CN115108966B - Benzoindole squaraine metal ion probe and preparation method and application thereof - Google Patents
Benzoindole squaraine metal ion probe and preparation method and application thereof Download PDFInfo
- Publication number
- CN115108966B CN115108966B CN202210718684.3A CN202210718684A CN115108966B CN 115108966 B CN115108966 B CN 115108966B CN 202210718684 A CN202210718684 A CN 202210718684A CN 115108966 B CN115108966 B CN 115108966B
- Authority
- CN
- China
- Prior art keywords
- compound
- metal ion
- ion probe
- reaction
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 54
- 239000000523 sample Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- IHXWECHPYNPJRR-UHFFFAOYSA-N 3-hydroxycyclobut-2-en-1-one Chemical compound OC1=CC(=O)C1 IHXWECHPYNPJRR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- HIYWOHBEPVGIQN-UHFFFAOYSA-N 1h-benzo[g]indole Chemical compound C1=CC=CC2=C(NC=C3)C3=CC=C21 HIYWOHBEPVGIQN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 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 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 23
- 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 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 17
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009987 spinning Methods 0.000 claims description 2
- 238000000862 absorption spectrum Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 7
- 239000007850 fluorescent dye Substances 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 32
- 238000012360 testing method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000029011 Copper metabolism disease Diseases 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000008832 photodamage Effects 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/60—Naphtho [b] pyrroles; Hydrogenated naphtho [b] pyrroles
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
-
- 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
-
- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
Abstract
The invention discloses a benzoindole squaraine metal ion probe and a preparation method and application thereof, and the metal ion probe is a compound with a benzoindole squaraine structure, has the advantages of simple preparation method, easily obtained raw materials and excellent photo-thermal stability; for Fe 3+ 、Cu 2+ 、Hg 2+ Has good colorimetric and fluorescent recognition capability, and can be used for Fe 3+ 、Cu 2+ 、Hg 2+ The identification process of the fluorescent dye has obvious color change, and the absorption spectrum and the fluorescence emission spectrum of the fluorescent dye are also changed, so that the fluorescent dye has short response time and high sensitivity and is not interfered by other ions.
Description
Technical Field
The invention belongs to the technical field of chemical analysis and test, and particularly relates to a benzindole squaraine metal ion probe, and a preparation method and application thereof.
Background
Iron and copper are two microelements necessary for the human body and play an important role in many vital activities. Iron is involved in the processes of oxygen transport and proton transfer in blood, and is an important component of various enzymes and hemoglobin; once the iron element in the human body is deficient, the physiological function system is disturbed, thereby causing diseases; while excess iron is potentially harmful, it may promote oxidation of fats, proteins and other components of the cell to become toxic. Likewise, the lack or excess of copper ions in the body can also lead to disturbances in growth and metabolism, leading to serious disorders of copper metabolism. In addition, mercury is a heavy metal element with high toxicity to humans and the environment, and its accumulation in the body causes serious health problems. Therefore, the development can efficiently and selectively detect Fe in natural environment and organism 3+ 、Cu 2+ 、Hg 2+ Is of interest. Detection goldThe traditional methods of the genus ion are: atomic absorption spectrophotometry, inductively coupled plasma atomic emission spectrometry, electrochemical analysis, and the like. The above methods often require the use of expensive instrumentation and specialized inspectors, which are not suitable for mass and real-time inspection. The fluorescent probe detection method has the advantages of high sensitivity, low cost, easiness in operation and the like. Currently used for detecting Fe 3+ 、Cu 2+ 、Hg 2+ The fluorescent probe molecules of (2) often have the defects of complex preparation, low selectivity, insufficient absorption and emission wavelength, and the like. Therefore, the probe molecule with high sensitivity, high selectivity and strong absorption and fluorescence emission in the near infrared region is developed to detect Fe in natural environment and organism 3+ 、Cu 2+ 、Hg 2+ It is important.
