CN117843969A - Composite fluorescent sensing material and preparation method and application thereof - Google Patents
Composite fluorescent sensing material and preparation method and application thereof Download PDFInfo
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- 239000011540 sensing material Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 155
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 23
- 238000012544 monitoring process Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 29
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- -1 alkylnitrobenzene Chemical compound 0.000 claims description 22
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 18
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 12
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 claims description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000004530 micro-emulsion Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- LAXFTJSQHNKERQ-UHFFFAOYSA-N 2-sulfanylbenzene-1,3-diol Chemical compound OC1=CC=CC(O)=C1S LAXFTJSQHNKERQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000005844 heterocyclyloxy group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000004971 nitroalkyl group Chemical group 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 41
- 238000001514 detection method Methods 0.000 abstract description 27
- 230000035945 sensitivity Effects 0.000 abstract description 15
- 238000004523 catalytic cracking Methods 0.000 abstract description 2
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 2
- 238000001833 catalytic reforming Methods 0.000 abstract description 2
- 238000004939 coking Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 39
- 239000007850 fluorescent dye Substances 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 239000012071 phase Substances 0.000 description 21
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 238000006862 quantum yield reaction Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 8
- 230000005284 excitation Effects 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- 235000011056 potassium acetate Nutrition 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 8
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 6
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 4
- FTBCOQFMQSTCQQ-UHFFFAOYSA-N 4-bromobenzenethiol Chemical compound SC1=CC=C(Br)C=C1 FTBCOQFMQSTCQQ-UHFFFAOYSA-N 0.000 description 4
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000028571 Occupational disease Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 208000019425 cirrhosis of liver Diseases 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- BBCAQPYJVYMQFB-UHFFFAOYSA-N sodium;2-methylpropane Chemical compound [Na+].C[C-](C)C BBCAQPYJVYMQFB-UHFFFAOYSA-N 0.000 description 1
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
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Abstract
The invention relates to the technical field of fluorescent material preparation, and discloses a composite fluorescent sensing material, a preparation method and application thereof. The composite fluorescent sensing material comprises: a covalent organic framework material containing a repeating unit represented by the formula (11), and a compound represented by the formula (1) supported on the covalent organic framework material. The composite fluorescent sensing material provided by the invention is directly oriented to the leakage monitoring and detection problems of hydrogen sulfide gas in petrochemical industry, and can be used for rapidly detecting the leaked hydrogen sulfide in the environment with high sensitivity and high selectivity, so that the safety of personnel, environment and equipment is ensured, and the composite fluorescent sensing material can be used in catalytic cracking, hydrocracking, catalytic reforming, coking and other devices.
Description
Technical Field
The invention relates to the technical field of fluorescent material preparation, in particular to a composite fluorescent sensing material and a preparation method and application thereof.
Background
Hydrogen sulfide (H) 2 S) is colorless gas, has the odor of the smelly eggs, has corrosiveness, combustibility and explosiveness, has extremely high toxicity and has the lethal concentration of only 120ppm, and is common oilfield associated gas. Hydrogen sulfide is listed in the hazardous chemical directory of first-order major supervision (An-prison Bo-San [2011 ]]95) and "category of occupational disease risk factors catalogue" (state Wei Ji control of issuing [2015 ]]92). The hydrogen sulfide poisoning accident has the characteristics of burst, population, high mortality rate and the like, so that the rapid, effective, convenient, high-sensitivity and high-selectivity detection of the hydrogen sulfide is realized, the harm caused by the hydrogen sulfide is reduced, and the urgent need for protecting the health of people in China, the national environmental safety and the economic development is met.
Current methods for hydrogen sulfide detection can be divided into: detection tube methods, colorimetric methods, iodometric methods and the like based on chemical reactions, which are low in cost but require special personnel to operate, have complex detection processes and low sensitivity; high-sensitivity detection of hydrogen sulfide can be realized by gas chromatography-mass spectrometry (GC-MS), spectrophotometry and the like based on large instruments, but the technology has the defects of high equipment price, large volume, poor portability and the like, and cannot meet the requirement of on-site rapid detection. Compared with the above method, the fluorescence sensing technology has been paid attention to because of the advantages of portability, high sensitivity, low cost, strong interference resistance, capability of realizing real-time detection and the like, and has been applied to detection of various toxic and harmful substances.
In recent years, fluorescent probes for detecting hydrogen sulfide have been receiving attention from scholars at home and abroad because hydrogen sulfide is an important active species in organisms, and abnormal concentration changes are often accompanied by the occurrence of many diseases such as inflammation, cancer, alzheimer's disease, liver cirrhosis, and the like. The design of hydrogen sulfide probes is mainly based on several reaction mechanisms: reduction of azide, cleavage of alkoxy/thioxy bonds, nucleophilic reactions, substitution of copper complexes, formation of sulfide precipitates, and the like. The molecular backbone of the probe is mostly based on organic molecules such as coumarin, BODIPY (BODIPY), rhodamine, terpyridine, fluorescein, porphyrin, and the like. Although these probes have shown great advantages in the detection of hydrogen sulfide in organisms, the detection medium is in a liquid phase and requires a long time for reaction, and thus they do not meet the requirements for hydrogen sulfide gas detection in the petrochemical industry and the like.
The report about the fluorescent method for detecting the gaseous hydrogen sulfide in the petrochemical industry environment is less, the reported literature and patent have the defects of complex preparation process, single detection form and the like of the fluorescent probe, and most of the problems are limited by preparing the probe into fluorescent test paper, and the operation flow is simple, but the reaction time is longer and the sensitivity is lower. In view of the reported shortcomings of the fluorescent sensing materials, the development of a stable sensing material which has high sensitivity (ppb level), good selectivity and can rapidly detect hydrogen sulfide in real time (second level) is still a problem to be solved. However, most fluorescent sensing materials formed by supermolecule self-assembly have low luminous efficiency and poor stability due to aggregation-induced fluorescence quenching effect caused by pi-pi accumulation among molecules. In addition, as the specific surface area of the material is small and the stacking is tight, target molecules cannot penetrate into the material, the capture of the sensing material to the target molecules is limited, and the improvement of selectivity and sensitivity is not facilitated.
