CN113666949B - Gold (III) complex-perylene diimide derivative and fluorescent sensing tube and tubular fluorescent sensor prepared from same - Google Patents
Gold (III) complex-perylene diimide derivative and fluorescent sensing tube and tubular fluorescent sensor prepared from same Download PDFInfo
- Publication number
- CN113666949B CN113666949B CN202111006034.8A CN202111006034A CN113666949B CN 113666949 B CN113666949 B CN 113666949B CN 202111006034 A CN202111006034 A CN 202111006034A CN 113666949 B CN113666949 B CN 113666949B
- Authority
- CN
- China
- Prior art keywords
- iii
- complex
- gold
- perylene diimide
- diimide derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- CBMIPXHVOVTTTL-UHFFFAOYSA-N gold(3+) Chemical compound [Au+3] CBMIPXHVOVTTTL-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 102
- 150000001875 compounds Chemical class 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- -1 bend-modified perylene diimide anhydride Chemical class 0.000 abstract description 11
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 238000010791 quenching Methods 0.000 abstract description 6
- 230000000171 quenching effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000010931 gold Substances 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000006073 displacement reaction Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 90
- 238000006243 chemical reaction Methods 0.000 description 57
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000007787 solid Substances 0.000 description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 24
- 239000007789 gas Substances 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- 238000005303 weighing Methods 0.000 description 19
- 238000004440 column chromatography Methods 0.000 description 18
- 239000003480 eluent Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 238000001514 detection method Methods 0.000 description 17
- 238000000926 separation method Methods 0.000 description 17
- 238000001914 filtration Methods 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 8
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 7
- DHYHYLGCQVVLOQ-UHFFFAOYSA-N 3-bromoaniline Chemical compound NC1=CC=CC(Br)=C1 DHYHYLGCQVVLOQ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910002666 PdCl2 Inorganic materials 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 235000019260 propionic acid Nutrition 0.000 description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011540 sensing material Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- ACBVWHXLASEZRF-UHFFFAOYSA-N 2-(2,6-ditert-butylphenyl)pyridine Chemical compound CC(C)(C)C(C=CC=C1C(C)(C)C)=C1C1=NC=CC=C1 ACBVWHXLASEZRF-UHFFFAOYSA-N 0.000 description 4
- 229960001701 chloroform Drugs 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- MYKHTOBDZZVWKK-UHFFFAOYSA-M lithium methanol chloride Chemical compound [Li+].[Cl-].CO MYKHTOBDZZVWKK-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- PJUOHDQXFNPPRF-UHFFFAOYSA-N 2,6-diphenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=N1 PJUOHDQXFNPPRF-UHFFFAOYSA-N 0.000 description 2
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 2
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- WRYNUJYAXVDTCB-UHFFFAOYSA-M acetyloxymercury Chemical compound CC(=O)O[Hg] WRYNUJYAXVDTCB-UHFFFAOYSA-M 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001917 fluorescence detection Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 201000004624 Dermatitis Diseases 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 238000001871 ion mobility spectroscopy Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/12—Gold compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- 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
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides a gold (III) complex-perylene diimide derivative and a fluorescent sensing tube and a tubular fluorescent sensor prepared from the same.A ring metal alkynyl gold (III) structure which is flexible, rotatable, good in chemical stability and has the characteristic of a planar structure is introduced into a bend-modified perylene diimide anhydride site, and the non-planarity of the formed structure is utilized to effectively inhibit the stronger intermolecular stacking effect of perylene diimide, avoid aggregation-induced fluorescence quenching and improve the luminous efficiency of the perylene diimide; the cyclometalated Au (III) complex and the perylene diimide can also form an ideal energy donor-acceptor pair, so that the apparent Stokes displacement of the system is effectively widened, and a foundation is laid for the structural optimization of the sensor to be built. The gold (III) complex-perylene diimide derivative has good fluorescence performance, and the tubular fluorescent sensor has high sensitivity.
Description
Technical Field
The invention belongs to the technical field of small-molecule fluorescent sensing materials, and particularly relates to a gold (III) complex-perylene diimide derivative and a fluorescent sensing tube and a tubular fluorescent sensor prepared from the same.
Background
The diversified demands of residents on indoor decoration lead to more and more furniture which only pays attention to aesthetic property, environmental protection and health, and increasingly serious indoor air pollution not only can cause environmental pollution, but also can threaten human health. The formaldehyde is used as a source of diseases, is a first invisible killer which harms public health indoors, and is one of indexes of public place health standards in China. Formaldehyde, also known as formaldehyde, is a colorless gas, but it has a certain pungent odor and can enter the human body through the respiratory tract. Because formaldehyde has the characteristic of stronger adhesiveness, the hardness of the board can be enhanced, the insect-proof and corrosion-proof functions are better, and the manufactured furniture is low in price and is favored by interior decoration. However, people can easily feel irritation and harm after being in the formaldehyde atmosphere for a long time, and the irritation and harm of formaldehyde to human bodies are mainly reflected in skin allergy, abnormal immune function and the like. When the formaldehyde content in the air exceeds the standard, various cancers and skin diseases are easily caused. The world health organization and international cancer research institute evaluated formaldehyde as a class I human carcinogen in 6 months 2014. Therefore, the development of equipment capable of detecting formaldehyde in real time, online, portable and sensitive manner is of great significance.