Squaraine is a D-A-D conjugated organic molecule formed by condensing two identical or different electron-rich electron-donating units (donor, D or D') and a strong electron-withdrawing squaraine unit (A), and has a zwitterionic structure with stable resonance. Most squaraines absorb and emit strongly in the visible and near infrared regions with molar extinction coefficients (. Epsilon.) of up to 10 5 M -1 cm -1 The method comprises the steps of carrying out a first treatment on the surface of the And squaraine has the advantages of easy aggregation, simple synthetic route, good photo/thermal stability, strong structural modification, and the like. Therefore, squaraine molecules have been widely used in many fields such as photoconductive data storage, organic light emitting diodes, organic field effect transistors, organic solar cells, two-photon absorption, nonlinear optics, near infrared fluorescent probes, biomarkers, photodynamic therapy, and the like. In fact, the quaternary ring in the center of squaraine has two oxygen atoms, which can be directly used as coordination points with metal ions; the combination of oxygen atoms and metal ions is one of the most effective methods of influencing electron distribution in the central four-membered ring, often resulting in significant changes in the photophysical properties of squaraine compounds, thereby increasing the sensitivity of the probe molecule. In addition, the oxygen atom can be further substituted and modified by sulfur atom, nitrogen atom and the like, so that the binding capacity with metal ions is changed, the photophysical properties of the oxygen atom are regulated, and probe molecules with different response phenomena are obtained.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, a first object of the present invention is to provide a benzindole squaraine metal ion probe;
the second aim is to provide a preparation method of the benzoindole squaraine metal ion probe;
third object is to provide a method for detecting Fe by using the benzoindole squaraine metal ion probe 3+ 、Cu 2+ 、Hg 2+ Is used in the field of applications.
In order to achieve the above purpose, the invention provides a benzindole squaraine metal ion probe, which has the following structural formula (I):
wherein R is 1 、R 2 Is an oxygen atom or a sulfur atom.
Further, in the structural formula (I) of the metal ion probe:
when R is 1 、R 2 When the two are oxygen atoms, the two are compounds II, and the structural formula of the two is shown as (II);
when R is 1 、R 2 When the oxygen atom and the sulfur atom are respectively, the compound is a compound III, and the structural formula of the compound is shown as (III);
when R is 1 、R 2 When the two are sulfur atoms, the two are compounds IV, and the structural formula of the compounds is shown as (IV);
the structural formulas of the compound II, the compound III and the compound IV are respectively shown as follows:
further, the preparation methods of the compound II, the compound III and the compound IV comprise the following specific steps:
1) Preparation of Compound II
1, 2-trimethyl-1H-benzo [ e ]]Indole addition CH 3 NO 2 Adding iodine after stirring and dissolvingReacting n-butane for 14-18h after heating to 100 ℃ to obtain a reaction solution I, concentrating the reaction solution I, slowly dripping the reaction solution I into ethyl acetate, precipitating, filtering, stirring and washing a filter cake with petroleum ether, and filtering to obtain a light grey green precipitate B-C4;
adding B-C4, squaric acid and quinoline into a mixed solvent with the volume ratio of toluene to n-butanol being 1:1, adding a water separator, refluxing for 9 hours to obtain a reaction liquid II, concentrating the reaction liquid II under reduced pressure, dripping the reaction liquid II into ethyl acetate, separating out solids, carrying out suction filtration, spinning the filtrate, adding petroleum ether, stirring and washing for two times, and carrying out suction filtration to obtain a brown green solid which is a metal ion probe, namely a compound II;
2) Preparation of Compound III
Under the condition of room temperature, reacting a compound II with phosphorus pentasulfide in pyridine for 26 hours to obtain a reaction solution III, purifying by column chromatography to obtain a target product, and then washing with n-hexane to obtain a pure dark green solid which is a metal ion probe, namely the compound III;
3) Preparation of Compound IV
Under the anhydrous and anaerobic condition, adding the compound II, the Lawson reagent and hexamethylphosphoric triamide into degassed toluene, carrying out reflux reaction for 2.5 hours, stopping the reaction to obtain a reaction solution IV, dripping the reaction solution IV into anhydrous diethyl ether, carrying out suction filtration to obtain a solid, dissolving the solid with dichloromethane, purifying by column chromatography, and then recrystallizing to obtain a bright copper solid, wherein the bright copper solid is the metal ion probe, namely the compound IV.