Disclosure of Invention
The invention aims to solve the problems of complex detection process, low sensitivity, high equipment price, large volume, poor portability and the like of the existing hydrogen sulfide detection technology, and the problems of easy fluorescence quenching, low luminous efficiency, poor stability, poor sensitivity and the like of a fluorescence sensing material.
In order to achieve the above object, a first aspect of the present invention provides a composite fluorescent sensing material comprising: a covalent organic framework material containing a repeating unit represented by formula (11), and a compound represented by formula (1) supported on the covalent organic framework material;
wherein K1 and K2 are each independently selected from pyridine, pyridinylalkyl, phenylcyano, alkylphenylcyano, nitrobenzene, alkylnitrobenzene, hydroxy, mercapto, hydroxybenzene, alkylhydroxybenzene, mercaptophenyl, alkylmercapto mercapto;
wherein R1 is selected from any one of the following groups:
n is an integer of 1 to 10;
r2 is selected from pyridine, alkylpyridine, phenylcyano, alkylphenylcyano, nitrobenzene, nitroalkyl, phenylmercaptoalkyl, cyanocycloalkyl, cyanoheterocyclyl, alkylnitrobenzene, alkyl, alkyloxy, alkenyl, hydroxy, phenylhydroxy, aryl, heteroaryl, heteroaryloxy, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclyloxy, or phenylmercapto.
Preferably, the compound represented by formula (1) is supported on the inner walls of the cells of the covalent organic framework material containing the repeating unit represented by formula (11).
Preferably, R2 is selected from nitro C1-12 straight or branched alkyl, nitrophenyl C1-C12 alkyl, phenylmercapto C1-C12 cycloalkyl, cyanoC 1-C12 cycloalkyl or cyanoC 1-C12 heterocyclyl.
Preferably, R2 is selected from nitro C1-C6 alkyl, nitrophenyl C1-C6 alkyl, phenylmercapto C1-C6 cycloalkyl, cyanoC 1-C6 cycloalkyl or cyanoC 1-C12 heterocyclyl
Preferably, R2 is selected from any one of the following groups:
the second aspect of the present invention provides a method for preparing a composite fluorescent sensing material, the method comprising the steps of:
s21: mixing a compound shown in a formula (12), a compound shown in a formula (13), a compound shown in a formula (1) and an organic solvent to obtain an oil phase;
s22: scandium triflate, a surfactant and water are mixed to obtain a water phase;
s23: mixing the water phase and the oil phase, emulsifying to form micro emulsion, and performing polymerization reaction at an emulsion interface to obtain a primary product;
s24: transferring the preliminary product into acetic acid aqueous solution for crystallization to obtain a composite fluorescent sensing material;
wherein, K1 and K2 are as defined above.
Preferably, the compound represented by formula (12), the compound represented by formula (13) and the compound represented by formula (1) are used in a molar ratio of 1:1:2-10.
Preferably, the molar ratio of the surfactant, scandium triflate and the compound shown in the formula (1) is 0.02-0.2:0.1-0.3:1.
Preferably, in step S21, the organic solvent is selected from chloroform, dichloromethane or ethyl acetate.
Preferably, in step S24, the conditions for crystallization include: the temperature is-5 ℃ to 5 ℃ and the time is 24-48 hours.
Preferably, the preparation method of the compound represented by formula (1) comprises the steps of:
s11: reacting a compound shown in a formula (2) with a compound shown in a formula (3) in the presence of a catalyst system A in an inert atmosphere to obtain a compound shown in a formula (4);
s12: reacting a compound shown in a formula (4) with a compound shown in a formula (5) in the presence of a catalyst system B in an inert atmosphere to obtain a compound shown in a formula (6);
s13: reacting a compound shown in a formula (3) with a compound shown in a formula (7) in the presence of a catalyst system A in an inert atmosphere to obtain a compound shown in a formula (8);
s14: reacting a compound shown in a formula (8) with a compound shown in a formula (9) in the presence of a catalyst system B in an inert atmosphere to obtain a compound shown in a formula (10);
s15: reacting a compound shown in a formula (6) with a compound shown in a formula (10) in the presence of a catalyst C in an inert atmosphere to obtain a compound shown in a formula (1);
wherein R1 is as defined in claim 1 and R2 is as defined in claim 1, 3, 4 or 5;
X1-X4 are each independently selected from halogen;
the catalyst system A contains acetate and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride;
the catalyst system B contains tetrakis (triphenylphosphine) palladium and a carbonate;
the catalyst C is sodium tert-butoxide.
Preferably, in step S11, the molar ratio of acetate in catalyst system a to the amount of compound of formula (2) is from 2 to 10:1; the molar ratio of the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride to the compound shown in the formula (2) in the catalyst system A is 0.05-0.4:1;
preferably, in step S13, the molar ratio of acetate in catalyst system a to the amount of compound of formula (7) is from 2 to 5:1; the molar ratio of the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride to the compound represented by the formula (7) in the catalyst system A is 0.1-0.3:1.
Preferably, in step S12, the molar ratio of tetrakis (triphenylphosphine) palladium to the amount of the compound represented by formula (5) in catalyst system B is 0.03 to 0.2:1; the molar ratio of carbonate in the catalyst system B to the amount of the compound represented by the formula (5) is 1-5:1;
preferably, in step S14, the molar ratio of tetrakis (triphenylphosphine) palladium to the amount of the compound represented by formula (8) used in catalyst system B is from 0.05 to 0.1:1; the molar ratio of carbonate to the amount of compound of formula (8) in catalyst system B is 1-3:1.
Preferably, the temperature of the reaction in step S11 is 50-90 ℃;
preferably, the temperature of the reaction in step S12 is 60-90 ℃;
preferably, the temperature of the reaction in step S13 is 60-80 ℃;
preferably, the temperature of the reaction in step S14 is 70-80 ℃.