At present, the standard GB/T50325-containing 2020 of formaldehyde detection in China requires the room to be closed for 12 hours, and the maximum allowable mass concentration of formaldehyde in the air is 0.08mg/m3. The main detection method comprises the following steps: AHMT spectrophotometry, phenol reagent spectrophotometry gas chromatography, acetylacetone spectrophotometry, electrochemical sensors and the like, but the measurement is too professional, so that the ordinary family is difficult to carry out autonomous detection, and only professional persons can be required to carry out detection, which is time-consuming and labor-consuming. Therefore, the development of a portable detection technology capable of directly detecting formaldehyde has extremely important practical value. As is well known, fluorescence sensing is a new generation of micro-trace substance detection technology which is internationally recognized after ion mobility spectrometry. However, the existing fluorescence detection technology still has the defects of low sensitivity, poor interference resistance, sample pretreatment, difficult low-concentration detection and the like, and the essence of the technology is that the performance of a sensing material is poor and a sensing device is incomplete, so that the development of a novel fluorescence sensor with excellent sensing performance is very important.
The perylene diimide derivative has attracted attention in the fields of photoelectric functional materials, catalytic synthesis and the like due to excellent photoelectric property, photochemical stability and thermal stability. In particular, as a high-performance fluorescent material, some applications have been obtained in fluorescence sensing. However, due to the strong intermolecular stacking effect of the perylene diimide, the derivative of the perylene diimide is easy to generate H-aggregation, so that the luminous efficiency of the material is reduced, the solubility is reduced, and the practical application of the material is further influenced.
Although the laminated structure fluorescent sensor has the advantages of small volume, high signal-to-noise ratio and easy array, and can be used for rapidly detecting some important chemical substances, the laminated structure fluorescent sensor also has the problems of large volume of an air chamber, unreasonable distribution of a gas flow field of a substance to be detected and the like, so that a novel thin film fluorescent sensor integrating the advantages of high signal-to-noise ratio, small volume, high sensitivity, more reasonable gas flow field and the like is needed to be developed.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a gold (iii) complex-perylene diimide derivative and a fluorescent sensing tube and a tubular fluorescent sensor prepared from the same, wherein the gold (iii) complex-perylene diimide derivative has good fluorescent properties, and the tubular fluorescent sensor has high sensitivity.
The invention is realized by the following technical scheme:
a gold (III) complex-perylene diimide derivative has a structural formula shown as follows:
wherein n in the structural formula is an integer of 0-9;
and
the 3-position, the 4-position or the 5-position of the upper phenyl group is connected.
Preferably, it is one of the following compounds:
the synthesis method of the gold (III) complex-perylene diimide derivative comprises the following steps:
1) synthesis of Compound 1 represented by the following formula
2) Synthesis of Compound 2
Mixing tetrachloroperylene tetracarboxylic anhydride and p-bromoaniline or m-bromoaniline, adding propionic acid under the protection of nitrogen, heating and stirring for reaction, washing and drying the obtained product to obtain a product compound 2;
the reaction equation is as follows:
3) synthesis of Compound 3
Mixing the compound 2, tert-butylphenol and potassium carbonate, adding DMF (dimethyl formamide) under the protection of nitrogen, heating and stirring for reaction, adding an HCl solution after the reaction is finished to precipitate, dissolving the obtained filter cake with dichloromethane after the reaction is filtered, and performing column chromatography separation by taking dichloromethane as an eluent to obtain a product compound 3;
the reaction equation is as follows:
4) synthesis of Compound 4
Mixing compound 3, CuI, PPh3And PdCl2(PPh)2Mixing, adding tetrahydrofuran and triethylamine under the protection of nitrogen, heating and stirring for reaction to obtain a reaction solution 1, reducing pressure to remove the tetrahydrofuran and the triethylamine, dissolving the obtained solid in the tetrahydrofuran, adding tetrabutylammonium fluoride, stirring to obtain a reaction solution 2, quenching with hydrochloric acid, reducing pressure to remove the tetrahydrofuran and water, and performing column chromatography separation by using dichloromethane as an eluent to obtain a product compound 4;
the reaction equation is as follows:
5) synthesis of gold (III) complex-perylene diimide derivatives
Mixing the compound 1, the compound 4 and the CuI, adding dichloromethane and triethylamine in a nitrogen atmosphere, stirring for reaction, filtering after the reaction is finished, collecting filtrate, and performing column chromatography separation by using dichloromethane as an eluent to obtain a product, namely a gold (III) complex-perylene diimide derivative;
the reaction equation is as follows:
a preparation method of a fluorescent sensing tube comprises the following steps:
1) dissolving the gold (iii) complex-perylene diimide derivative according to claim 1 or 2 in chloroform to obtain a gold (iii) complex-perylene diimide derivative solution;
2) adding the gold (III) complex-perylene diimide derivative solution into a silica gel matrix, uniformly stirring, and performing vacuum drying to obtain a gold (III) complex-perylene diimide derivative fluorescent material;
3) and embedding the gold (III) complex-perylene diimide derivative fluorescent material in the transparent tube along the axial direction to obtain the fluorescent sensing tube.
Preferably, the transparent tube is filled with glass fiber or metal sponge at both ends.
Preferably, the outer diameter of the transparent tube is 1-3 mm, and the inner diameter is 0.6-1.2 mm.
The fluorescent sensing tube prepared by the preparation method.
A tubular fluorescence sensor comprising the fluorescence sensing tube of claim 7.
Preferably, the fluorescent sandwich layer structure further comprises a laminated structure fluorescent sensor, and the fluorescent sensing tube is inserted between the light source and the photosensitive sandwich layer of the laminated structure fluorescent sensor.
The gold (III) complex-perylene diimide derivative or the fluorescent sensing tube or the tubular fluorescent sensor is applied to detection of formaldehyde gas.