Further, the benzoindole squaraine metal ion probe is used for detecting Fe 3+ 、Cu 2+ 、Hg 2+ Is used in the field of applications.
By adopting the scheme, the invention has the following beneficial effects:
1. the probe provided by the invention is blue or blue-green in acetonitrile solution, has strong absorption at 600-700nm and strong fluorescence emission at 650-850nm, and the absorption and emission are both in a near infrared region, so that the probe has the advantages of small photodamage, strong tissue penetrating capacity, low self fluorescence interference and the like. The solution of the probe in the invention is added with Fe respectively 3+ 、Cu 2+ 、Hg 2+ The color change is obvious after the color change, naked eye detection can be carried out without other equipment, and the corresponding absorption spectrum and fluorescence emission spectrum are also changed, so that the color comparison and spectrum test can be carried out on Fe 3+ 、Cu 2+ 、Hg 2+ The double-channel detection is carried out, and the method is not interfered by other metal ions, so that the method has good application prospect.
2. The metal ion probe has the advantages of simple synthetic route, readily available raw materials and simple operation.
3. The metal ion probe adds Fe 3+ 、Cu 2+ 、Hg 2+ Immediately after that, the response phenomenon appears, the response time is extremely short, the sensitivity is high, and the minimum detection limit is 1.14-6.28 mu M.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a fluorescence emission spectrum of compound IV tested for selectivity to different metal ions.
FIG. 2 is a scheme for the preparation of Compound II.
FIG. 3 is a scheme for the preparation of compound III.
FIG. 4 is a flow chart of the preparation of Compound IV.
FIG. 5 is an absorption spectrum of compound II tested for selectivity to different metal ions.
FIG. 6 is a graph showing the recognition of Fe by other metal ions for Compound II 3+ And testing the interference.
FIG. 7 shows the addition of Fe in different equivalent ratios to Compound II 3+ Absorption spectrum after solution.
FIG. 8 shows the addition of Fe to compound III 3+ The absorption wavelength then varies with time at 663 nm.
FIG. 9 is a colorimetric development of compound III on different metal ions.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the examples are not intended to limit the invention in any way, and unless specifically indicated otherwise, the reagents, methods and apparatus to which the invention relates are those conventional in the art.
Example 1: preparation of benzoindole squaraine metal ion probe
1. Experimental method
The method comprises the following specific steps:
1) The preparation of the compound II is shown in the figure 2;
1, 2-trimethyl-1H-benzo [ e ]]Indole (10.00 g,47.50 mmol) was added to 80mL CH 3 NO 2 Adding n-butyl iodide (21.50 g,95.50 mmol) after stirring and dissolving, heating to 100 ℃ for reaction for 14h, monitoring by TLC to find that partial raw materials still remain unreacted in the system, adding 1.8mL of n-butyl iodide, continuing to react for 4h at 100 ℃, stopping the reaction to obtain reaction liquid I, concentrating the reaction liquid I to 50mL, slowly dropwise adding the reaction liquid I into 350mL of ethyl acetate, precipitating and separating out, filtering, stirring and washing a filter cake with petroleum ether, and filtering again to obtain pale green precipitate B-C4, wherein the B-C4 is 16g, and the yield is 86%;