Preferably, in step S11, the molar ratio of the compound represented by formula (2) to the amount of the compound represented by formula (3) is 1:1 to 1.5;
preferably, in step S12, the molar ratio of the compound represented by formula (4) to the amount of the compound represented by formula (5) is 2-2.5:1;
preferably, in step S13, the molar ratio of the compound represented by formula (3) to the amount of the compound represented by formula (7) is 4 to 6:1;
preferably, in step S14, the molar ratio of the compound represented by formula (8) to the amount of the compound represented by formula (9) is 0.4 to 0.6:1.
Preferably, in step S15, the molar ratio of the catalyst C to the amount of the compound represented by formula (10) is 1:1 to 1.5;
preferably, the molar ratio of the compound of formula (6) to the amount of the compound of formula (10) is 2-4:1, preferably 2-2.2:1.
Preferably, in step S15, the conditions of the reaction include: the reaction temperature is 90-120 ℃.
The third aspect of the invention provides an application of the composite fluorescent sensing material or the composite fluorescent sensing material prepared by the method in leakage monitoring or detection of hydrogen sulfide gas.
The invention provides a composite fluorescent sensing material rich in multiple hydrogen sulfide action sites, which takes polyhydroxy covalent organic framework materials (COFs) as a material platform, adopts a synthesis method of emulsion interface self-assembly, and embeds a fluorescent probe which is shown in a formula (1) and can perform specific recognition with hydrogen sulfide into the mesoporous interior of the COFs in a monomer form through non-covalent bond action. The rapid (second-level) and high-sensitivity (< 1 ppm) detection of the hydrogen sulfide is realized through the synergistic specific recognition action mechanism of the COFs and the fluorescent probe on the hydrogen sulfide. Compared with the traditional fluorescent probe detection means, the specific synergistic recognition action mechanism has higher sensitivity and quicker response time. The composite fluorescent sensing material has high fluorescence quantum yield of 40-70%, and mainly benefits from embedding fluorescent probe molecules into COFs mesoporous in a monomer form, and the method eliminates aggregation-induced fluorescence quenching effect caused by pi-pi accumulation among traditional fluorescent probe molecules, so that the sensing material has high fluorescence emission efficiency.
The composite fluorescent sensing material provided by the invention is directly oriented to the leakage monitoring and detection problems of hydrogen sulfide gas in petrochemical industry, and can be used for rapidly detecting the leaked hydrogen sulfide in the environment with high sensitivity and high selectivity, so that the safety of personnel, environment and equipment is ensured, and the composite fluorescent sensing material can be used in catalytic cracking, hydrocracking, catalytic reforming, coking and other devices.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a compound shown in formula 1-1 in example 1.
FIG. 2 is a mass spectrum of the compound shown in formula 1-1 in example 1.
FIG. 3 is a graph showing the fluorescence emission spectrum of the composite fluorescent sensing material prepared in example 1.
Fig. 4 is a scanning electron microscope image of the composite fluorescent sensing material prepared in example 1.
FIG. 5 is an ultraviolet-visible absorption spectrum of the composite fluorescent sensing material prepared in example 1.
FIG. 6 is a timing chart showing the fluorescence change of the composite fluorescent sensing material prepared in example 1 with respect to hydrogen sulfide vapors of different concentrations.
FIG. 7 is a timing chart showing the change in fluorescence of the fluorescent probe of comparative example 1 for hydrogen sulfide vapors of different concentrations.
FIGS. 8-13 are timing diagrams of fluorescence change of the composite fluorescent sensing material of example 1 for different concentrations of interfering gas.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a composite fluorescent sensing material comprising: a covalent organic framework material containing a repeating unit represented by formula (11), and a compound represented by formula (1) supported on the covalent organic framework material;
wherein K1 and K2 are each independently selected from pyridine, pyridinylalkyl, phenylcyano, alkylphenylcyano, nitrobenzene, alkylnitrobenzene, hydroxy, mercapto, hydroxybenzene, alkylhydroxybenzene, mercaptophenyl, alkylmercapto mercapto;
wherein R1 is selected from any one of the following groups:
n is an integer of 1 to 10;
r2 is selected from pyridine, alkylpyridine, phenylcyano, alkylphenylcyano, nitrobenzene, alkylnitrobenzene, alkyl, alkyloxy, alkenyl, hydroxy, phenylhydroxy, aryl, heteroaryl, heteroaryloxy, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclyloxy, or phenylmercapto.
In a preferred embodiment, the compound of formula (1) is supported on the inner walls of the pores of the covalent organic framework material containing the repeating unit of formula (11).
In the present invention, a covalent organic framework material containing a repeating unit represented by formula (11) that can have a synergistic effect with the fluorescent probe represented by formula (1) is selected to prepare a composite fluorescent sensing material. The covalent organic framework material has the following advantages:
1. the mesoporous size and physicochemical properties of the COFs are suitable for loading fluorescent probe molecules on the inner wall of a pore canal of the COFs in a monomer form through non-covalent bond interaction (H bond and the like), and the mode can eliminate aggregation-induced fluorescence quenching effect caused by pi-pi accumulation among the fluorescent probe molecules, so that the sensing material achieves high-efficiency fluorescence emission efficiency.
2. The COFs structure contains a group capable of non-covalent interaction with hydrogen sulfide, and when hydrogen sulfide is captured by a recognition group in the COFs, the change of a fluorescent signal of a probe molecule can be triggered by influencing the energy of the excited state of the COFs, so that the detection sensitivity is further improved.
3. The COFs has a high specific surface area and a regular pore structure, so that hydrogen sulfide molecules can easily enter the COFs, and the probability and the quantity of contact between the hydrogen sulfide and the composite fluorescent sensing material are improved.
Preferably, R2 is selected from nitro C1-12 straight or branched alkyl, nitrophenyl C1-C12 alkyl, phenylmercapto C1-C12 cycloalkyl, cyanoC 1-C12 cycloalkyl or cyanoC 1-C12 heterocyclyl.