Compared with the prior art, the invention has the following beneficial effects:
the gold (III) complex-perylene diimide derivative disclosed by the invention introduces a ring metal alkynyl gold (III) structure which is flexible and rotatable, has good chemical stability and has the characteristic of a planar structure into a bend-modified perylene diimide anhydride site, effectively inhibits stronger intermolecular stacking action of perylene diimide by utilizing the non-planarity of the formed structure, avoids aggregation-induced fluorescence quenching, and improves the luminous efficiency of the perylene diimide. In addition, the cyclometalated Au (III) complex and the perylene diimide can also form a pair of ideal energy donor-acceptor pairs, so that the apparent Stokes shift of the system is effectively widened, and a foundation is laid for the structural optimization of a sensor to be built. Meanwhile, the introduction of the tert-butylphenol group can not only enhance the solubility, but also further distort the perylene anhydride molecular plane. The non-planar fluorescent functional molecules can be accumulated to form rich pore channel structures in the process of preparing the fluorescent material, and effective enrichment of a detection object is realized under the capillary condensation effect, so that the microenvironment where the fluorescent molecules are located is changed, and further the fluorescence intensity or wavelength is changed.
The invention also discloses a synthesis method of the gold (III) complex-perylene diimide derivative, which is simple to operate, easy to obtain raw materials, low in equipment requirement and suitable for large-scale production.
The gold (III) complex-perylene diimide derivative solution is dripped into the silica gel matrix for sample mixing treatment, and the fluorescent sensing material with excellent photo-thermal stability, uniform size, low cost and controllability is prepared. The fluorescent sensing material prepared in the way has large specific surface area and porosity, is rich in molecular channels, can ensure that molecules of a substance to be detected can be well diffused in the material, and further improves the sensing selectivity and sensitivity. By adopting the silica gel as the substrate, the air resistance of the fluorescent sensing tube can be reduced, the enrichment effect on the object to be detected can be enhanced, and the detection limit is further reduced. In addition, the fluorescent sensing material is embedded in the transparent tube, the two ends of the tube naturally form the air inlet and the air outlet, the interior of the tube is a sensing air cavity, a special air chamber is not required to be designed, and good air tightness can be achieved without extra sealing, so that the effectiveness of sensing detection is improved. The preparation method of the gold (III) complex-perylene diimide derivative fluorescent sensing tube is simple and convenient to operate and mild in reaction conditions.
The prepared fluorescent sensing tube has the advantages of good stability, strong anti-interference, high sensitivity and long service life, and can be used for detecting formaldehyde gas.
Furthermore, the transparent tube with the smaller diameter is selected, so that the cost can be saved, the actual volume of the sensor can be reduced to a great extent, and the portable tester is paved. And the inner diameter of the fluorescent sensing tube is a transparent tube with a smaller diameter, so that the effective contact area between the object to be detected and the fluorescent material is further increased on the premise of saving the filling amount of the fluorescent material.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a target fluorescent compound Au-PBI prepared in example 1 of the present invention;
FIG. 2 is a high resolution mass spectrum of Au-PBI of the target fluorescent compound prepared in example 1 of the present invention; (a) measured data and (b) simulated data.
FIG. 3 is a monitoring chart of photochemical stability of a fluorescence sensor tube made by the present invention;
FIG. 4 is a histogram of the fluorescence sensor tube made according to the present invention sensing formaldehyde and common interferents;
FIG. 5 is a graph showing the analysis of the kinetics curve of formaldehyde sensing by the fluorescence sensor tube according to the present invention;
FIG. 6 is a diagram of the repeatability of the fluorescence sensor tube made according to the present invention to formaldehyde gas;
FIG. 7 is a test chart of the response sensitivity of the fluorescent sensing tube prepared according to the present invention to formaldehyde gas;
FIG. 8 is a fluorescence sensing response diagram of formaldehyde gas content in a real environment of the fluorescence sensing tube prepared by the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
the invention discloses a gold (III) complex-perylene diimide derivative, which has the following structural formula:
wherein n in the structural formula is an integer of 0-9; the cyclometalated Au (III) complex segment and the perylene diimide derivative segment are connected into p-benzene or m-benzene.
The invention also discloses a method for synthesizing the gold (III) complex-perylene diimide derivative, which comprises the following steps:
1) synthesis of Compound 1
The precursor compounds of the cyclometallated Au (III) complex fragment of the formula are of the formula:
in the formula, n represents an integer of 0-9; it is prepared by the methods provided in the references "J.Am.chem.Soc.2007, 129, page 4350-.
2) Synthesis of Compound 2
Weighing tetrachloroperylene tetracarboxylic anhydride, p-bromoaniline or m-bromoaniline, placing the tetrachloroperylene tetracarboxylic anhydride, p-bromoaniline or m-bromoaniline into a reaction vessel, adding propionic acid into the reaction vessel under the protection of nitrogen, heating to 150-180 ℃, stirring for reaction for 15-20 hours, cooling to room temperature, adding a proper amount of water, filtering to obtain a mauve solid, namely a compound 2, and performing vacuum drying on the obtained compound 2 at 40-60 ℃ for later use;
the reaction equation is as follows:
3) synthesis of Compound 3
Weighing a compound 2, tert-butylphenol and potassium carbonate, placing the compound 2, tert-butylphenol and potassium carbonate in a reaction container, adding DMF (dimethyl formamide) into the reaction container under the protection of nitrogen, heating to 70-100 ℃, stirring for reaction for 20-28 hours, cooling to room temperature, adding a proper amount of 6mol/L HCl, precipitating, filtering, dissolving an obtained filter cake with dichloromethane, and performing column chromatography separation by using dichloromethane as an eluent to obtain a red solid, namely a compound 3;
the reaction equation is as follows:
4) synthesis of Compound 4
Weighing compound 3, CuI, PPh3And PdCl2(PPh)2Adding tetrahydrofuran and triethylamine into a reaction vessel under the protection of nitrogen, heating to 60-100 ℃, stirring and reacting for 12-18 hours to obtain a reaction solution, removing the solvent under reduced pressure, dissolving the obtained solid in a small amount of tetrahydrofuran, adding a proper amount of tetrabutylammonium fluoride, stirring for 10-30 minutes at room temperature, and adding salt into the reaction solutionQuenching with acid, removing solvent under reduced pressure, and separating with column chromatography with dichloromethane as eluent to obtain red solid compound 4;
the reaction equation is as follows:
5) synthesis of gold (III) complex-perylene diimide derivatives
Weighing a compound 1, a compound 4 and CuI, placing the compound 1, the compound 4 and the CuI in a reaction vessel, adding dichloromethane and triethylamine in the reaction vessel, stirring the mixture at room temperature for 8-12 hours, filtering the mixture, collecting filtrate, and performing column chromatography separation by using dichloromethane as eluent to obtain red solid, namely the gold (III) complex-perylene diimide derivative;
the reaction equation is as follows:
the method comprises the following steps of:
in the step 2), the molar ratio of the consumption of tetrachloroperylene tetracarboxylic anhydride, p-bromoaniline or m-bromoaniline and propionic acid is 1 (1.8-2.5) to 0.5-0.8;
in the step 3), the molar ratio of the compound 2, the tert-butylphenol, the potassium carbonate and the DMF is 1 (8.5-12.5) to 2.5-7.5 to 0.42-0.76;
in the step 4), the compound 3, CuI and PPh3、PdCl2(PPh)2The molar ratio of the tetrahydrofuran to the triethylamine is 1 (8.5-12.5) to 2.5-7.5 to 0.42-0.76 to 0.04-0.09 to 0.05-0.12);
in the step 5), the molar ratio of the compound 4 to the compound 1 to the CuI to the dichloromethane to the triethylamine is 1 (1.5-3.5) to 0.15-0.35 to 0.09-0.24 to 0.01-0.05.
