CN115108966A - Benzoindole squarylium cyanine metal ion probe and preparation method and application thereof - Google Patents
Benzoindole squarylium cyanine metal ion probe and preparation method and application thereof Download PDFInfo
- Publication number
- CN115108966A CN115108966A CN202210718684.3A CN202210718684A CN115108966A CN 115108966 A CN115108966 A CN 115108966A CN 202210718684 A CN202210718684 A CN 202210718684A CN 115108966 A CN115108966 A CN 115108966A
- 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.)
- Granted
Links
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 58
- 239000000523 sample Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 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 15
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 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 33
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 24
- 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 22
- 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 22
- 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
- 239000007787 solid Substances 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 239000012295 chemical reaction liquid Substances 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 125000004434 sulfur atom Chemical group 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- IHXWECHPYNPJRR-UHFFFAOYSA-N 3-hydroxycyclobut-2-en-1-one Chemical compound OC1=CC(=O)C1 IHXWECHPYNPJRR-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
- 238000010992 reflux Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 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
- 238000002156 mixing Methods 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
- 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
- 239000002904 solvent Substances 0.000 claims description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000862 absorption spectrum Methods 0.000 abstract description 12
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 9
- 230000004044 response Effects 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 33
- 238000012360 testing method Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 10
- 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
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000000463 material Substances 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
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 239000007850 fluorescent dye Substances 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
- 238000001228 spectrum Methods 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
- 239000003480 eluent Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- WJZSZXCWMATYFX-UHFFFAOYSA-N 1,1,2-trimethylbenzo[e]indole Chemical compound C1=CC=CC2=C(C(C(C)=N3)(C)C)C3=CC=C21 WJZSZXCWMATYFX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- -1 cyanine compound Chemical class 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 201000010099 disease 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
- 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 230000004060 metabolic process Effects 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
- 238000012545 processing Methods 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
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Pathology (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a benzindole squarylium cyanine metal ion probe, a preparation method and application thereof, wherein the metal ion probe related to the invention is a compound with a benzindole squarylium cyanine structure, and 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 on Fe 3+ 、Cu 2+ 、Hg 2+ Takes place during the identification process ofObvious color change, change of absorption spectrum and fluorescence emission spectrum, short response time, high sensitivity and no interference of other ions.
Description
Technical Field
The invention belongs to the technical field of chemical analysis and test, and particularly relates to a benzindole squarylium cyanine metal ion probe and a preparation method and application thereof.
Background
Iron and copper are two essential trace elements for human body, and play an important role in many life activities. Iron participates in processes such as 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 can be disturbed, thereby causing diseases; excess iron is also potentially harmful and may promote oxidation of fats, proteins and other components in the cell to become toxic. Similarly, deficiency or excess of copper ions in the body also causes disorders in growth and metabolism, thereby causing serious copper metabolic disorder diseases. In addition, mercury is a heavy metal element having high toxicity to humans and the environment, and its accumulation in the body causes serious health problems. Therefore, the development of a method for detecting Fe in the natural environment and in the living body with high efficiency and high selectivity 3+ 、Cu 2+ 、Hg 2+ The method of (2) is receiving attention. Conventional methods for detecting metal ions include: atomic absorption spectrophotometry, inductively coupled plasma atomic emission spectrometry, electrochemical analysis, and the like. The above methods often require the use of expensive instruments and specialized testing personnel, and are not suitable for large-scale testing and real-time testing. 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 often have the defects of complex preparation, low selectivity, insufficient red absorption and emission wavelength and the like. Therefore, probe molecules with the characteristics of high sensitivity, high selectivity, strong absorption in a near infrared region and fluorescence emission are developed to detect Fe in natural environment and in organisms 3+ 、Cu 2+ 、Hg 2+ It is of great importance.