Preferably, R2 is selected from nitro C1-C6 alkyl, nitrophenyl C1-C6 alkyl, phenylmercapto C1-C6 cycloalkyl, cyanoC 1-C6 cycloalkyl or cyanoC 1-C12 heterocyclyl
Further preferably, R2 is selected from any one of the following groups:
the second aspect of the present invention provides a method for preparing a composite fluorescent sensing material, the method comprising the steps of:
s21: mixing a compound shown in a formula (12), a compound shown in a formula (13), a compound shown in a formula (1) and an organic solvent to obtain an oil phase;
s22: scandium triflate, a surfactant and water are mixed to obtain a water phase;
s23: mixing the water phase and the oil phase, emulsifying to form micro emulsion, and performing polymerization reaction at an emulsion interface to obtain a primary product;
s24: transferring the preliminary product into acetic acid aqueous solution for crystallization to obtain a composite fluorescent sensing material;
wherein, K1 and K2 are as defined above.
In a preferred embodiment, K1 and K2 are the same substituent.
In a preferred embodiment, the compound represented by formula (12), the compound represented by formula (13) and the compound represented by formula (1) are used in a molar ratio of 1:1:2-10 in order to improve the fluorescence quantum yield and sensitivity of the composite fluorescent material. Specifically, it may be 1:1:2, 1:1:3, 1:1:4, 1:1:5, 1:1:6, 1:1:7, 1:1:8, 1:1:9, or 1:1:10.
In a preferred embodiment, in step S23, the volume ratio of the aqueous phase to the oil phase is 1:1-3.
In a preferred embodiment, in step S24, the aqueous acetic acid solution is obtained from acetic acid and water in a volume ratio of 1-3:10.
In a preferred embodiment, scandium triflate is used as a catalyst in the preparation method of the composite fluorescent sensing material.
In a preferred embodiment, there are no particular requirements for the selection of the surfactant, and various surfactants conventionally used in the art are used. Such as dodecyl trimethyl ammonium bromide, sodium stearyl sulfate, sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide, and the like.
In a preferred embodiment, the surfactant, scandium triflate and the compound of formula (1) are used in a molar ratio of 0.02-0.2:0.1-0.3:1.
In a preferred embodiment, in step S21, the organic solvent is selected from chloroform, dichloromethane or ethyl acetate.
In a preferred embodiment, in step S24, the crystallization conditions include: the temperature is-5 ℃ to 5 ℃ and the time is 24-48 hours.
In a preferred embodiment, the method for producing the compound represented by formula (1) comprises the steps of:
s11: reacting a compound shown in a formula (2) with a compound shown in a formula (3) in the presence of a catalyst system A in an inert atmosphere to obtain a compound shown in a formula (4);
s12: reacting a compound shown in a formula (4) with a compound shown in a formula (5) in the presence of a catalyst system B in an inert atmosphere to obtain a compound shown in a formula (6);
s13: reacting a compound shown in a formula (3) with a compound shown in a formula (7) in the presence of a catalyst system A in an inert atmosphere to obtain a compound shown in a formula (8);
s14: reacting a compound shown in a formula (8) with a compound shown in a formula (9) in the presence of a catalyst system B in an inert atmosphere to obtain a compound shown in a formula (10);
s15: reacting a compound shown in a formula (6) with a compound shown in a formula (10) in the presence of a catalyst C in an inert atmosphere to obtain a compound shown in a formula (1);
wherein R1 is as defined in claim 1 and R2 is as defined in claim 1, 3, 4 or 5;
X1-X4 are each independently selected from halogen;
the catalyst system A contains acetate and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride;
the catalyst system B contains tetrakis (triphenylphosphine) palladium and a carbonate;
catalyst C is tert-butyl sodium.
In a preferred embodiment, in step S11, the molar ratio of acetate in the catalyst system a to the amount of compound of formula (2) is from 2 to 10:1; the molar ratio of the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride to the compound shown in the formula (2) in the catalyst system A is 0.05-0.4:1;
in a preferred embodiment, in step S13, the molar ratio of acetate in the catalyst system a to the amount of compound of formula (7) is from 2 to 5:1; the molar ratio of the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride to the compound represented by the formula (7) in the catalyst system A is 0.1-0.3:1.
In a preferred embodiment, in step S12, the molar ratio of tetrakis (triphenylphosphine) palladium in catalyst system B to the amount of compound of formula (5) is from 0.03 to 0.2:1; the molar ratio of carbonate to the amount of compound of formula (5) in catalyst system B is 1-5:1.
In a preferred embodiment, in step S14, the molar ratio of tetrakis (triphenylphosphine) palladium to the amount of the compound of formula (8) used in the catalyst system B is from 0.05 to 0.1:1; the molar ratio of carbonate to the amount of compound of formula (8) in catalyst system B is 1-3:1.
In the present invention, the inert atmosphere is argon.
In a preferred embodiment, the temperature of the reaction in step S11 is 50-90 ℃. Specifically, it may be 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃.
In a preferred embodiment, the temperature of the reaction in step S12 is 60-90 ℃. Specifically, it may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃.
In a preferred embodiment, the temperature of the reaction in step S13 is 60-80 ℃. Specifically, it may be 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
In a preferred embodiment, the temperature of the reaction in step S14 is 70-80 ℃. Specifically, it may be 70 ℃, 75 ℃ or 80 ℃.
In a preferred embodiment, in step S11, the molar ratio of the compound represented by formula (2) to the amount of the compound represented by formula (3) is 1:1 to 1.5. Specifically, it may be 1:1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5.
In a preferred embodiment, in step S12, the molar ratio of the compound represented by formula (4) to the amount of the compound represented by formula (5) is 2 to 2.5:1. Specifically, it may be 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1 or 2.5:1.
In a preferred embodiment, in step S13, the molar ratio of the compound represented by formula (3) to the amount of the compound represented by formula (7) is 4 to 6:1. Specifically, it may be 4:1, 4.5:1, 5:1, 5.5:1 or 6:1.
In a preferred embodiment, in step S14, the molar ratio of the compound represented by formula (8) to the amount of the compound represented by formula (9) is 0.4 to 0.6:1. Specifically, it may be 0.4:1, 0.5:1 or 0.6:1.
In a preferred embodiment, in step S15, the molar ratio of catalyst C to the amount of compound of formula (10) is 1:1 to 1.5.