B-C4 (10.00 g,25.4 mmol), squaric acid (1.45 g,12.7 mmol) and quinoline (3.30 g,25.4 mmol) are added into 150mL of a mixed solvent with the volume ratio of toluene to n-butanol being 1:1, reflux is carried out for 9h in boiling water to obtain a reaction liquid II, the reaction liquid II is concentrated to 20mL under reduced pressure and then is dripped into 300mL of ethyl acetate, solid is separated out, the filtrate is dried by spin, 200mL of petroleum ether is added for stirring and washing twice after suction filtration, brown green solid is obtained after suction filtration, and is a metal ion probe, namely a compound II, the compound II is 4.16g, and the yield is 54%;
2) The preparation of the compound III is shown in the figure 3;
reacting compound II (0.54 g,0.89 mmol) with phosphorus pentasulfide (0.79 g,1.80 mmol) in pyridine (6 mL) at room temperature for 26h to obtain a reaction solution III, purifying by column chromatography (200-300 silica gel, eluting with dichloromethane) to obtain a target product, and washing with n-hexane to obtain a pure dark green solid which is a metal ion probe, namely compound III, wherein the compound III is 0.39g, and the yield is 69%;
3) The preparation of the compound IV is shown in the figure 4;
under anhydrous and anaerobic conditions, adding a compound II (0.20 g,0.33 mmol), a Lawson reagent (0.27 g,0.66 mmol) and hexamethylphosphoric triamide (HMPA, 0.13 mL) into 15mL of degassed toluene, carrying out reflux reaction for 2.5h, stopping the reaction to obtain a reaction solution IV, dripping the reaction solution IV into 100mL of anhydrous diethyl ether, carrying out suction filtration to obtain a solid, dissolving the solid with dichloromethane, purifying by column chromatography (100-200 meshes of silica gel, eluent is dichloromethane: petroleum ether=1:1), and then recrystallizing (dichloromethane: ethanol=1:3) to obtain a bright copper solid which is a metal ion probe, wherein the compound IV is 0.07g, and the yield is 33%;
and carrying out structural identification on the obtained compound II, compound III and compound IV through nuclear magnetic resonance hydrogen spectrum and carbon spectrum respectively.
2. Experimental results
Compound II: 1 H NMR(400MHz,Chloroform-d,ppm)δ8.20(d,J＝8.5Hz,2H,ArH),7.90(d,J＝8.6Hz,2H,ArH),7.87(d,J＝8.4Hz,2H,ArH)7.58(t,J＝7.7Hz,2H,ArH),7.42(t,J＝7.6Hz,2H,ArH),7.29(d,J＝8.7Hz,2H,ArH),6.03(s,2H,＝CH),4.12(s,4H,CH 2 ),2.09(s,12H,CH 3 ),1.90-1.83(m,4H,CH 2 ),1.54-1.46(m,4H,CH 2 ),1.01(t,J＝7.4Hz,6H,CH 3 ). 13 CNMR(101MHz,Chloroform-d,ppm)δ178,171.4,139.7,134.4,131.2,129.7,129.6 128.7,127.3,124.3,122.6,110.2,86.3,51.2,43.7,29.4,26.8,20.4,13.9.
compound iii: 1 H NMR(400MHz,Chloroform-d,ppm)δ8.22(d,J＝8.5Hz,2H,ArH),7.90(t,J＝7.1Hz,4H,ArH),7.57(t,J＝7.8Hz,2H,ArH),7.42(t,J＝7.6Hz,2H,ArH),7.34(d,J＝8.9Hz,2H,ArH),6.50(s,2H,＝CH),4.22(t,J＝7.5Hz,4H,CH 2 ),2.11(s,12H,CH 3 ),1.90(q,J＝7.8Hz,4H,CH 2 ),1.54-1.47(m,4H,CH 2 ),1.01(t,J＝7.5Hz,6H,CH 3 ). 13 C NMR(101MHz,Chloroform-d,ppm)δ205.7,182.8,177.9,173.2,139.6,134.7,131.4,129.8，129.7，128.6,127.4,124.5,122.5,110.4,88.9,51.3,43.8,29.5,26.7,20.4,14.0.
compound IV: 1 H NMR(400MHz,Chloroform-d,ppm)δ8.21(d,J＝8.5Hz,2H,ArH),7.91(t,J＝8.0Hz,4H,ArH),7.59(t,J＝7.7Hz,2H,ArH),7.45(t,J＝7.6Hz,2H,ArH),7.37(d,J＝8.0Hz,2H,ArH),6.63(s,2H,＝CH),4.36(t,J＝7.6Hz,4H,CH 2 ),2.14(s,12H,CH 3 ),1.93-1.86(m,4H,CH 2 ),1.56-1.46(m,4H,CH 2 ),1.02(t,J＝6Hz,6H,CH 3 ). 13 C NMR(101MHz,Chloroform-d,ppm)δ204.5,185.1,174.9,139.4,135.0,131.4,129.7,129.6,128.6,127.3,124.6,122.7,110.7,87.5,51.6,45.2,29.4,27.6,20.3,13.9.