The squaraine is a D-A-D type conjugated organic molecule formed by condensing two same or different electron-rich electron-donating units (donor, D or D') and a squaric acid core unit (acceptor, A) with strong electron-withdrawing property, and has a resonance stable zwitterion structure. 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 (ii) a And the squarylium cyanine also has the advantages of easy aggregation, simple synthetic route, good light/heat 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, and photodynamic therapy. In fact, the four-membered ring at the center of squaraine has two oxygen atoms, which can be directly used as coordination sites with metal ions; the combination of oxygen atoms and metal ions is one of the most effective methods for influencing the electron distribution in the central quaternary ring, and often leads to the remarkable change of the photophysical properties of the squarylium cyanine compound, thereby improving the sensitivity of probe molecules. In addition, the oxygen atom can be further substituted and modified by a sulfur atom, a nitrogen atom and the like, so that the binding capacity with metal ions is changed, the photophysical properties of the metal ions are adjusted, and probe molecules with different response phenomena are obtained.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, a first object of the present invention is to provide a benzindole squaraine metal ion probe;
the second purpose is to provide a preparation method of the benzindole squarylium cyanine metal ion probe;
the third purpose is to provide a benzindole squarylium cyanine metal ion probe for detecting Fe 3+ 、Cu 2+ 、Hg 2+ The use of (1).
In order to achieve the purpose, the invention provides a benzindole squarylium cyanine 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, the metal ion probe has a structural formula (I) in which:
when R is 1 、R 2 When all oxygen atoms are oxygen atoms, the compound is a compound II, and the structural formula of the compound II is shown as (II);
when R is 1 、R 2 When the two are respectively oxygen atom and sulfur atom, the compound is a compound III, and the structural formula is shown as (III);
when R is 1 、R 2 When the sulfur atoms are all sulfur atoms, the compound is a compound IV, and the structural formula of the compound IV is shown as (IV);
the structural formulas of the compound II, the compound III and the compound IV are respectively as follows:
further, the preparation methods of the compound II, the compound III and the compound IV comprise the following steps:
1) preparation of Compound II
1,1, 2-trimethyl-1H-benzo [ e ]]Indole is added with CH 3 NO 2 Adding n-butyl iodide after stirring and dissolving, heating to 100 ℃ for reaction for 14-18h, stopping the reaction to obtain a reaction solution I, concentrating the reaction solution I, slowly dropwise adding the reaction solution I into ethyl acetate, precipitating, performing suction filtration, stirring and washing a filter cake with petroleum ether, and performing suction filtration to obtain a light-grey-green precipitate B-C4;
adding B-C4, squaric acid and quinoline into a blending solvent with the volume ratio of toluene to n-butyl alcohol 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, performing suction filtration, spin-drying the filtrate, adding petroleum ether, stirring and washing twice, and performing suction filtration to obtain a brownish green solid which is a metal ion probe, namely a compound II;
2) preparation of Compound III
Reacting the compound II with phosphorus pentasulfide in pyridine for 26 hours at room temperature to obtain a reaction solution III, purifying by column chromatography to obtain a target product, and washing by using normal hexane to obtain a pure dark green solid which is a metal ion probe, namely the compound III;
3) preparation of Compound IV
Adding a compound II, a Lawson reagent, hexamethylphosphoric triamide into degassed toluene under anhydrous and anaerobic conditions, carrying out reflux reaction for 2.5h, stopping the reaction to obtain a reaction liquid IV, dripping the reaction liquid IV into anhydrous 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 which is a metal ion probe, namely the compound IV.
Further, the benzindole squarylium cyanine metal ion probe is used for detecting Fe 3+ 、Cu 2+ 、Hg 2+ The use of (1).
By adopting the scheme, the invention has the following beneficial effects:
1. the probe is blue or blue-green in acetonitrile solution, has strong absorption at the position of 600-700nm and strong fluorescence emission at the position of 650-850nm, and has the advantages of small light damage, strong tissue penetrating capability, low autofluorescence interference and the like. The solution of the probe of the invention is added with Fe respectively 3+ 、Cu 2+ 、Hg 2+ Obvious color change can be presented later, naked eye detection can be carried out without other equipment, and simultaneously, corresponding absorption spectrum and fluorescence emission spectrum also change, so that Fe can be detected by colorimetric and spectroscopic tests 3+ 、Cu 2+ 、Hg 2+ The double-channel detection is carried out, and the interference of other metal ions is avoided, so that the method has a good application prospect.