In a preferred embodiment, the molar ratio of the compound of formula (6) to the amount of the compound of formula (10) is 2-4:1, preferably 2-2.2:1.
In a preferred embodiment, in step S15, the conditions of the reaction include: the reaction temperature is 90-120 ℃. Specifically, it may be 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃.
The third aspect of the invention provides an application of the composite fluorescent sensing material or the composite fluorescent sensing material prepared by the method in leakage monitoring or detection of hydrogen sulfide gas.
In the present invention, there is provided a composite fluorescent sensing material comprising a covalent organic framework material comprising a repeating unit represented by formula (11) and a compound represented by formula (1) supported on the covalent organic framework material. The covalent organic framework material provides a material platform for the fluorescent probe by virtue of the characteristics of large specific surface area and regular pore canal structure, and can also be used for synergetic and specific recognition of hydrogen sulfide by virtue of the groups such as (hydroxy) contained in the covalent organic framework material and the fluorescent probe. Compared with a single fluorescent probe, the composite fluorescent sensing material has higher sensitivity and higher fluorescence quantum yield, can also show identification capability for hydrogen sulfide with the concentration as low as 0.1ppm, and is particularly suitable for leakage monitoring of hydrogen sulfide gas in petrochemical industry.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The raw materials used in the following examples and comparative examples are commercially available products unless otherwise specified.
Example 1
1. Preparation of fluorescent Probe represented by formula (1-1):
s11: taking p-bromophenol (formula 2-1) and adding dipentanoyl diboron (formula 3), potassium acetate and 1,1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride into a round-bottom flask, adding 60 ml of 1, 4-dioxane, introducing argon under stirring to deoxidize for 10 minutes, then reacting at 80 ℃ in an argon atmosphere for 10 hours, and separating by column chromatography after the reaction is finished to obtain a product shown in formula (4-1); wherein, the mol ratio of the p-bromophenol to the bisvaleryldiboron is 1:1.2; the molar ratio of the potassium acetate to the p-bromophenol is 3:1; the molar ratio of the 1,1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride to the p-bromophenol is 0.05:1;
s12: taking a product shown in a formula (4-1) obtained in the step S11, adding 2, 7-dibromofluorene (formula 5-1), tetraphenylphosphine palladium and potassium carbonate into the round-bottomed flask, then adding 50 ml of 1, 4-dioxane and 8 ml of water, introducing argon under stirring to deoxidize for 10 minutes, then reacting for 8 hours at 80 ℃ in an argon atmosphere, and separating by column chromatography after the reaction is finished to obtain the product shown in the formula (6-1); wherein the molar ratio of the product shown in the formula (4-1) to 2, 7-dibromofluorene is 2.5:1, the molar ratio of tetraphenylphosphine palladium to 2, 7-dibromofluorene is 0.11:1, and the molar ratio of potassium carbonate to 2, 7-dibromofluorene is 5:1;
s13: taking 2, 7-dibromofluorene, adding dipentanoyl diboron, potassium acetate and 1,1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride into a round-bottom flask, adding 50 ml of 1, 4-dioxane, introducing argon under stirring to deoxidize for 7 minutes, then reacting for 10 hours at 80 ℃ in an argon atmosphere, and separating by column chromatography after the reaction is finished to obtain a product shown in a formula (8-1); wherein, the mol ratio of the bispentanoyl diboron to the 2, 7-dibromofluorene is 4:1, the mol ratio of the potassium acetate to the 2, 7-dibromofluorene is 4.5:1, 1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride to the 2, 7-dibromofluorene is 0.1:1;
s14: taking the product shown in the formula (8-1) obtained in the step S13, adding p-bromobenzaldehyde (formula 9-1), tetraphenylphosphine palladium and potassium carbonate into the round-bottomed flask, adding 50 ml of 1, 4-dioxane and 7 ml of water, introducing argon under stirring to deoxidize for 10 minutes, then reacting for 8 hours at 80 ℃ in an argon atmosphere, and separating by column chromatography after the reaction is finished to obtain the product shown in the formula (10-1); wherein the molar ratio of the compound shown in the formula (8-1) to the p-bromobenzaldehyde is 0.4:1, the molar ratio of the tetraphenylphosphine palladium to the compound shown in the formula (8-1) is 0.05:1, and the molar ratio of the potassium carbonate to the compound shown in the formula (8-1) is 3:1;
s15: adding 10ml of DMF (dimethyl formamide) into a round bottom flask, introducing argon under stirring to deoxidize for 10 minutes, then adding sodium tert-butoxide into the flask, vigorously stirring for 10 minutes, preparing a DMF solution from the product obtained in the step S14, slowly adding the DMF solution into the round bottom flask, reacting for 2 hours at room temperature (about 25 ℃) in an argon atmosphere, and separating the obtained product by column chromatography after the reaction is finished; wherein, the mol ratio of the product obtained in the step S12 to the product obtained in the step S14 is 2.4:1, and the mol ratio of the sodium tert-butoxide to the product obtained in the step S14 is 1:1.5;
the nuclear magnetic characterization result of the product obtained in the step S15 is shown in figure 1; the mass spectrum characterization result of the product obtained in the step S15 is shown in fig. 2. The structure of the product collected in step S15 is shown in formula (1-1).
2. Preparation of a composite fluorescent sensing material-1:
s21: adding a compound shown in a formula (12), a compound shown in a formula (13-1) and a compound shown in a formula (1-1) into chloroform according to a molar ratio of 1:1:5 to obtain an oil phase;
s22: mixing a catalyst (scandium triflate), a surfactant (dodecyl trimethyl ammonium bromide) and water to obtain a water phase; wherein the molar ratio of the dodecyl trimethyl ammonium bromide to scandium triflate to the compound shown in the formula (11-1) is 0.05:0.2:1;
s23: mixing the water phase and the oil phase in equal volume to form microemulsion, and carrying out polymerization reaction at an emulsion interface at room temperature (about 25 ℃) to form a hollow polymer, namely a primary product, along with slow development of a chloroform solution;
s24: and transferring the preliminary product into acetic acid aqueous solution, and crystallizing for 30 hours at the temperature of minus 5 ℃ to obtain the composite fluorescent sensing material which is yellow powdery crystal.