The invention discloses a method for preparing a fluorescent sensing tube by adopting the gold (III) complex-perylene diimide derivative, which comprises the following steps:
1) taking gold (III) complex-perylene diimide derivative, adding trichloromethane solvent to prepare the gold (III) complex-perylene diimide derivative with the concentration of 1 multiplied by 10-6～1×10-4Obtaining a gold (III) complex-perylene diimide derivative assembly structure by using a mol/L gold (III) complex-perylene diimide derivative solution, standing, sealing and storing for later use;
2) dropwise adding the gold (III) complex-perylene diimide derivative solution prepared in the step 1) into a silica gel matrix, uniformly stirring, drying at 40-60 ℃ for 18-24 hours in a vacuum drying oven under 3000Pa pressure, taking out, sealing and storing to prepare the fluorescent material based on the gold (III) complex-perylene diimide derivative;
3) embedding the gold (III) complex-perylene diimide derivative fluorescent material prepared in the step 2) into a transparent tube along the axial direction, and then using glass fiber or metal sponge as interception barriers at two ends to prepare a fluorescent sensing tube;
4) inserting the fluorescent sensing tube prepared in the step 3) into a fluorescent sensor (notice number: CN206740651U) in the cavity of the gas chamber, thereby preparing a tubular fluorescent sensor;
5) an air inlet and an air exhaust port are formed in the tubular fluorescent sensor, one end of the air exhaust port is connected with the miniature air pump, and one end of the air inlet is connected with a working port of the two-position three-way electromagnetic valve.
6) The air inlet of the two-position three-way electromagnetic valve is connected with an air tank, and the air outlet is communicated with the atmosphere.
In the step 2), the volume of the gold (III) complex-perylene diimide derivative solution dripped into the silica gel matrix is 10-1000 mu L.
The transparent tube is a hard cylindrical transparent tube, such as a glass tube, a quartz tube and a polytetrafluoroethylene tube, and has a length of about 15-50 mm, an outer diameter of 1-3 mm and an inner diameter of 0.6-1.2 mm. The length of the fluorescent sensing material embedded in the transparent tube is 1-5 mm.
The invention adopts the two-position three-way electromagnetic valve as the gas path switching valve to replace the manual sample feeding mode, and can play the effects of reducing errors, intelligently, conveniently and integrally pressurizing and increasing gas, thereby further improving the sensitivity.
The tubular fluorescent sensor based on the gold (III) complex-perylene diimide derivative can be used for detecting formaldehyde gas.
Example 1
Synthesis of gold (III) Complex-perylene diimide derivative (in this example, n ═ 4)
Wherein the raw materials are selected from para-bromoaniline and 2, 6-di (tert-butyl) phenylpyridine.