example 2: selective testing of metal ion probes for different metal ions
1. Experimental materials
The metal ion probe Compound II, compound III and Compound IV prepared in example 1
2. Experimental method
10mL of CH of metal ion probe compound II or compound III or compound IV was added to 21 test tubes numbered 1-21, respectively 3 CN solution (1.0X10) -5 mol/L), and 50 mu L of aqueous solutions (Fe) of different metal ions are respectively added into test tubes No. 2-21 3+ 、Fe 2+ 、Hg 2+ 、Na + 、K + 、Li + 、Ca 2+ 、Ba 2+ 、Al 3+ 、Pb 2+ 、Mn 2+ 、Co 2+ 、Cu 2+ 、Ag + 、Zn 2+ 、Cd 2+ 、Mg 2+ 、Ni 2+ 、Cr 3+ 、Cr 2+ C=0.04 mol/L), and after shaking, standing for 30min, and performing absorption spectrum and fluorescence emission spectrum tests.
3. Experimental results
As shown in FIGS. 1, 5 and 9, fe is added 3+ 、Cu 2+ 、Hg 2+ After that, the color of the solution of the metal ion probe compound II or the compound III or the compound IV is obviously changed, the intensity of the absorption spectrum and the emission spectrum is obviously reduced, and the color and the spectrum of the solution are not obviously changed after other metal ions are added, which indicates that the metal ion probe is specific to Fe 3+ 、Cu 2+ 、Hg 2+ Has good effectIs a function of the identification ability of the device.
Example 3: other metal ion to metal ion probe recognition of Fe 3+ Interference testing at the time
1. Experimental materials
Metal ion Probe Compound II prepared in example 1
2. Experimental method
10mL of the metal ion probe compound II (1.0X10) was added to 21 test tubes numbered 1-21 -5 mol/L) CH 3 CN solutions, 50. Mu.L of Fe was added to test tubes No. 2-21, respectively 3+ The aqueous solution (0.04 mol/L) was then added to test tubes No. 3-21 with 50. Mu.L of different metal ions (Fe) 2+ 、Hg 2+ 、Na + 、K + 、Li + 、Ca 2+ 、Ba 2+ 、Al 3+ 、Pb 2+ 、Mn 2+ 、Co 2+ 、Cu 2+ 、Ag + 、Zn 2+ 、Cd 2+ 、Mg 2+ 、Ni 2+ 、Cr 3+ 、Cr 2+ C=0.04 mol/L) of the aqueous solution, and standing for 30min after shaking, and performing absorption spectrum and fluorescence emission spectrum tests.
3. Experimental results
As shown in FIG. 6, the results indicate that the probe molecule is specific to Fe 3+ The recognition is not interfered by other metal ions.
Example 4: metal ion probe pair of different concentration Fe 3+ 、Cu 2+ 、Hg 2+ Response to aqueous solutions
1. Experimental materials
Metal ion Probe Compound II prepared in example 1
2. Experimental method
To 31 test tubes numbered 1-31, 10mL of probe compound II (1.0X10) -5 mol/L) CH 3 CN solution, and then Fe (0.0-20.0 equivalent) with different equivalent ratios is added into each test tube 3+ Or Cu 2+ Or Hg 2+ (0.01 mol/L) aqueous solution, and standing for 30min after shaking, and performing absorption spectrum and fluorescence emission spectrum tests.
3. Experimental results
As shown in fig. 7, with Fe 3+ Or Cu 2+ Or Hg 2+ The equivalent weight is increased, the absorption spectrum and the emission spectrum of the probe molecules are sequentially reduced, and experimental data are processed and calculated to obtain the probe molecule pair Fe 3+ 、Cu 2+ 、Hg 2+ The minimum limit of detection of (2) is 1.14-6.28. Mu.M.