Example 2
1. Preparation of fluorescent Probe represented by formula (1-2):
s11: taking 4-bromothiophenol (formula 2-2) in a round bottom flask, adding dipyryl diboron, potassium acetate and 1,1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride into the flask, adding 60 ml of 1, 4-dioxane, introducing argon under stirring to deoxidize for 10 minutes, then reacting for 17 hours at 90 ℃ in an argon atmosphere, and separating by column chromatography after the reaction is finished to obtain a product shown in formula (4-2); wherein, the mol ratio of 4-bromothiophenol to bispentanoyl diboron is 1:1, the mol ratio of potassium acetate to 4-bromothiophenol is 3:1, and the mol ratio of 1,1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride to 4-bromothiophenol is 0.05:1;
s12: taking a product obtained in the step S11, putting the product into a round-bottom flask, adding 2, 7-dibromofluorene (formula 5-1), tetraphenylphosphine palladium and potassium carbonate into the round-bottom flask, then adding 50 ml of 1, 4-dioxane and 8 ml of water, introducing argon into the round-bottom flask under the stirring condition to deoxidize for 10 minutes, then reacting the mixture for 8 hours at 80 ℃ in the argon atmosphere, and separating the mixture by column chromatography after the reaction is finished to obtain a product shown in a formula (6-2); wherein the molar ratio of the compound shown in the formula (4-2) to the 2, 7-dibromofluorene is 2:1, the molar ratio of the tetraphenylphosphine palladium to the 2, 7-dibromofluorene is 0.11:1, and the molar ratio of the potassium carbonate to the 2, 7-dibromofluorene is 5:1;
s13: 2, 7-dibromofluorene (formula 5-1) is taken and put into a round bottom flask, dipentanoyl diboron (formula 3), potassium acetate and 1,1' -bis (diphenyl phosphino) ferrocene palladium (II) dichloride are added into the flask, 50 ml of 1, 4-dioxane is added, argon is introduced into the flask under stirring condition to deoxidize for 15 minutes, then the mixture is reacted for 12 hours at 70 ℃ in the argon atmosphere, and after the reaction is finished, the mixture is separated by column chromatography to obtain a product shown in formula (8-2); wherein, the mol ratio of the bispentanoyl diboron to the 2, 7-dibromofluorene is 4:1, and the mol ratio of the potassium acetate to the 2, 7-dibromofluorene is 4.5:1, 1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride to the 2, 7-dibromofluorene is 0.1:1;
s14: taking the product obtained in the step S13, adding p-bromobenzaldehyde (formula 9-1), tetraphenylphosphine palladium and potassium carbonate into the round-bottomed flask, adding 50 ml of 1, 4-dioxane and 7 ml of water, introducing argon to deoxidize for 10 minutes under stirring, then reacting for 8 hours at 80 ℃ in an argon atmosphere, and separating by column chromatography after the reaction is finished to obtain the product of formula (10-2); wherein the molar ratio of the compound shown in the formula (8-2) to the p-bromobenzaldehyde is 0.44:1, the molar ratio of the tetraphenylphosphine palladium to the compound shown in the formula (8-2) is 0.05:1, and the molar ratio of the potassium carbonate to the compound shown in the formula (8-2) is 3:1;
s15: adding 10ml of DMF (dimethyl formamide) into a round bottom flask, introducing argon under stirring to deoxidize for 10 minutes, then adding g of sodium tert-butoxide into the flask, vigorously stirring for 10 minutes, preparing a DMF solution from the product obtained in the step S14, slowly adding the DMF solution into the round bottom flask, reacting for 4 hours at room temperature (about 25 ℃) in an argon atmosphere, and separating the obtained product by column chromatography after the reaction is finished; wherein, the mol ratio of the product obtained in the step S12 to the product obtained in the step S14 is 3:1, and the mol ratio of the sodium tert-butoxide to the product obtained in the step S14 is 1:1.5;
the product collected in the step S15 has been proved to have the structure shown in the formula (1-2) by nuclear magnetism and mass spectrum.
2. The preparation process of the composite fluorescent sensing material-2 is as follows:
s21: adding a compound shown in a formula (12), a compound shown in a formula (13-1) and a compound shown in a formula (1-2) into chloroform according to a molar ratio of 1:1:5 to obtain an oil phase;
s22: mixing a catalyst (scandium triflate), a surfactant (dodecyl trimethyl ammonium bromide) and water to obtain a water phase; wherein the molar ratio of the dodecyl trimethyl ammonium bromide to scandium triflate to the compound shown in the formula (1-2) is 0.1:0.2:1;
s23: mixing the water phase and the oil phase in equal volume to form microemulsion, and carrying out polymerization reaction at an emulsion interface at room temperature (about 25 ℃) to form a hollow polymer, namely a primary product, along with slow development of a chloroform solution;
s24: the preliminary product is transferred to acetic acid aqueous solution to be crystallized for 48 hours at the temperature of 0 ℃ to obtain the composite fluorescent sensing material which is orange powdery crystal.
Example 3
The preparation process of the composite fluorescent sensing material-3 is as follows:
s41: adding a compound shown in a formula (12), a compound shown in a formula (13-2) and a compound shown in a formula (1-2) into chloroform according to a molar ratio of 1:1:5 to obtain an oil phase;
s42: mixing a catalyst (scandium triflate), a surfactant (dodecyl trimethyl ammonium bromide) and water to obtain a water phase;
s43: mixing the water phase and the oil phase, emulsifying to form micro emulsion, and carrying out polymerization reaction at an emulsion interface at room temperature (about 25 ℃), wherein the emulsion slowly develops along with a chloroform solution to form a hollow polymer, namely a primary product;
s44: and transferring the preliminary product into acetic acid aqueous solution, and crystallizing for 48 hours at the temperature of minus 2 ℃ to obtain the composite fluorescent sensing material which is light white powdery crystal.
Comparative example 1
A fluorescent probe is provided, and the structural formula of the fluorescent probe is shown as a formula (1-1).