1) Synthesis of Compound 1-1
Weighing 1.43g of 2, 6-di (tert-butyl) phenylpyridine and 2.65g of mercury acetate, putting the weighed materials into a 100mL two-necked bottle, adding 40mL of ethanol, refluxing for 24 hours at 85 ℃, adding a lithium chloride-methanol solution (0.60g of lithium chloride is dissolved in 10mL of methanol), reacting for half an hour at 60 ℃, adding 40mL of deionized water, precipitating, filtering, washing with deionized water, and drying the obtained white solid a at 50 ℃ in vacuum for later use; 308mg of the white solid a and 246mg of potassium chloroaurate were weighed into a 100mL two-necked flask. Under the protection of nitrogen, adding 45mL of acetonitrile into the reaction system, heating to 80 ℃, stirring for reacting for 24 hours, cooling to room temperature, and spin-drying. Mixing with dichloromethane: performing column chromatography separation with petroleum ether (1:1) as eluent to obtain yellow solid compound 1-1. The resulting solid was dried under vacuum at 50 ℃. The reaction equation is as follows:
2) synthesis of Compound 2-1
Weighing 3.0g of tetrachloroperylene tetracarboxylic anhydride and 11.3g of para-bromoaniline in a 100mL single-neck bottle, adding 50mL of propionic acid under the protection of nitrogen, heating to 160 ℃, stirring for reacting for 16 hours, cooling to room temperature, adding a proper amount of water to generate a precipitate, filtering to obtain a filter cake, and drying the obtained solid compound 2-1 at 50 ℃ in vacuum for later use. The reaction equation is as follows:
3) synthesis of Compound 3-1
Weighing 1.50g of compound 2-1, 3.46g of tert-butylphenol and 1.16g of potassium carbonate, placing the mixture in a 100mL two-port bottle, adding 50mL of DMF (dimethyl formamide) into a reaction container under the protection of nitrogen, heating to 90 ℃, stirring for reacting for 24 hours, cooling to room temperature, adding a proper amount of 6mol/L HCl, precipitating, filtering, dissolving the obtained filter cake with dichloromethane, and performing column chromatography separation by taking dichloromethane as eluent to obtain a red solid, namely the compound 3-1;
the reaction equation is as follows:
4) synthesis of Compound 4-1
Weighing 100mg of compound 3-1, 2.90mg of CuI, and 4.05mg of PPh3And 54.30mg of PdCl2(PPh)2Adding 6mL of tetrahydrofuran and 12mL of triethylamine into a 50mL two-mouth bottle under the protection of nitrogen, heating to 80 ℃, stirring for reacting for 16 hours to obtain a reaction solution, removing the solvent under reduced pressure, dissolving the obtained solid in a small amount of tetrahydrofuran, adding a proper amount of tetrabutylammonium fluoride, stirring for 15 minutes at room temperature, quenching the reaction solution with hydrochloric acid, removing the solvent under reduced pressure, and performing column chromatography separation by using dichloromethane as an eluent to obtain a red solid, namely the compound 4-1;
the reaction equation is as follows:
5) synthesis of gold (III) complex-perylene diimide derivatives
Weighing 17mg of compound 1-1, 11.82mg of compound 4-1 and 0.50mg of CuI in a 25mL two-necked bottle, adding 9mL of dichloromethane and 0.50mL of triethylamine in a nitrogen atmosphere, stirring at room temperature for 10 hours, filtering, collecting filtrate, and performing column chromatography separation by taking dichloromethane as an eluent to obtain a red solid, namely the gold (III) complex-perylene diimide derivative;
the reaction equation is as follows:
the results of the structural characterization data of the gold (III) complex-perylene diimide derivative (Au-PBI) prepared by the invention are shown in the figure 1 and the figure 2.
Example 2
Synthesis of gold (III) Complex-perylene diimide derivative (in this example, n ═ 0)
Wherein the raw materials are selected from p-bromoaniline and 2, 6-diphenylpyridine.
1) Synthesis of Compound 1-2
Weighing 1.60g of 2, 6-diphenylpyridine and 4.4g of mercuric acetate, putting the weighed materials into a 100mL two-neck bottle, adding 40mL of ethanol, refluxing for 24 hours at 85 ℃, adding a lithium chloride-methanol solution (1.0g of lithium chloride is dissolved in 20mL of methanol), reacting for half an hour at 60 ℃, adding 60mL of deionized water, precipitating, filtering, washing with deionized water, and drying the obtained white solid a at 50 ℃ in vacuum for later use; 308mg of the white solid a and 246mg of potassium chloroaurate were weighed into a 100mL two-necked flask. Under the protection of nitrogen, adding 45mL of acetonitrile into the reaction system, heating to 80 ℃, stirring for reacting for 24 hours, cooling to room temperature, and spin-drying. Mixing the raw materials in a ratio of dichloromethane: performing column chromatography separation with petroleum ether (1:1) as eluent to obtain yellow solid, i.e. compound 1-2. The resulting solid was dried under vacuum at 50 ℃. The reaction equation is as follows:
2) synthesis of Compound 2-1
Weighing 3.0g of tetrachloroperylene tetracarboxylic anhydride and 11.3g of para-bromoaniline in a 100mL single-neck bottle, adding 50mL of propionic acid under the protection of nitrogen, heating to 160 ℃, stirring for reacting for 16 hours, cooling to room temperature, adding a proper amount of water to generate a precipitate, filtering to obtain a filter cake, and drying the obtained solid compound 2-1 at 50 ℃ in vacuum for later use. The reaction equation is as follows:
3) synthesis of Compound 3-1
Weighing 1.50g of compound 2-1, 3.46g of tert-butylphenol and 1.16g of potassium carbonate, placing the mixture in a 100mL two-necked bottle, adding 50mL of DMF (dimethyl formamide) into a reaction container under the protection of nitrogen, heating to 90 ℃, stirring for reacting for 24 hours, cooling to room temperature, adding a proper amount of 6mol/L HCl, precipitating, filtering, dissolving the obtained filter cake with dichloromethane, and performing column chromatography separation by using dichloromethane as an eluent to obtain a red solid, namely the compound 3-1;
the reaction equation is as follows:
4) synthesis of Compound 4-1
Weighing 100mg of compound 3-1, 2.90mg of CuI, and 4.05mg of PPh3And 54.30mg of PdCl2(PPh)2Adding 6mL of tetrahydrofuran and 12mL of triethylamine into a 50mL two-mouth bottle under the protection of nitrogen, heating to 80 ℃, stirring for reacting for 16 hours to obtain a reaction solution, removing the solvent under reduced pressure, dissolving the obtained solid in a small amount of tetrahydrofuran, adding a proper amount of tetrabutylammonium fluoride, stirring for 15 minutes at room temperature, quenching the reaction solution with hydrochloric acid, removing the solvent under reduced pressure, and performing column chromatography separation by using dichloromethane as an eluent to obtain a red solid, namely the compound 4-1;
the reaction equation is as follows:
5) synthesis of gold (III) complex-perylene diimide derivatives
Weighing 17mg of compound 1-2, 11.82mg of compound 4-1 and 0.50mg of CuI in a 25mL two-necked bottle, adding 9mL of dichloromethane and 0.50mL of triethylamine in a nitrogen atmosphere, stirring at room temperature for 10 hours, filtering, collecting filtrate, and performing column chromatography separation by taking dichloromethane as an eluent to obtain a red solid, namely the gold (III) complex-perylene diimide derivative;
the reaction equation is as follows:
example 3
Synthesis of gold (III) Complex-perylene diimide derivative (in this example, n ═ 4)
Wherein the raw materials are selected from m-bromoaniline and 2, 6-di (tert-butyl) phenylpyridine.
1) Synthesis of Compound 1-1
Weighing 1.43g of 2, 6-di (tert-butyl) phenylpyridine and 2.65g of mercury acetate, putting the weighed materials into a 100mL two-necked bottle, adding 40mL of ethanol, refluxing for 24 hours at 85 ℃, adding a lithium chloride-methanol solution (0.60g of lithium chloride is dissolved in 10mL of methanol), reacting for half an hour at 60 ℃, adding 40mL of deionized water, precipitating, filtering, washing with deionized water, and drying the obtained white solid a at 50 ℃ in vacuum for later use; 308mg of the white solid a and 246mg of potassium chloroaurate were weighed into a 100mL two-necked flask. Under the protection of nitrogen, adding 45mL of acetonitrile into the reaction system, heating to 80 ℃, stirring for reacting for 24 hours, cooling to room temperature, and spin-drying. Mixing the raw materials in a ratio of dichloromethane: and (3) performing column chromatography separation by using petroleum ether (1:1) as an eluent to obtain a yellow solid. The resulting solid was dried under vacuum at 50 ℃. The reaction equation is as follows:
2) synthesis of Compound 2-2
Weighing 3.0g of tetrachloroperylene tetracarboxylic anhydride and 11.3g of m-bromoaniline in a 100mL single-neck bottle, adding 50mL of propionic acid under the protection of nitrogen, heating to 160 ℃, stirring for reacting for 16 hours, cooling to room temperature, adding a proper amount of water to generate precipitate, filtering to obtain a filter cake, and drying the obtained solid compound 2-2 at 50 ℃ in vacuum for later use. The reaction equation is as follows:
3) synthesis of Compound 3-2
Weighing 1.50g of compound 2-2, 3.46g of tert-butylphenol and 1.16g of potassium carbonate, placing the mixture in a 100mL two-port bottle, adding 50mL of DMF (dimethyl formamide) into a reaction container under the protection of nitrogen, heating to 90 ℃, stirring for reacting for 24 hours, cooling to room temperature, adding a proper amount of 6mol/L HCl, precipitating, filtering, dissolving the obtained filter cake with dichloromethane, and performing column chromatography separation by taking dichloromethane as eluent to obtain a red solid, namely the compound 3-2;
the reaction equation is as follows:
4) synthesis of Compound 4-2
Weighing 100mg of compound 3-2, 2.90mg of CuI, and 4.05mg of PPh3And 54.30mg of PdCl2(PPh)2Adding 6mL of tetrahydrofuran and 12mL of triethylamine into a 50mL two-mouth bottle under the protection of nitrogen, heating to 80 ℃, stirring for reacting for 16 hours to obtain a reaction solution, removing the solvent under reduced pressure, dissolving the obtained solid in a small amount of tetrahydrofuran, adding a proper amount of tetrabutylammonium fluoride, stirring for 15 minutes at room temperature, quenching the reaction solution with hydrochloric acid, removing the solvent under reduced pressure, and performing column chromatography separation by using dichloromethane as an eluent to obtain a red solid, namely the compound 4-2;
the reaction equation is as follows:
5) synthesis of gold (III) complex-perylene diimide derivatives
Weighing 17mg of compound 1-1, 11.82mg of compound 4-2 and 0.50mg of CuI in a 25mL two-necked bottle, adding 9mL of dichloromethane and 0.50mL of triethylamine in a nitrogen atmosphere, stirring at room temperature for 10 hours, filtering, collecting filtrate, and performing column chromatography separation by taking dichloromethane as an eluent to obtain a red solid, namely the gold (III) complex-perylene diimide derivative;
the reaction equation is as follows:
example 4
Preparing a fluorescence sensing tube based on a gold (III) complex-perylene diimide derivative:
1) the gold (III) complex-perylene diimide derivative in example 1 was taken and added with chloroform solvent to prepare a gold (III) complex-perylene diimide derivative with a concentration of 1X 10-6～1×10-4Obtaining a gold (III) complex-perylene diimide derivative assembly structure by using a mol/L gold (III) complex-perylene diimide derivative solution, standing, sealing and storing for later use;
2) dropwise adding the gold (III) complex-perylene diimide derivative solution prepared in the step 1) into a silica gel matrix, uniformly stirring, drying at 40-60 ℃ for 18-24 hours in a vacuum drying oven under 3000Pa pressure, taking out, sealing and storing to prepare the fluorescent material based on the gold (III) complex-perylene diimide derivative;
3) embedding the gold (III) complex-perylene diimide derivative fluorescent material prepared in the step 2) into a transparent tube along the axial direction, and then using glass fiber or metal sponge as interception barriers at two ends to prepare the fluorescent sensing tube.
Example 5
To verify the effectiveness of the present invention, a number of laboratory research experiments were conducted on the fluorescent sensor tube prepared in example 4, and the experimental conditions were as follows:
1) photochemical stability testing of fluorescent materials
Photobleaching is a very important factor limiting the practical application of fluorescent sensors, and therefore, it is necessary to study the photochemical stability of the materials before they are used for fluorescence detection. The results of the correlation tests are shown in fig. 3. The test result shows that the fluorescence intensity of the prepared fluorescence sensing tube is basically unchanged after being continuously irradiated by 24 hours of light, which shows that the fluorescence sensing tube has excellent photochemical stability and lays a solid foundation for the research of later sensing behaviors.
2) Sensing test of fluorescence sensing tube on formaldehyde and common interferents
And (3) measuring the actual sample of the fluorescent sensing tube by adopting a fluorescent sensing detection platform. Wherein, the sample to be analyzed is formaldehyde, and the interferents are selected from common solvents and substances (benzene, acetone, dichloromethane, trichloromethane, normal hexane, ethanol, tetrahydrofuran, water, air, perfume, milk and the like) in living environment.
The operation process is as follows:
firstly, a small amount of different samples to be detected are packaged in a 200mL double-hole closed brown gas tank and are kept stand for 48 hours at room temperature for later use;
secondly, placing the embedded fluorescent sensing tube in a sensor, and respectively testing 30 analytes at room temperature;
thirdly, when the analyte is tested, a trace sample is introduced by using an electromagnetic valve, the air inlet of the electromagnetic valve is connected with one port of the air tank in the step I, and the working port of the electromagnetic valve is connected with the air inlet of the fluorescent sensing tube. The sample introduction time is about 1-8 seconds, the pump speed is 50-600 mL/min, and after recovery, the test is repeated.
3) Repeatability test of fluorescent sensing tube on formaldehyde gas
The detection repeatability is one of the key indexes of whether the instrument can be put into practical application, so that the self-made fluorescent sensing tube is used for repeatedly detecting the formaldehyde gas for 130 times, and the result shown in figure 6 shows that the fluorescent sensing tube still has good responsiveness after being tested for multiple times, can be repeatedly used for multiple times, saves resources and reduces cost.
4) Formaldehyde gas detection limit test by fluorescent sensing tube
The sensitivity is also one of the performance indexes of the sensor, and the value of the sensor can be exerted in practical application only if the detection limit is low enough, so that the self-made sensor is used for testing formaldehyde gas with different concentrations, and the objects to be tested with different concentrations are obtained by adopting a method of diluting response times by using air. As can be seen from FIG. 7, at low concentrations, the fluorescence intensity of the material decreases linearly with increasing concentration of formaldehyde gas, followed by a slow appearanceA platform. Further, the lowest detection concentration of the sensor to formaldehyde can reach 0.01mg/m3And the concentration of the formaldehyde gas can be monitored in real time when the concentration is lower than the standard of the formaldehyde content of the national indoor living environment.
5) Method for testing content of formaldehyde gas in real environment by using fluorescent sensing tube
The sampler is used for collecting newly-finished indoor air, and the sampling is carried out for multiple times respectively from different articles and different heights. And (3) placing the sample in a gas tank, detecting according to the step 2), and analyzing to obtain that the environment to be detected contains formaldehyde and is excessive as shown in figure 8. The sensor can be used for real environment detection, and needs to be further developed and optimized, so that a portable formaldehyde tester is developed.
In conclusion, the fluorescent material based on the gold (III) complex-perylene diimide derivative disclosed by the invention can sensitively sense formaldehyde gas, and has extremely high practicability. The invention has simple operation and mild reaction condition, and the prepared fluorescent sensing tube has good stability and long service life and is an excellent formaldehyde gas sensing module. In addition, through the device, a portable special formaldehyde gas detector can also be developed.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. A gold (III) complex-perylene diimide derivative is characterized in that the structural formula is as follows:
wherein n in the structural formula is an integer of 0-9;
and
the 3-, 4-or 5-position of the upper phenyl group is linked.
2. A gold (III) complex-perylene diimide derivative is characterized by being one of the following compounds:
3. a method for preparing a fluorescent sensor tube is characterized by comprising the following steps:
1) dissolving the gold (iii) complex-perylene diimide derivative according to claim 1 or 2 in chloroform to obtain a gold (iii) complex-perylene diimide derivative solution;
2) adding the gold (III) complex-perylene diimide derivative solution into a silica gel matrix, uniformly stirring, and performing vacuum drying to obtain a gold (III) complex-perylene diimide derivative fluorescent material;
3) and embedding the gold (III) complex-perylene diimide derivative fluorescent material in the transparent tube along the axial direction to obtain the fluorescent sensing tube.
4. The method of claim 3, wherein the transparent tube is filled with glass fiber or metal sponge at both ends.
5. The method for preparing a fluorescence sensor tube according to claim 3, wherein the transparent tube has an outer diameter of 1 to 3mm and an inner diameter of 0.6 to 1.2 mm.
6. The fluorescence sensor tube obtained by the production method according to any one of claims 3 to 5.
7. A tubular fluorescence sensor comprising the fluorescence sensor tube of claim 6.
8. The tube-type fluorescence sensor according to claim 7, further comprising a stacked-structure fluorescence sensor, wherein the fluorescence sensing tube is interposed between a light source and the photosensitive interlayer of the stacked-structure fluorescence sensor.