Example 5: metal ion probe pair Fe 3+ 、Cu 2+ 、Hg 2+ Response of aqueous solutions over time
1. Experimental materials
The metal ion Probe Compound III prepared in example 1
2. Experimental method
To a double-sided quartz cuvette was added 2mL of probe compound III (1.0X10) -5 mol/L) CH 3 CN solution, testing its absorption spectrum and fluorescence emission spectrum, adding Fe into cuvette after testing 3+ Or Cu 2+ Or Hg 2+ (0.01 mol/L) aqueous solution, absorption spectrum and fluorescence emission spectrum tests were performed immediately after shaking, followed by absorption spectrum and fluorescence emission spectrum tests every 2 minutes.
3. Experimental results
As shown in FIG. 8, when Fe is added 3+ Or Cu 2+ Or Hg 2+ After that, the intensities at the maximum absorption wavelength and the maximum emission wavelength of the probe molecule are immediately reduced, and then the probe molecule tends to be stable, which indicates that the probe molecule has a high response speed to metal ions.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. Benzoindole squaraine metal ion probe for detecting Hg 2+ The application of the metal ion probe is characterized in that the metal ion probe is a compound II, a compound III and a compound IV, and the structure is as follows:
2. the benzindole squaraine metal ion probe according to claim 1 for detection of Hg 2+ The preparation method of the compound II, the compound III and the compound IV is characterized by comprising the following specific steps:
1) Preparation of Compound II
1, 2-trimethyl-1H-benzo [ e ]]Indole addition CH 3 NO 2 Adding n-butyl iodide after stirring and dissolving, heating to 100 ℃ for reaction for 14-18 hours, stopping the reaction to obtain a reaction solution I, concentrating the reaction solution I, slowly dripping the reaction solution I into ethyl acetate, precipitating, filtering, stirring and washing a filter cake with petroleum ether, and filtering to obtain a light gray green precipitate B-C4;
adding B-C4, squaric acid and quinoline into a mixed solvent with the volume ratio of toluene to n-butanol being 1:1, adding a water separator, refluxing for 9 hours to obtain a reaction liquid II, concentrating the reaction liquid II under reduced pressure, dripping the reaction liquid II into ethyl acetate, separating out solids, carrying out suction filtration, spinning the filtrate, adding petroleum ether, stirring and washing for two times, and carrying out suction filtration to obtain a brown green solid which is a metal ion probe, namely a compound II;
2) Preparation of Compound III
Under the condition of room temperature, reacting a compound II with phosphorus pentasulfide in pyridine for 26 hours to obtain a reaction solution III, purifying by column chromatography to obtain a target product, and then washing with n-hexane to obtain a pure dark green solid which is a metal ion probe, namely the compound III;
3) Preparation of Compound IV
Under the anhydrous and anaerobic condition, adding the compound II, the Lawson reagent and hexamethylphosphoric triamide into degassed toluene, carrying out reflux reaction for 2.5 hours, stopping the reaction to obtain a reaction solution IV, dripping the reaction solution IV into anhydrous diethyl ether, carrying out suction filtration to obtain a solid, dissolving the solid with dichloromethane, purifying by column chromatography, and then recrystallizing to obtain a bright copper solid, wherein the bright copper solid is the metal ion probe, namely the compound IV.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210718684.3A CN115108966B (en) | 2022-06-23 | 2022-06-23 | Benzoindole squaraine metal ion probe and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210718684.3A CN115108966B (en) | 2022-06-23 | 2022-06-23 | Benzoindole squaraine metal ion probe and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115108966A CN115108966A (en) | 2022-09-27 |
| CN115108966B true CN115108966B (en) | 2023-06-09 |
Family