Test example 1
The compounds represented by the formulas (1-1) and (2-1), and the composite fluorescent sensing materials prepared in examples 1-3 were examined for fluorescence quantum yield, and the results are shown in tables 1 and 2, respectively.
The test method is as follows: dissolving a sample to be tested in chloroform solution drops, then dropping the chloroform solution drops on a polytetrafluoroethylene film, drying the chloroform solution drops, obtaining an optimal excitation wavelength by measuring a fluorescence excitation spectrum of the sample, and exciting the chloroform solution drops by using the optimal excitation wavelength to obtain the strongest fluorescence emission wavelength; the fluorescence quantum yield is tested by using a Hamamatsu C11247 fluorescence quantum yield spectrometer, a single-wavelength scanning mode is selected for testing, the fluorescence quantum yield of the sample is measured under the optimal excitation wavelength, and 3 diaphragms are tested in parallel for each sample drop, and the average value is obtained.
Wherein excitation was performed using a 385nm light source, the result of measuring the fluorescence emission spectrum of the composite fluorescent sensing material prepared in example 1 is shown in fig. 3.
TABLE 1
| Numbering device | Optimal excitation wavelength/nm | Wavelength/nm of strongest fluorescence emission | Fluorescence quantum yield/% |
| (1-1) | 385 | 450 | 40 |
| (2-1) | 385 | 455 | 45 |
TABLE 2
| Numbering device | Optimal excitation wavelength/nm | Wavelength/nm of strongest fluorescence emission | Fluorescence quantum yield/% |
| Example 1 | 385 | 450 | 55 |
| Example 2 | 386 | 457 | 60 |
| Example 3 | 382 | 460 | 67 |
As can be seen from tables 1 and 2, the composite fluorescent sensing material prepared by the method of the present invention has excellent fluorescence quantum yield.
Test example 2
The composite fluorescent sensing material prepared in example 1 was characterized by SEM, and the results are shown in fig. 4.
As can be seen from fig. 4, the composite fluorescent sensing material obtained in example 1 is hollow nano-microsphere, and the size is between hundreds of nanometers and micrometers.
Test example 3
The composite fluorescent sensing material prepared in example 1 was characterized using an ultraviolet-visible spectrophotometer, and the results are shown in fig. 5.
As can be seen from fig. 5, the characteristic peak of the ultraviolet-visible absorption spectrum of the composite fluorescent sensing material prepared in example 1 is 360 nm.
Test example 4
The response of the composite fluorescent sensing materials prepared in examples 1-3 and the fluorescent probe provided in comparative example 1 to hydrogen sulfide was tested.
The self-built instrument is adopted for detection, and the self-built instrument comprises a gas sample injection system, an excitation light source, a detection light source, a receiver and a fluorescence signal display system. And placing the sample to be tested into a gas sample injection system, opening excitation light, wherein the sample to be tested shows a fluorescence curve, and blowing hydrogen sulfide vapor with different concentrations into the gas sample injection system to obtain a curve graph of the fluorescence intensity along with the change of the hydrogen sulfide concentration.
The fluorescence change time sequence diagram of the composite fluorescence sensing material prepared in the embodiment 1 for the hydrogen sulfide vapor with different concentrations is shown in fig. 6, and the detection limit is 0.1ppm. The detection limits of the composite sensing materials of example 2 and example 3 were 0.13 and 0.15ppm, respectively, and were comparable to the materials shown in example 1. The timing chart of fluorescence change of the fluorescent probe described in comparative example 1 for hydrogen sulfide vapor of different concentrations is shown in FIG. 7.
As can be seen from fig. 6 and 7, the composite fluorescent sensing material prepared in example 1 has higher detection sensitivity than the fluorescent probe of comparative example 1. The composite fluorescent sensing material prepared by taking the COFs as a framework and embedding the fluorescent probe into the COFs structure in a non-covalent bonding mode is proved to improve the detection sensitivity of hydrogen sulfide.
Test example 5
The fluorescent probe and the complex fluorescent sensor prepared in example 1 were tested for response to an interfering gas. The interfering gas includes: methanol vapor, acetone vapor, n-hexane vapor, benzene vapor, tetrahydrofuran vapor, 1,4 dioxane vapor, ethyl acetate vapor, methylene chloride vapor, water vapor, and ethanol vapor. The test method was the same as in test example 5.
The fluorescence change timing diagrams of the composite fluorescence sensing material prepared in example 1 for different interference gases are shown in fig. 8-13. The interference gas in fig. 8 is methanol vapor, the interference gas in fig. 9 is acetone vapor, the interference gas in fig. 10 is n-hexane vapor, the interference gas in fig. 11 is benzene vapor, the interference gas in fig. 12 is tetrahydrofuran vapor, and the interference gas in fig. 13 is 1, 4-dioxane vapor.
The graph shows that the interference gas can not influence the detection result of the hydrogen sulfide, and the composite fluorescent sensing material prepared by the method has excellent selectivity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (18)
1. A composite fluorescent sensing material, the composite fluorescent sensing material comprising: a covalent organic framework material containing a repeating unit represented by formula (11), and a compound represented by formula (1) supported on the covalent organic framework material;
wherein K1 and K2 are each independently selected from pyridine, pyridinylalkyl, phenylcyano, alkylphenylcyano, nitrobenzene, alkylnitrobenzene, hydroxy, mercapto, hydroxybenzene, alkylhydroxybenzene, mercaptophenyl, alkylmercapto mercapto;
wherein R1 is selected from any one of the following groups:
n is an integer of 1 to 10;
r2 is selected from pyridine, alkylpyridine, phenylcyano, alkylphenylcyano, nitrobenzene, nitroalkyl, phenylmercaptoalkyl, cyanocycloalkyl, cyanoheterocyclyl, alkylnitrobenzene, alkyl, alkyloxy, alkenyl, hydroxy, phenylhydroxy, aryl, heteroaryl, heteroaryloxy, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclyloxy, or phenylmercapto.
2. The composite fluorescent sensing material according to claim 1, wherein the compound represented by formula (1) is supported on the inner walls of the cells of the covalent organic framework material containing the repeating unit represented by formula (11).
3. The composite fluorescent sensing material of claim 1 or 2, wherein R2 is selected from nitro C1-12 straight or branched alkyl, nitrophenyl C1-C12 alkyl, phenylmercapto C1-C12 cycloalkyl, cyanoc 1-C12 cycloalkyl or cyanoc 1-C12 heterocyclyl.
4. A composite fluorescent sensing material according to any one of claims 1-3, wherein R2 is selected from nitro C1-C6 alkyl, nitrophenyl C1-C6 alkyl, phenylmercapto C1-C6 cycloalkyl, cyanoc 1-C6 cycloalkyl or cyanoc 1-C12 heterocyclyl.
5. The composite fluorescent sensing material of any one of claims 1-4, wherein R2 is selected from any one of the following groups:
6. a method for preparing a composite fluorescent sensing material, which is characterized by comprising the following steps:
s21: mixing a compound shown in a formula (12), a compound shown in a formula (13), a compound shown in a formula (1) and an organic solvent to obtain an oil phase;
s22: scandium triflate, a surfactant and water are mixed to obtain a water phase;
s23: mixing the water phase and the oil phase, emulsifying to form micro emulsion, and performing polymerization reaction at an emulsion interface to obtain a primary product;
s24: transferring the preliminary product into acetic acid aqueous solution for crystallization to obtain a composite fluorescent sensing material;
wherein K1 and K2 are as defined in claim 1.
7. The method according to claim 6, wherein the compound represented by formula (12), the compound represented by formula (13) and the compound represented by formula (1) are used in a molar ratio of 1:1:2-10.
8. The method according to claim 6 or 7, wherein the molar ratio of the surfactant, scandium triflate and the compound of formula (1) is used in an amount of 0.02-0.2:0.1-0.3:1.
9. The method according to any one of claims 6 to 8, wherein in step S21, the organic solvent is selected from chloroform, dichloromethane or ethyl acetate.
10. The method according to any one of claims 6 to 9, wherein in step S24, the crystallization conditions include: the temperature is-5 ℃ to 5 ℃ and the time is 24-48 hours.
11. The method according to claim 5, wherein the method for producing the compound represented by formula (1) comprises the steps of:
s11: reacting a compound shown in a formula (2) with a compound shown in a formula (3) in the presence of a catalyst system A in an inert atmosphere to obtain a compound shown in a formula (4);
s12: reacting a compound shown in a formula (4) with a compound shown in a formula (5) in the presence of a catalyst system B in an inert atmosphere to obtain a compound shown in a formula (6);
s13: reacting a compound shown in a formula (3) with a compound shown in a formula (7) in the presence of a catalyst system A in an inert atmosphere to obtain a compound shown in a formula (8);
s14: reacting a compound shown in a formula (8) with a compound shown in a formula (9) in the presence of a catalyst system B in an inert atmosphere to obtain a compound shown in a formula (10);
s15: reacting a compound shown in a formula (6) with a compound shown in a formula (10) in the presence of a catalyst C in an inert atmosphere to obtain a compound shown in a formula (1);
wherein R1 is as defined in claim 1 and R2 is as defined in claim 1, 3, 4 or 5;
X1-X4 are each independently selected from halogen;
the catalyst system A contains acetate and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride;
the catalyst system B contains tetrakis (triphenylphosphine) palladium and a carbonate;
the catalyst C is sodium tert-butoxide.
12. The method according to claim 11, wherein in step S11, the molar ratio of acetate in the catalyst system a to the amount of the compound represented by formula (2) is 2 to 10:1; the molar ratio of the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride to the compound shown in the formula (2) in the catalyst system A is 0.05-0.4:1;
preferably, in step S13, the molar ratio of acetate in catalyst system a to the amount of compound of formula (7) is from 2 to 5:1; the molar ratio of the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride to the compound represented by the formula (7) in the catalyst system A is 0.1-0.3:1.
13. The process according to claim 11 or 12, characterized in that in step S12 the molar ratio of tetrakis (triphenylphosphine) palladium in catalyst system B to the amount of compound of formula (5) is 0.03-0.2:1; the molar ratio of carbonate in the catalyst system B to the amount of the compound represented by the formula (5) is 1-5:1;
preferably, in step S14, the molar ratio of tetrakis (triphenylphosphine) palladium to the amount of the compound represented by formula (8) used in catalyst system B is from 0.05 to 0.1:1; the molar ratio of carbonate to the amount of compound of formula (8) in catalyst system B is 1-3:1.
14. The method according to any one of claims 10 to 12, wherein the temperature of the reaction in step S11 is 50 to 90 ℃;
preferably, the temperature of the reaction in step S12 is 60-90 ℃;
preferably, the temperature of the reaction in step S13 is 60-80 ℃;
preferably, the temperature of the reaction in step S14 is 70-80 ℃.
15. The method according to claim 10, wherein in step S11, the molar ratio of the compound represented by formula (2) to the amount of the compound represented by formula (3) is 1:1 to 1.5;
preferably, in step S12, the molar ratio of the compound represented by formula (4) to the amount of the compound represented by formula (5) is 2-2.5:1;
preferably, in step S13, the molar ratio of the compound represented by formula (3) to the amount of the compound represented by formula (7) is 4 to 6:1;
preferably, in step S14, the molar ratio of the compound represented by formula (8) to the amount of the compound represented by formula (9) is 0.4 to 0.6:1.
16. The method according to any one of claims 10 to 14, wherein in step S15, the molar ratio of catalyst C to the amount of the compound of formula (10) is 1:1 to 1.5;
preferably, the molar ratio of the compound of formula (6) to the amount of the compound of formula (10) is 2-4:1, preferably 2-2.2:1.
17. The method according to claim 10 or 15, wherein in step S15, the reaction conditions include: the reaction temperature is 90-120 ℃.
18. Use of a composite fluorescent sensing material according to any one of claims 1 to 5 or prepared by a method according to any one of claims 6 to 17 in monitoring or detecting leakage of hydrogen sulphide gas.
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