2. The metal ion probe related by the invention has the advantages of simple synthetic route, easily obtained raw materials and simple operation.
3. The metal ion probe related by the invention is added with Fe 3+ 、Cu 2+ 、Hg 2+ The response phenomenon appears immediately, the response time is very 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 scheme for the preparation of compound II.
FIG. 2 is a scheme for the preparation of compound III.
FIG. 3 is a flow chart of the preparation of Compound IV.
FIG. 4 is an absorption spectrum of compound II for selectivity test of different metal ions.
FIG. 5 is the fluorescence emission spectrum of compound IV for different metal ion selectivity tests.
FIG. 6 shows the recognition of Fe by other metal ions to compound II 3+ And (4) testing the interference.
FIG. 7 shows that different equivalent ratios of Fe are added to compound II 3+ Absorption spectrum after solution.
FIG. 8 shows the addition of Fe to Compound III 3+ The absorption wavelength at 663nm changes with time.
FIG. 9 is a colorimetric color development of compound III on different metal ions.
Detailed Description
The present invention is described in detail below with reference to the attached drawings and examples, which are not intended to limit the invention in any way, except as specifically stated, reagents, methods and apparatus that are conventional in the art.
Example 1: preparation of benzindole squarylium cyanine metal ion probe
1. Experimental methods
The method comprises the following specific steps:
1) the preparation of the compound II, the preparation flow is shown in figure 2;
1,1, 2-trimethyl-1H-benzo [ e]Indole (10.00g, 47.50mmol) was added to 80mL CH 3 NO 2 Adding n-iodo-butyl after stirring and dissolvingAlkane (21.50g, 95.50mmol), heating to 100 ℃ for 14h, detecting by TLC that part of raw materials in the system still remain unreacted, adding 1.8mL of n-butyl iodide, continuing to heat to 100 ℃ for 4h, stopping the reaction to obtain a reaction solution I, concentrating the reaction solution I to 50mL, slowly dripping the reaction solution I into 350mL of ethyl acetate, precipitating, filtering, stirring and washing a filter cake with petroleum ether, and filtering to obtain a light grey green precipitate B-C4, wherein the B-C4 is 16g, and the yield is 86%;
adding B-C4(10.00g, 25.4mmol), squaric acid (1.45g, 12.7mmol) and quinoline (3.30g, 25.4mmol) into a blending solvent with a volume ratio of 150mL of toluene to n-butanol of 1:1, refluxing in boiling water for 9h to obtain a reaction solution II, concentrating the reaction solution II under reduced pressure to 20mL, dropping into 300mL of ethyl acetate, precipitating a solid, performing suction filtration, spin-drying the filtrate, adding 200mL of petroleum ether, stirring and washing twice, and performing suction filtration to obtain a brownish green solid which is a metal ion probe, namely a compound II, wherein the compound II is 4.16g, and the yield is 54%;
2) the preparation of compound III, the preparation flow is shown in figure 3;
reacting the compound II (0.54g, 0.89mmol) and phosphorus pentasulfide (0.79g, 1.80mmol) in pyridine (6mL) at room temperature for 26h to obtain a reaction liquid III, purifying by column chromatography (200-300 silica gel, and an eluent is dichloromethane) to obtain a target product, and washing by using n-hexane to obtain a pure dark green solid which is a metal ion probe, namely the compound III, wherein the compound III is 0.39g, and the yield is 69%;
3) the preparation of the compound IV is shown in figure 4;
adding a compound II (0.20g, 0.33mmol), a Lawson reagent (0.27g, 0.66mmol) and hexamethylphosphoric triamide (HMPA, 0.13mL) into 15mL degassed toluene under anhydrous and anaerobic conditions, carrying out reflux reaction for 2.5h, stopping the reaction to obtain a reaction liquid IV, dripping the reaction liquid IV into 100mL anhydrous ether, carrying out suction filtration to obtain a solid, dissolving the solid with dichloromethane, purifying by column chromatography (100-200 mesh silica gel, eluent dichloromethane: petroleum ether: 1), and then recrystallizing (dichloromethane: ethanol: 1:3) to obtain a bright copper-colored solid which is a metal ion probe, namely the compound IV, wherein the compound IV is 0.07g, and the yield is 33%;
and carrying out structure identification on the obtained compound II, compound III and compound IV through nuclear magnetic resonance hydrogen spectrum and carbon spectrum respectively.