ID=83327912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210718684.3A Active CN115108966B (en) | 2022-06-23 | 2022-06-23 | Benzoindole squaraine metal ion probe and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115108966B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003091689A2 (en) * | 2002-03-28 | 2003-11-06 | Rutgers, The State Of University Of New Jersey | Bis-transition-metal-chelate-probes |
| WO2010121900A1 (en) * | 2009-04-21 | 2010-10-28 | Basf Se | Dye sensitized solar cell |
| CN103214410A (en) * | 2013-04-03 | 2013-07-24 | 四川大学 | Series of asymmetrical squarine micromolecules as well as preparation method and application thereof |
| CN104163785A (en) * | 2014-06-16 | 2014-11-26 | 四川大学 | A series of asymmetric squarine micromolecules containing indoline derivative structure, and application thereof |
| CN104254576A (en) * | 2012-03-30 | 2014-12-31 | 巴斯夫欧洲公司 | Quinolinium dyes with fluorinated counter anion for dye sensitized solar cells |
| CN105061294A (en) * | 2015-08-07 | 2015-11-18 | 常州大学 | Benzindole squarylium cyanine colorimetric probe, preparation method therefor and application thereof |
| CN105623648A (en) * | 2016-02-02 | 2016-06-01 | 常州大学 | Benzindole and aniline derivative based asymmetric squaraine colorimetric probe and preparation method and application thereof |
| CN107533170A (en) * | 2015-05-20 | 2018-01-02 | 富士胶片株式会社 | Infrared ray absorbing composition, infrared ray cut off filter, layered product, pattern formation method and solid-state imaging element |
| CN107686668A (en) * | 2017-09-01 | 2018-02-13 | 常州大学 | A kind of preparation and application of the sour cyanines probe in water solubility side of sulfonic group modification |
| CN114315691A (en) * | 2022-01-17 | 2022-04-12 | 常州大学 | Asymmetric squarylium cyanine colorimetric probe for identifying copper ions and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8547533B2 (en) * | 2009-12-28 | 2013-10-01 | The United States Of America, As Represented By The Secretary, Department Of Health And Human Services | Composite probes and use thereof in super resolution methods |
-
2022
- 2022-06-23 CN CN202210718684.3A patent/CN115108966B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003091689A2 (en) * | 2002-03-28 | 2003-11-06 | Rutgers, The State Of University Of New Jersey | Bis-transition-metal-chelate-probes |
| WO2010121900A1 (en) * | 2009-04-21 | 2010-10-28 | Basf Se | Dye sensitized solar cell |
| CN104254576A (en) * | 2012-03-30 | 2014-12-31 | 巴斯夫欧洲公司 | Quinolinium dyes with fluorinated counter anion for dye sensitized solar cells |
| CN103214410A (en) * | 2013-04-03 | 2013-07-24 | 四川大学 | Series of asymmetrical squarine micromolecules as well as preparation method and application thereof |
| CN104163785A (en) * | 2014-06-16 | 2014-11-26 | 四川大学 | A series of asymmetric squarine micromolecules containing indoline derivative structure, and application thereof |
| CN107533170A (en) * | 2015-05-20 | 2018-01-02 | 富士胶片株式会社 | Infrared ray absorbing composition, infrared ray cut off filter, layered product, pattern formation method and solid-state imaging element |
| CN105061294A (en) * | 2015-08-07 | 2015-11-18 | 常州大学 | Benzindole squarylium cyanine colorimetric probe, preparation method therefor and application thereof |
| CN105623648A (en) * | 2016-02-02 | 2016-06-01 | 常州大学 | Benzindole and aniline derivative based asymmetric squaraine colorimetric probe and preparation method and application thereof |
| CN107686668A (en) * | 2017-09-01 | 2018-02-13 | 常州大学 | A kind of preparation and application of the sour cyanines probe in water solubility side of sulfonic group modification |
| CN114315691A (en) * | 2022-01-17 | 2022-04-12 | 常州大学 | Asymmetric squarylium cyanine colorimetric probe for identifying copper ions and application thereof |
Non-Patent Citations (10)
| Title |
|---|
| A novel squarylium dye for monitoring oxidative processes in lipid membranes;Valeriya M Trusova，等;J Fluoresc .;第19卷(第6期);第1017-1023页 * |