9. Use of the gold (iii) complex-perylene diimide derivative according to claim 1 or 2 or the fluorescence sensing tube according to claim 6 or the tubular fluorescence sensor according to claim 7 or 8 for detecting formaldehyde gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111006034.8A CN113666949B (en) | 2021-08-30 | 2021-08-30 | Gold (III) complex-perylene diimide derivative and fluorescent sensing tube and tubular fluorescent sensor prepared from same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111006034.8A CN113666949B (en) | 2021-08-30 | 2021-08-30 | Gold (III) complex-perylene diimide derivative and fluorescent sensing tube and tubular fluorescent sensor prepared from same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113666949A CN113666949A (en) | 2021-11-19 |
| CN113666949B true CN113666949B (en) | 2022-07-12 |
Family
ID=78547603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111006034.8A Active CN113666949B (en) | 2021-08-30 | 2021-08-30 | Gold (III) complex-perylene diimide derivative and fluorescent sensing tube and tubular fluorescent sensor prepared from same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113666949B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262396A (en) * | 2014-09-10 | 2015-01-07 | 天津理工大学 | Bay-position gold-substituted perylene diimide derivative |
| CN106632326A (en) * | 2016-11-16 | 2017-05-10 | 陕西师范大学 | Di-pyrene modified perylene bisimide derivative fluorescent probe and synthesis method and application thereof |
| CN107698614A (en) * | 2017-08-29 | 2018-02-16 | 陕西师范大学 | A kind of carborane diimide derivative and synthetic method and the sensor array based on it and preparation method and application |
| CN110143976A (en) * | 2019-06-14 | 2019-08-20 | 湘潭大学 | Based on branching porphyrin-imidodicarbonic diamide small molecule receptor synthetic method and application |
| CN110229315A (en) * | 2019-06-14 | 2019-09-13 | 湘潭大学 | A kind of broad-band gap copolymer acceptor material and preparation method thereof based on imidodicarbonic diamide |
| CN110330497A (en) * | 2019-07-15 | 2019-10-15 | 陕西师范大学 | A kind of dish alkene-diimide derivative and its synthetic method and the Application in Sensing to gas phase volatile aromatics |
| CN110790772A (en) * | 2018-08-02 | 2020-02-14 | 华南理工大学 | Hydroxyquinoline-based metal organic micromolecule complex material grafted with perylene diimide and aromatic group and preparation method and application thereof |
-
2021
- 2021-08-30 CN CN202111006034.8A patent/CN113666949B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262396A (en) * | 2014-09-10 | 2015-01-07 | 天津理工大学 | Bay-position gold-substituted perylene diimide derivative |
| CN106632326A (en) * | 2016-11-16 | 2017-05-10 | 陕西师范大学 | Di-pyrene modified perylene bisimide derivative fluorescent probe and synthesis method and application thereof |
| CN107698614A (en) * | 2017-08-29 | 2018-02-16 | 陕西师范大学 | A kind of carborane diimide derivative and synthetic method and the sensor array based on it and preparation method and application |
| CN110790772A (en) * | 2018-08-02 | 2020-02-14 | 华南理工大学 | Hydroxyquinoline-based metal organic micromolecule complex material grafted with perylene diimide and aromatic group and preparation method and application thereof |
| CN110143976A (en) * | 2019-06-14 | 2019-08-20 | 湘潭大学 | Based on branching porphyrin-imidodicarbonic diamide small molecule receptor synthetic method and application |
| CN110229315A (en) * | 2019-06-14 | 2019-09-13 | 湘潭大学 | A kind of broad-band gap copolymer acceptor material and preparation method thereof based on imidodicarbonic diamide |
| CN110330497A (en) * | 2019-07-15 | 2019-10-15 | 陕西师范大学 | A kind of dish alkene-diimide derivative and its synthetic method and the Application in Sensing to gas phase volatile aromatics |
Non-Patent Citations (1)
| Title |
|---|
| Excitation energy migration in covalently linked perylene bisimide macrocycles;Felix Schlosser等;《Chem. Sci.》;20120614;第3卷;第2778-2785页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113666949A (en) | 2021-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hill et al. | Breath analysis for medical diagnosis | |
| CN102721779A (en) | Detection method of selenium forms in plants | |
| CN107505405B (en) | Method for efficiently and rapidly extracting and measuring flavonoid pigment in Chinese rose petals | |
| Lin et al. | Using a PEDOT: PSS modified electrode for detecting nitric oxide gas | |
| Zhang et al. | Detection of gaseous amines with a fluorescent film based on a perylene bisimide-functionalized copolymer | |
| CN101788489B (en) | Sensitive thin-film material used for detecting drugs efficiently and preparation method thereof | |
| CN115232327B (en) | Metal organic framework material and preparation method and application thereof | |
| CN110330497B (en) | Brene-perylene diimide derivative, synthesis method thereof and sensing application of derivative to gas-phase volatile aromatic hydrocarbon | |
| CN111289581A (en) | Sensing material for formaldehyde detection and preparation method and application thereof | |
| CN113666949B (en) | Gold (III) complex-perylene diimide derivative and fluorescent sensing tube and tubular fluorescent sensor prepared from same | |
| Zhao et al. | Versatile computer-controlled system for characterization of gas sensing materials | |
| CN110964042B (en) | Preparation method and application of N, N-di (2-picolyl) amido BODIPY nickel ion fluorescent probe | |
| CN203324188U (en) | Fluorescent oxygen sensor | |
| CN110878100B (en) | Cyanide ion probe capable of being recognized by naked eyes, preparation method thereof and application of cyanide ion probe in detection of cyanide ions in water-containing system | |
| Itagaki et al. | Optical humidity sensor using porphyrin immobilized Nafion composite films | |
| CN109020999A (en) | A kind of preparation and application of two pyroles near-infrared pH fluorescence probe of the boron of fluorine containing piperidyl | |
| CN109879911B (en) | VOC (volatile organic compound) fluorescent sensing material based on cuprous complex | |
| CN107607477B (en) | Construction method and application of 8-hydroxyquinoline lithium boride modified polymer sensor array | |
| CN101477054A (en) | Oligo-thiophenes fluorescent sensing film production method and its use in methanal gas detection | |
| CN104897739A (en) | Organic semiconductor nanomaterial, preparation method and application of organic semiconductor nanomaterial as well as nitrogen dioxide gas sensor | |
| CN106674048B (en) | A kind of CN- detection reagents and its synthetic method and application | |
| CN110243898A (en) | A kind of preparation method based on annular metal iridium complex optical electro-chemistry molecular probe pH sensor | |
| Fan et al. | A new cataluminescence-based gas sensor for simultaneously discriminating benzene and ammonia | |
| CN110408397A (en) | A kind of CeCl3:Eu3+The preparation method of fluorescence probe array | |
| Liu et al. | High sensitive pyridine chemiresistive sensors based on azacyclobutane modified perylene bisimide derivatives |
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 |