CN108863912B - 一种三聚茚基n，n-二(2-吡啶甲基)胺类铜离子荧光探针的制备方法及其应用 - Google Patents
一种三聚茚基n，n-二(2-吡啶甲基)胺类铜离子荧光探针的制备方法及其应用 Download PDFInfo
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- CN108863912B CN108863912B CN201810445382.7A CN201810445382A CN108863912B CN 108863912 B CN108863912 B CN 108863912B CN 201810445382 A CN201810445382 A CN 201810445382A CN 108863912 B CN108863912 B CN 108863912B
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000000523 sample Substances 0.000 title claims abstract description 36
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 title claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 29
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 title claims description 25
- 229910001431 copper ion Inorganic materials 0.000 title abstract description 30
- 238000002360 preparation method Methods 0.000 title description 4
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- -1 2- picolyl Chemical group 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000013638 trimer Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229940125782 compound 2 Drugs 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010949 copper Substances 0.000 abstract description 9
- 238000001514 detection method Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 150000002469 indenes Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- DIGQNXIGRZPYDK-WKSCXVIASA-N (2R)-6-amino-2-[[2-[[(2S)-2-[[2-[[(2R)-2-[[(2S)-2-[[(2R,3S)-2-[[2-[[(2S)-2-[[2-[[(2S)-2-[[(2S)-2-[[(2R)-2-[[(2S,3S)-2-[[(2R)-2-[[(2S)-2-[[(2S)-2-[[(2S)-2-[[2-[[(2S)-2-[[(2R)-2-[[2-[[2-[[2-[(2-amino-1-hydroxyethylidene)amino]-3-carboxy-1-hydroxypropylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1-hydroxyethylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1,3-dihydroxypropylidene]amino]-1-hydroxyethylidene]amino]-1-hydroxypropylidene]amino]-1,3-dihydroxypropylidene]amino]-1,3-dihydroxypropylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1,3-dihydroxybutylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1-hydroxypropylidene]amino]-1,3-dihydroxypropylidene]amino]-1-hydroxyethylidene]amino]-1,5-dihydroxy-5-iminopentylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1,3-dihydroxybutylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1,3-dihydroxypropylidene]amino]-1-hydroxyethylidene]amino]-1-hydroxy-3-sulfanylpropylidene]amino]-1-hydroxyethylidene]amino]hexanoic acid Chemical compound C[C@@H]([C@@H](C(=N[C@@H](CS)C(=N[C@@H](C)C(=N[C@@H](CO)C(=NCC(=N[C@@H](CCC(=N)O)C(=NC(CS)C(=N[C@H]([C@H](C)O)C(=N[C@H](CS)C(=N[C@H](CO)C(=NCC(=N[C@H](CS)C(=NCC(=N[C@H](CCCCN)C(=O)O)O)O)O)O)O)O)O)O)O)O)O)O)O)N=C([C@H](CS)N=C([C@H](CO)N=C([C@H](CO)N=C([C@H](C)N=C(CN=C([C@H](CO)N=C([C@H](CS)N=C(CN=C(C(CS)N=C(C(CC(=O)O)N=C(CN)O)O)O)O)O)O)O)O)O)O)O)O DIGQNXIGRZPYDK-WKSCXVIASA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 102000012437 Copper-Transporting ATPases Human genes 0.000 description 1
- 102000000634 Cytochrome c oxidase subunit IV Human genes 0.000 description 1
- 108050008072 Cytochrome c oxidase subunit IV Proteins 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 208000002972 Hepatolenticular Degeneration Diseases 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 208000008948 Menkes Kinky Hair Syndrome Diseases 0.000 description 1
- 208000012583 Menkes disease Diseases 0.000 description 1
- 102000003792 Metallothionein Human genes 0.000 description 1
- 108090000157 Metallothionein Proteins 0.000 description 1
- CVRXLMUYFMERMJ-UHFFFAOYSA-N N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine Chemical compound C=1C=CC=NC=1CN(CC=1N=CC=CC=1)CCN(CC=1N=CC=CC=1)CC1=CC=CC=N1 CVRXLMUYFMERMJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010056677 Nerve degeneration Diseases 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 102000019197 Superoxide Dismutase Human genes 0.000 description 1
- 108010012715 Superoxide dismutase Proteins 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 208000018839 Wilson disease Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JAOSYYPULNBONK-UHFFFAOYSA-N n'-(pyridin-2-ylmethyl)ethane-1,2-diamine Chemical class NCCNCC1=CC=CC=N1 JAOSYYPULNBONK-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- YGPLLMPPZRUGTJ-UHFFFAOYSA-N truxene Chemical compound C1C2=CC=CC=C2C(C2=C3C4=CC=CC=C4C2)=C1C1=C3CC2=CC=CC=C21 YGPLLMPPZRUGTJ-UHFFFAOYSA-N 0.000 description 1
- 230000006444 vascular growth Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明公开了一种N，N‑二(2‑吡啶甲基)胺(DPA)为识别基团，三聚茚为荧光基团的Cu2+荧光探针，所述探针是N，N‑二(2‑吡啶甲基)胺取代的三聚茚衍生物，其化学结构式如式(1)所示。本发明的荧光探针在水与N，N‑二甲基甲酰胺混合溶液中对Cu2+有独特的荧光选择性、极高的灵敏性及较强的抗其他金属离子干扰能力，检测极限可低至30nM/L以。本发明是一种简单、快速、灵敏的铜离子检测探针，具有广阔的应用前景。
Description
技术领域
本发明涉及有机小分子荧光探针领域，尤其涉及一种Cu2+荧光探针N，N-二(2-吡啶甲基)胺取代的三聚茚衍生物。
背景技术
三聚茚(truxene)是一个三重对称性平面刚性的稠环芳烃，具有较大的刚性共轭结构和较高的光、热稳定性，是一类结构易于修饰的有机光电化合物。通过在三聚茚的5-位、10-位和15-位引入烷基链，可以有效改善三聚茚衍生物的溶解性能；三聚茚的2-位、7和12-位的化学反应活性高，易于进行功能化设计和修饰，是制备光电功能染料分子的理想化合物之一。二(2-吡啶甲基)胺(DPA)是N，N，N，N-四(2-吡啶甲基)乙二胺(TPEN)的衍生物。DPA中的三个N原子都含有未成键的电子，能有效地与金属离子进行络合。
铜是人体内继铁和锌之后的重要过渡金属元素，成人体内总铜含量一般是70～80毫克。它在我们许多生理过程中起到十分重要的作用，可通过与金属硫蛋白结合而影响过氧化物歧化酶，细胞色素氧化酶等的活性。当体内铜离子含量适量时，会促进人体对铁元素的吸收，所以当铜离子在人体内含量过少时，可能会导致贫血型疾病，其对肿瘤血管生长因子也起着重要调节作用。然而，当铜离子在人体内含量过多时，可以导致严重的神经退变型疾病，例如Menkes和Wilson疾病，人体长时间暴露在Cu2+的中会导致阿兹海默症。因此，对人体内铜离子的定量定性检测成为国内外研究人员十分关注的领域。荧光探针技术不仅方法简便，而且具有灵敏度高、响应时间短、选择性好、抗干扰力强、便于实时原位及远程检测等优点。然而目前文献报道中的铜离子荧光探针大多数是非水溶性的，将其应用于生命体中铜离子的检测受到限制，同时，金属铜也是环境中主要的污染源之一。基于此，开发新型铜离子荧光探针有着重要的实际应用价值。
发明内容
针对现有技术的不足，本发明通过分子设计，合成出一种具有响应时间快、较高选择性和低检测限的三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针。
本发明还提供上述三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针的制备方法。
本发明还提供上述三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针的应用。
技术方案：为了实现上述发明目的，本发明的技术方案是：一种三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针，其化学结构如式(1)所示：
上述三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针的合成方法，其特征在于，它是按以下步骤进行：
(1)将三聚茚甲醇化合物与二氯亚砜反应得到化合物2；
(2)将步骤(1)得到的化合物2与N，N-二(2-吡啶甲基)胺(DPA)反应即可制得荧光探针化合物1。
上述的三聚茚基N，N-二(2-吡啶甲基)胺类荧光探针的合成路线如下：
所述步骤(1)是采用下述方法完成：用干燥的甲苯25mL溶解苄醇三聚茚化合物1(1mmol)，氮气保护，在0℃下加入SOCl2(40mmol，150μl)，室温反应过夜。反应结束后用饱和的碳酸氢钠溶液淬灭，用二氯甲烷萃取三次，合并有机层，水洗，饱和食盐水洗，有机层用无水硫酸钠干燥，减压蒸馏除去有机溶剂，得到化合物2。
所述步骤(2)是采用下述方法完成：1mmol化合物2溶解于干燥的二氯甲烷25mL和新蒸馏的三乙胺5mL混合溶剂中，在氮气保护下加入1.5mmol N，N-二(2-吡啶甲基)胺，室温反应过夜。反应结束后用蒸馏水洗，用二氯甲烷萃取三次，合并有机层，用水洗，有机层用无水硫酸干燥，减压蒸馏除去有机溶剂后，并用柱层析洗脱分离得到化合物1。
所述的反应溶剂配比为二氯甲烷∶三乙胺＝5∶1；所述的柱层析分离洗脱剂配比为乙酸乙酯∶石油醚＝1∶1。
本发明还包括三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针的应用，式(1)化学物在N，N-二甲基甲酰胺(DMF)-水的环境中对Cu2+有独特的荧光选择性。
配置三聚茚基N，N-二(2-吡啶甲基)胺衍生物的DMF/H2O＝8∶2溶液，分别加入定量的MgSO4，Cd(NO3)2，CuCl2，KCl，SnCl2·3H2O，AgNO3，Pb(NO3)2，Ni(CH3COO)2，CrCl2，La(NO3)3·6H2O，Fe2(SO4)3，FeSO4，CaCO3溶液，通过荧光光谱测试来研究对不同离子的选择性，测其荧光发射波谱强度变化发现：本发明所述三聚茚基N，N-二(2-吡啶甲基)胺衍生物即式(1)化合物对Cu2+有独特的荧光选择性，如图2所示。逐渐加入Cu2+至1当量后，式(1)化合物在371nm处的荧光强度显著降低，如图3所示。因此，三聚茚基N，N-二(2-吡啶甲基)胺衍生物作为Cu2+荧光探针具有巨大重要的应用价值。
本发明提供了一种三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针，实验证明本发明所述式(1)化合物可与Cu2+在DMF-H2O(v/v＝8∶2)的混合溶液中以化学计量比为1∶1反应，如图4所示。在反应过程中，由于DPA与铜离子作用，从而使DPA与三聚茚基团发生光致能量传递，导致化合物1在371nm处荧光强度明显降低。由此可证实本发明所述式(1)化合物在DMF-H2O(v/v＝8∶2)的混合溶液中对Cu2+有独特的荧光选择性、极高的灵敏度及较强的抗其它金属离子干扰能力。
本发明的有益效果是：(1)探针的合成路线简单、反应条件温和，提纯方法简便；(2)本发明实现了铜离子探针的选择性快速检测，并且选择性好，抗其他金属离子干扰能力强，检测限低至30nM/L。因此，本发明是一种快速、灵敏的铜离子检测试剂，在分析化学检测领域具有广阔的应用前景。
附图说明
图1是实施例一中探针的1H NMR图谱；
图2是式(1)化合物(1×10-5M)的DMF-H2O(v/v＝8∶2)的溶液中加入10当量的不同金属离子后的荧光强度图；
图3是式(1)化合物(1×10-5M)的DMF-H2O(v/v＝8∶2)的溶液中进行Cu2+荧光滴定图。图中intensity为光强，wavelength为波长，eq为倍数；
图4是式(1)化合物与铜离子络合高分辨电喷雾质谱图；
图5是式(1)化合物(1×10-5M)和等当量的Cu2+共存的DMF-H2O(v/v＝8∶2)的溶液中加入10当量的其它金属离子后荧光强度的变化柱状图。
具体实施方式
下面结合实施例和附图对本发明做进一步的详细说明。
实施例一
目标化合物三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针的制备
(1)化合物2的合成：
氮气保护下，在50mL加入用三聚茚甲醇化合物(1mmol，540mg)，再加入干燥的甲苯25mL溶解，在0℃条件下加入SOCl2(40mmol，300μl)，室温反应过夜。反应结束后用饱和的碳酸氢钠溶液淬灭，用二氯甲烷萃取三次，合并有机层，水洗，饱和食盐水洗，有机层用无水硫酸钠干燥，减压蒸馏除去有机溶剂，得到0.531g固体产物2，产率95％。
(2)化合物1的合成：
在氮气保护下，化合物2(1mmol，558mg)溶解于干燥的二氯甲烷25mL和新蒸馏的三乙胺5mL混合溶剂中，再加入1.5mmol N，N-二(2-吡啶甲基)胺，室温反应过夜。反应结束后用蒸馏水洗，用二氯甲烷萃取三次，合并有机层，用水洗，有机层用无水硫酸干燥，减压蒸馏除去有机溶剂后，并用硅胶柱进行层析分离，洗脱剂为乙酸乙酯∶石油醚＝1∶1，得到淡黄色固体化合物1，产率为87％。其核磁图如图1所示。1H NMR(CDCl3.600MHz，ppm)δ：8.57(d，2H)，8.39-8.41(m，2H)，8.34(d，2H)，7.66-7.68(d，J＝8.4Hz，2H)，7.62-7.64(d，J＝8.4Hz，2H)，7.60-7.61(d，J＝3Hz，1H)，7.66-7.71(m，4H)，7.47-7.53(m，4H)，7.37-7.42(m，4H)，7.12-7.15(t，2H)，3.97(s，4H)，3.90(s，2H)，3.03-3.10(m，6H)，2.16-2.23(m，6H)，0.22-0.26(t，18H).