| AM1-MO理论对方酸染料结构和电子性质的研究;林童,彭必先;物理化学学报(第06期);第493-500页 * |
| Bi2S3-MnO2多功能纳米诊疗剂的制备及其性能研究;李廷华;中国优秀硕士学位论文全文数据库(第01期);第1-53页 * |
| Enhanced intersystem crossing rate in polymethine-like molecules: sulfur-containing squaraines versus oxygen-containing analogues;Davorin Peceli，等;J Phys Chem A .;第117卷(第11期);第2333-2346页 * |
| Fluorescence study of the membrane effects of aggregated lysozyme;Olga K Kutsenko，等;J Fluoresc .;第23卷(第6期);第1229-1237页 * |
| Synthesis of near-infrared absorbing pyrylium-squaraine dye for selective detection of Hg2+;Boddu Ananda Rao，等;Sensors and Actuators B: Chemical;第188卷(第11期);第847-856页 * |
| 一种基于水溶性半菁染料的Hg~(2+)识别探针;张超;欧阳峰;张兴旺;姜海燕;宋波;;山东化工(第17期);第19-20+25页 * |
| 反应型汞离子光化学传感器;冷冰;田禾;;化学进展(第05期);第67-74页 * |
| 基于方酸菁染料的光化学传感器的合成与应用研究;孙剑奇;中国优秀博士学位论文全文数据库(第11期);第1-155页 * |
| 方酸染料在离子识别中的研究;陈城;王如勇;傅南雁;;化学进展(第04期);第131-141页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115108966A (en) | 2022-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yan et al. | A selective turn-on fluorescent chemosensor based on rhodamine for Hg2+ and its application in live cell imaging | |
| CN112209871B (en) | Zinc ion fluorescent probe based on tetraphenylethylene and preparation method and application thereof | |
| CN113136205A (en) | Fluorescent carbon quantum dot, preparation method and application thereof in detecting superoxide anion | |
| CN109705111A (en) | A kind of mercury ion detecting probe and its preparation method and application | |
| CN107903257B (en) | Cyanine-based visible organic molecule fluorescent probe and preparation method thereof | |
| CN105319194B (en) | A kind of method that I and Hg2+ are continuously detected using aggregation-induced emission type fluorescence sense molecule | |
| CN109320535B (en) | Detect Cu2+Ratiometric fluorescent probe, preparation method and application thereof | |
| CN107417732A (en) | A kind of organic coordination compound mercury ion probe and preparation method and application | |
| CN115108966B (en) | Benzoindole squaraine metal ion probe and preparation method and application thereof | |
| CN110357896B (en) | Compound, preparation and application thereof in detecting divalent copper ions and strong acid pH | |
| CN109370573B (en) | Fluorescent probe for detecting bivalent mercury ions and temperature, preparation method and application thereof | |
| CN107235985A (en) | A kind of fluorescence probe for detecting bivalent cupric ion and preparation method and application | |
| CN108997401A (en) | A kind of fluorescence probe and preparation method thereof for detecting lead ion | |
| CN109053711B (en) | Probe compound for mercury ion detection and preparation method and application thereof | |
| CN113402470B (en) | Multichannel reversible colorimetric mercury ion fluorescent probe, preparation method and application | |
| CN111187289B (en) | Hydrogen peroxide fluorescent probe and preparation method and application thereof | |
| CN108191760B (en) | Fluorescent probe for detecting Cu (II) and preparation method and application thereof | |
| CN109632783B (en) | New application of indole chloride | |
| CN108485651B (en) | Application of diethyl amine acetate fluorescent micromolecules in quantitative detection of dopamine and Fe3+Method of ionizing | |
| CN113754555A (en) | Amido pyrene derivative fluorescent probe and preparation method and application thereof | |
| CN108299396B (en) | Organic compound for detecting metal ions in water environment and application thereof | |
| CN114409876B (en) | Polymer for identifying cadmium and zinc bimetallic ions, and preparation method, application and analysis method thereof | |
| CN116589493A (en) | Fluorescent probe based on mercapto naphthalimide and preparation method and application thereof | |
| CN110003175A (en) | A kind of compound and its application for detecting underwater gold category ion concentration | |
| CN112250674B (en) | 2, 3-diaminophenazine derivative and synthesis method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |