 206mg of isoniazid in absolute ethyl alcohol to obtain a mixed solution A; the concentration of ethanol is 95%;
placing the mixed solution A into a constant-temperature oil bath pot at 75 ℃ for reaction for 24 hours, cooling and filtering; washing with absolute ethanol for three times to obtain product B;
adding 150mL of methanol into the B product for dissolution, completely dissolving the B product until the B product is clear by ultrasonic treatment, sealing the B product by using tinfoil paper at room temperature, recrystallizing the B product, filtering and drying the crystal to obtain a probe G1;
3. the use according to claim 2, characterized in that the method for identifying cobalt ions in soil by the probe G1 comprises the following steps:
providing a sample: weighing 75g of cobalt oxide and kaolin, mixing to form a slurry, stirring, air-drying, grinding, adding an organic solvent DMSO, performing vibration extraction, drying the obtained supernatant to form solid powder, preparing cobalt ion to-be-detected solutions with different concentration gradients, detecting the concentration of cobalt metal in the to-be-detected solutions by ICP-MS, and dissolving the cobalt metal in secondary water to prepare 1X 10 -1 Co of mol.L-1 2+ A stock solution;
probe G1 was dissolved in DMSO to a concentration of 1X 10 -1 mol·L -1 Is a liquid to be measured; diluted with 1,4 dioxane to give a concentration of 1×10 -3 mol·L -1 Is added dropwise to the fluorescent reagent in a stepwise manner of 1X 10 -3 mol·L -1 The metal liquid to be tested is excited by 371nm excitation wavelength, and the fluorescence wavelength of fluorescence excitation is tested, when cobalt ions are added, the maximum fluorescence wavelength of reagent excitation is 410nm, and the fluorescence intensity is enhanced.
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| Comparison of charge transport and opto-electronic properties of pyrene and anthracene derivatives for OLED applications;Uzun, K. ET AL;Journal of Molecular Modeling;第27卷(第6期);174 * |
| Synthesis of isoniazid substituted pyrene (PINHy), and investigation of its optical and electrochemical features as tunable/flexible OLEDs，Journal of Materials Science: Materials in Electronics;Sayin, Serkan ET AL;Journal of Materials Science: Materials in Electronics;第28卷(第17期);13094-13100 * |
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