2. Results of the experiment
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.
a 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 Material
Metal ion Probe Compound II, Compound III, Compound IV prepared in example 1
2. Experimental methods
10mL of metal ion probe compound II or compound III or CH of compound IV are added to 21 test tubes numbered 1-21 respectively 3 CN solution (1.0X 10) -5 mol/L), respectively adding 50 mu L of different metal ion aqueous solutions (Fe) into test tubes 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+ And c is 0.04mol/L), standing for 30min after shaking, and performing absorption spectrum and fluorescence emission spectrum tests.
3. Results of the experiment
As shown in FIGS. 1, 5 and 9, Fe is added 3+ 、Cu 2+ 、Hg 2+ Then, the color of the metal ion probe compound II or compound III or compound IV solution 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 shows that the metal ion probe is used for detecting Fe 3+ 、Cu 2+ 、Hg 2+ Has good identification capability.
Example 3: other metal ion pair metal ion probe recognition Fe 3+ Interference testing of time
1. Experimental Material
Metal ion Probe Compound II prepared in example 1
2. Experimental methods
To 21 tubes numbered 1-21, 10mL of metal ion probe compound II (1.0X 10) -5 mol/L) of CH 3 CN solution, 50 mu L of Fe is added into test tubes No. 2-21 3+ Adding 50 μ L of different metal ions (Fe) into test tubes 3-21 in an aqueous solution (0.04mol/L) 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+ And c is 0.04mol/L) aqueous solution, shaking and standing for 30min, and performing absorption spectrum and fluorescence emission spectrum tests.
3. Results of the experiment
As shown in FIG. 6, the results indicate that the probe molecule pairs Fe 3+ The recognition is not interfered by other metal ions.
Example 4: metal ion probe for different concentration Fe 3+ 、Cu 2+ 、Hg 2+ Response of aqueous solution
1. Experimental Material
Metal ion Probe Compound II prepared in example 1
2. Experimental methods
To 31 tubes numbered 1-31, 10mL of probe compound II (1.0X 10) -5 mol/L) of CH 3 CN solution, and sequentially adding Fe (0.0-20.0 equivalents) with different equivalent ratios into each test tube 3+ Or Cu 2+ Or Hg 2+ And (0.01mol/L) water solution, shaking and standing for 30min, and performing absorption spectrum and fluorescence emission spectrum tests.
3. Results of the experiment
As shown in fig. 7, with Fe 3+ Or Cu 2+ Or Hg 2+ The equivalent weight is increased, the intensities of the absorption spectrum and the emission spectrum of the probe molecule are sequentially reduced, and the Fe of the probe molecule pair can be obtained by processing and calculating experimental data 3+ 、Cu 2+ 、Hg 2+ The lowest detection limit of (D) 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 Material
Metal ion Probe Compound III prepared in example 1
2. Experimental methods
To a two-sided quartz cuvette, 2mL of probe compound III (1.0X 10) -5 mol/L) of CH 3 CN solution, testing its absorption spectrum and fluorescence emission spectrum, adding Fe into the cuvette after testing 3+ Or Cu 2+ Or Hg 2+ (0.01mol/L) of an aqueous solution, and immediately after shaking, the absorption spectrum and fluorescence emission spectrum were measured, followed by measuring the absorption spectrum and fluorescence emission spectrum every 2 minutes.
3. Results of the experiment
As shown in FIG. 8, when Fe is added 3+ Or Cu 2+ Or Hg 2+ Then, the intensities at the maximum absorption wavelength and the maximum emission wavelength of the probe molecule are both reduced immediately and then tend to be stable, which indicates that the response speed of the probe molecule to the metal ions is high.
Finally, it is to be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (4)
1. A benzindole squarylium cyanine metal ion probe is characterized in that the metal ion probe has the following structural formula (I):
wherein R is 1 、R 2 Is an oxygen atom or a sulfur atom.
2. The benzindole squaraine metal ion probe of claim 1, wherein the metal ion probe has a structural formula (i):
when R is 1 、R 2 When all oxygen atoms are oxygen atoms, the compound is a compound II, and the structural formula of the compound II is shown as (II);
when R is 1 、R 2 When the two are respectively oxygen atom and sulfur atom, the compound is a compound III, and the structural formula is shown as (III);
when R is 1 、R 2 When the sulfur atoms are all sulfur atoms, the compound is a compound IV, and the structural formula of the compound IV is shown as (IV);
the structural formulas of the compound II, the compound III and the compound IV are respectively as follows:
3. the benzindole squarylium cyanine metal ion probe according to claim 2, wherein the preparation method of the compound II, the compound III and the compound IV comprises the following steps:
1) preparation of Compound II
1,1, 2-trimethyl-1H-benzo [ e ]]Indole is added to CH 3 NO 2 Adding n-butyl iodide after stirring and dissolving, heating to 100 ℃ for reaction for 14-18h, stopping the reaction to obtain a reaction solution I, concentrating the reaction solution I, slowly dropwise adding the reaction solution I into ethyl acetate, precipitating, performing suction filtration, stirring and washing a filter cake with petroleum ether, and performing suction filtration to obtain a light-grey-green precipitate B-C4;
adding B-C4, squaric acid and quinoline into a blending solvent with the volume ratio of toluene to n-butyl alcohol 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, performing suction filtration, spin-drying the filtrate, adding petroleum ether, stirring and washing twice, and performing suction filtration to obtain a brownish green solid which is a metal ion probe, namely a compound II;
2) preparation of Compound III
Reacting the compound II with phosphorus pentasulfide in pyridine for 26 hours at room temperature to obtain a reaction solution III, purifying by column chromatography to obtain a target product, and washing by using normal hexane to obtain a pure dark green solid which is a metal ion probe, namely the compound III;
3) preparation of Compound IV
Adding a compound II, a Lawson reagent, hexamethylphosphoric triamide into degassed toluene under anhydrous and anaerobic conditions, carrying out reflux reaction for 2.5h, stopping the reaction to obtain a reaction liquid IV, dripping the reaction liquid IV into anhydrous 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 which is a metal ion probe, namely the compound IV.
4. The method for detecting Fe by using the benzindole squaraine metal ion probe according to any one of claims 1-3 3+ 、Cu 2+ 、Hg 2+ The use of (1).
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 true CN115108966A (en) | 2022-09-27 |
| CN115108966B 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 (11)
| 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 |
| US20120309045A1 (en) * | 2009-12-28 | 2012-12-06 | Knutson Jay R | Composite Probes and Use Thereof in Super Resolution Methods |
| 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 |
-
2022
- 2022-06-23 CN CN202210718684.3A patent/CN115108966B/en active Active
Patent Citations (11)
| 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 |
| US20120309045A1 (en) * | 2009-12-28 | 2012-12-06 | Knutson Jay R | Composite Probes and Use Thereof in Super Resolution Methods |
| 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 |
|---|
| BODDU ANANDA RAO，等: "Synthesis of near-infrared absorbing pyrylium-squaraine dye for selective detection of Hg2+", SENSORS AND ACTUATORS B: CHEMICAL, vol. 188, no. 11, pages 847 - 856 * |
| DAVORIN PECELI，等: "Enhanced intersystem crossing rate in polymethine-like molecules: sulfur-containing squaraines versus oxygen-containing analogues", J PHYS CHEM A ., vol. 117, no. 11, pages 2333 - 2346 * |
| OLGA K KUTSENKO，等: "Fluorescence study of the membrane effects of aggregated lysozyme", J FLUORESC ., vol. 23, no. 6, pages 1229 - 1237 * |
| VALERIYA M TRUSOVA，等: "A novel squarylium dye for monitoring oxidative processes in lipid membranes", J FLUORESC ., vol. 19, no. 6, pages 1017 - 1023, XP019750483, DOI: 10.1007/s10895-009-0501-z * |
| 冷冰;田禾;: "反应型汞离子光化学传感器", 化学进展, no. 05, pages 67 - 74 * |
| 孙剑奇: "基于方酸菁染料的光化学传感器的合成与应用研究", 中国优秀博士学位论文全文数据库, no. 11, pages 1 - 155 * |
| 张超;欧阳峰;张兴旺;姜海燕;宋波;: "一种基于水溶性半菁染料的Hg~(2+)识别探针", 山东化工, no. 17, pages 19 - 20 * |
| 李廷华: "Bi2S3-MnO2多功能纳米诊疗剂的制备及其性能研究", 中国优秀硕士学位论文全文数据库, no. 01, pages 1 - 53 * |
| 林童,彭必先: "AM1-MO理论对方酸染料结构和电子性质的研究", 物理化学学报, no. 06, pages 493 - 500 * |
| 陈城;王如勇;傅南雁;: "方酸染料在离子识别中的研究", 化学进展, no. 04, pages 131 - 141 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115108966B (en) | 2023-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103865520B (en) | Based on zinc ion fluorescent and the application thereof of chelation evoked Fluorescence Increasing | |
| CN112159522B (en) | Water-soluble rhodamine-based fluorescent/colorimetric dual-mode probe and preparation method and application thereof | |
| CN109705111A (en) | A kind of mercury ion detecting probe and its preparation method and application | |
| CN107739394B (en) | A kind of Supramolecular self assembly body and the preparation method and application thereof for copper ion fluoroscopic examination | |
| CN114315691B (en) | Asymmetric squaraine colorimetric probe for identifying copper ions and application thereof | |
| CN104788344B (en) | The one class difunctional fluorescent probe with anthracene as parent, preparation method and application | |
| CN105319194B (en) | A kind of method that I and Hg2+ are continuously detected using aggregation-induced emission type fluorescence sense molecule | |
| CN108997401A (en) | A kind of fluorescence probe and preparation method thereof for detecting lead ion | |
| CN100560583C (en) | Detect the near infrared fluorescent probe and the preparation method and use of zinc ion in cell | |
| CN107382900B (en) | Preparation method and application of pH fluorescent probe | |
| CN110357896B (en) | Compound, preparation and application thereof in detecting divalent copper ions and strong acid pH | |
| CN115108966B (en) | Benzoindole squaraine metal ion probe and preparation method and application thereof | |
| CN105085340B (en) | Diphenylethene group dual cyano benzene two-photon fluorescence probe for detecting and displaying intracellular Hg ion | |
| CN107235985A (en) | A kind of fluorescence probe for detecting bivalent cupric ion and preparation method and application | |
| CN114874188B (en) | Lipid-droplet fluorescent probe containing carbazole-pyridine formylhydrazine group and preparation method and application thereof | |
| CN115677554A (en) | 3,4-dithioether maleimide derivative fluorescent molecule based on aggregation-induced emission, and preparation method and application thereof | |
| CN110003175A (en) | A kind of compound and its application for detecting underwater gold category ion concentration | |
| CN114014891B (en) | Purine ring modified fluorescent probe and application thereof in detection of cobalt ions | |
| CN107831165B (en) | Double-channel copper ion detection test paper and preparation method thereof | |
| CN110590784B (en) | Derivative based on pyrrolopyrroledione and preparation method and application thereof | |
| CN114507239A (en) | Spiropyran N-amphetamine compound colorimetric probe for detecting copper ions and preparation method thereof | |
| CN108191760B (en) | Fluorescent probe for detecting Cu (II) and preparation method and application thereof | |
| CN110066290B (en) | Organic silicon Schiff base fluorescent probe and application thereof | |
| CN107098852A (en) | The amine-modified pyrene derivatives fluorescence probe of two (2 picolines) and its synthetic method and application | |
| CN112358485A (en) | Fluorescent probe for visual detection of copper ions in plant root system and preparation method 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 |