实施例二
三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针对不同金属离子的选择性
从实施例二中荧光探针储备液中取出1mL加入到10mL的容量瓶中，分别加入10当量的竞争金属离子标准溶液，其中一个加入10当量的氯化铜标准溶液，定容至10mL。竞争金属离子包括Mg2+、Cd2+、Sn2+、Ag+、Pb2+、Cr2+、K+、La3+、Fe3+、Fe2+、Ca2+，后以310nm为激发光检测溶液的荧光发射光谱变化，由图2可以发现，其他金属离子对DPA-三聚茚衍生物的荧光几乎没有影响，而二价铜离子溶液的加入使DPA-三聚茚衍生物的荧光明显减弱。
实施例三
三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针随二价铜离子的加入当量的增加荧光图谱的变化
取实施例一制备的三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针溶于DMF-H2O(v/v＝8∶2)的溶液中，制成10-4mol/L储备液。从储备液中取出1mL加入到10mL的容量瓶中，加入不同当量(0.1-1.0eq)的二价铜离子(氯化铜)标准溶液，定容至10mL，以310nm为激发光测量其荧光性质。荧光光谱如图3所示。由图3可见，三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针溶液的荧光峰随着二价铜离子的加入当量的增加荧光逐渐减弱。
实施例四
三聚茚基N，N-二(2-吡啶甲基)胺类铜离子荧光探针在检测铜离子时对不同金属离子的抗干扰性。
从实施例二中荧光探针的储备液中取出1mL加入到10mL的容量瓶中，加入等当量氯化铜标准溶液，分别加入10当量其他金属离子，定容至10mL。竞争金属离子包括Mg2+、Cd2 +、Sn2+、Ag+、Pb2+、Cr2+、K+、La3+、Fe3+、Fe2+、Ca2+，后以310nm为激发波长检测溶液的荧光发射光谱变化，由图5可以发现，其他金属离子对检测铜离子的三聚茚基N，N-二(2-吡啶甲基)胺类衍生物的荧光几乎没有影响，说明DPA-三聚茚铜离子荧光探针在检测铜离子时对其他金属离子有良好的抗干扰性。
Claims (3)
1.一种三聚茚基N,N-二(2-吡啶甲基)胺类Cu2+荧光探针，其特征在于：它是N,N-二(2-吡啶甲基)胺取代的三聚茚衍生物，分子式为C52H55N3，其化学结构式如式(1)所示：
式(1)化合物在N,N-二甲基甲酰胺-水v/v＝8∶2混合溶液中对Cu2+有独特的荧光选择性。
2.权利要求1所述三聚茚基N,N-二(2-吡啶甲基)胺类Cu2+荧光探针的合成方法，其特征在于，它是按以下步骤进行：
(1)将三聚茚甲醇化合物与二氯亚砜反应得到化合物2，其结构式如下：
(2)将步骤(1)得到的化合物2与N,N-二(2-吡啶甲基)胺(DPA)反应得到荧光探针化合物1，其结构式如下：
3.根据权利要求2所述的三聚茚基N,N-二(2-吡啶甲基)胺类Cu2+荧光探针的合成方法，其特征在于，所述步骤(1)是采用下述方法完成：将1mmol三聚茚甲醇溶解于干燥的甲苯25mL，氮气保护，在0℃下加入40mmol二氯亚砜，室温反应过夜；反应结束后用饱和的碳酸氢钠溶液淬灭，用二氯甲烷萃取三次，合并有机层，水洗，饱和食盐水洗，有机层用无水硫酸钠干燥，减压蒸馏除去有机溶剂，得到化合物2。
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