CN105949122B - The composite nano materials of organic naphthalene and inorganic phosphate - Google Patents
The composite nano materials of organic naphthalene and inorganic phosphate Download PDFInfo
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- CN105949122B CN105949122B CN201610257304.5A CN201610257304A CN105949122B CN 105949122 B CN105949122 B CN 105949122B CN 201610257304 A CN201610257304 A CN 201610257304A CN 105949122 B CN105949122 B CN 105949122B
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 229910052816 inorganic phosphate Inorganic materials 0.000 title claims abstract description 35
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 100
- 239000000463 material Substances 0.000 claims abstract description 98
- 150000001875 compounds Chemical class 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 62
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 57
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 41
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 36
- 239000010949 copper Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 29
- 150000002500 ions Chemical class 0.000 claims description 26
- 235000019441 ethanol Nutrition 0.000 claims description 25
- 238000010521 absorption reaction Methods 0.000 claims description 21
- 239000011651 chromium Substances 0.000 claims description 21
- 229910052793 cadmium Inorganic materials 0.000 claims description 18
- 235000011187 glycerol Nutrition 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 12
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 11
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 10
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims description 6
- 229930182470 glycoside Natural products 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 5
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 4
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229960005069 calcium Drugs 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 3
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 210000004027 cell Anatomy 0.000 abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 239000012472 biological sample Substances 0.000 abstract description 6
- 230000003595 spectral effect Effects 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 2
- 210000000170 cell membrane Anatomy 0.000 abstract description 2
- 208000007578 phototoxic dermatitis Diseases 0.000 abstract description 2
- 231100000018 phototoxicity Toxicity 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 34
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 24
- 229910021645 metal ion Inorganic materials 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052745 lead Inorganic materials 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 8
- 239000006143 cell culture medium Substances 0.000 description 8
- 230000009514 concussion Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- 230000002459 sustained effect Effects 0.000 description 8
- 238000007605 air drying Methods 0.000 description 7
- 239000008139 complexing agent Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000010226 confocal imaging Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001538 azepines Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 230000029142 excretion Effects 0.000 description 2
- 229910003471 inorganic composite material Inorganic materials 0.000 description 2
- 230000003834 intracellular effect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- SNDPXSYFESPGGJ-UHFFFAOYSA-N 2-aminopentanoic acid Chemical class CCCC(N)C(O)=O SNDPXSYFESPGGJ-UHFFFAOYSA-N 0.000 description 1
- 208000004998 Abdominal Pain Diseases 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 206010003591 Ataxia Diseases 0.000 description 1
- 208000014644 Brain disease Diseases 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010019280 Heart failures Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000008763 Mercury poisoning Diseases 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000562569 Riodinidae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 208000029028 brain injury Diseases 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
-
- 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"
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The composite nano materials of organic naphthalene and inorganic phosphate, the structure with general formula I.The composite nano materials can be identified heavy metal, adsorb and clear in living cells.Apparent different identification signal is presented in it during heavy metal adsorption in living cells.This kind of material has the water solubility of certain level, while having good permeability of cell membrane, while also having lower bio-toxicity, phototoxicity, photobleaching.Its spectral region and the spectral region of biological sample have sufficiently large difference.
Description
Technical field
The present invention relates to the composite material that one kind can be used for identification and the absorption of heavy metal in living cells, especially fluorescence has
The composite material of machine naphthalene and inorganic phosphate.
Background technology
Heavy metal refers to that density is more than 4.5 grams of metals per cubic centimeter, such as lead (Pb), cadmium (Cd), chromium (Cr), mercury
(Hg), copper (Cu), golden (Au), silver-colored (Ag) etc..Heavy metal in human body can and the strong interaction of the generations such as protein and enzyme,
Them are made to lose activity, it is also possible to be accumulated in certain organs of human body, slow poisoning can be caused.Such as mercury (Hg), it is to people
Main harm nervous system, makes brain injury, causes caused by mercury poisoning brain disease four limbs fiber crops, and ataxia, the visual field narrows, hearing
The symptoms such as difficulty, severe one heart failure and it is dead.Poisoning pathological change of oral cavity, nausea, emesia, abdominal pain, diarrhea can occur compared with severe one
Etc. symptoms, the systems such as mucocutaneous and uropoiesis, reproduction can also be damaged.Toxicity is more under microbial action, after methylating
Greatly.Therefore, by the way that be identified, adsorb and excrete to heavy metal in living cells with the good method of bio-compatibility will be beneficial
It is removed in intracellular heavy metal.
Organic naphthalene is that one kind has both to heavy metal identification, absorption in living cells with the compound porous nano material of inorganic phosphate
With a kind of important organic/inorganic composite material of excretion.Identify that organic molecule and heavy metal adsorption are received relative to existing heavy metal
For rice material, such organic-inorganic composite material has had both the dual work of detection and absorption excretion to intracellular heavy metal
With being a kind of composite material with very big potential application ability.Relative to conventional material, such compound porous nano material can
It implements function such as：(1) " first fluorescence " can be achieved and identifies heavy metal；(2) material is based on to heavy metal adsorption so that material
Most of heavy metal in adherent cell；(3) according in material it is organic with inorganic part to the difference of heavy metal adsorption,
So that the heavy metal in Materials Inorganic partial competitive absorption organic moiety, and cause change in fluorescence, realize " rear fluorescence " identification
Heavy metal adsorption drains situation.It is accordingly organic to be also rarely reported with inorganic composite nano material.Therefore, low no toxicity, high film are logical
Permeability, highly selective identification, the organic and inorganic compounding for adsorbing and excreting heavy metal in living biological samples (cell or tissue)
Porous nanometer material is one novel developing direction of biological species material, and it is still a blank neck that its design, which is synthesized and prepared,
Domain.
Invention content
The purpose of the present invention first consists in the composite nano materials for providing a kind of organic naphthalene and inorganic phosphate, described multiple
Closing nano material has the structure of general formula I：
In general formula I：
The X is selected from X1、X2And X3：
R1、R2And R3It is each independently selected from：-(CH2)pCOOH、-(CH2)pOH、-(CH2OCH2)pCOOH、-(CH2OCH2)pOH、-CH[(CH2)pCOOH]2、-NH(CH2)pCOOH、-CH[(CH2)pOH]2、-CH[(CH2O CH2)pCOOH]2、-CH
[(CH2OCH2)pOH]2, wherein p is the integer of 1-8
The L is selected from：-NH(CH2)qCH3、-NH(CH2)qNH2、-NH(CH2)qOH、-NH(CH2)qCOOH、-N[(CH2)qCH3]2、-N[(CH2)qNH2]2、-N[(CH2)qOH]2、-N[(CH2)qCOOH]2, a- crown ether-b, the a- crown ether-b of azepine, wherein
Q is the integer of 1-8, and a is the integer of 1-20, and b is the integer of 1-8；
The M is inorganic phosphate salt material；
The n is the integer of 1-8.
The purpose of another aspect of the present invention is to provide the preparation method of above-mentioned composite nano materials, the method includes
Following steps：
1) bromo- 1, the 8- naphthalenes glycosides of 4-, 4- bromines acenaphthenequinone respectively with L-H in molar ratio 1:1-1:6 reactions, prepare compound i and change
Close object ii；
Reaction temperature be 0-200 DEG C, the reaction time be 1-36 hour, reaction dissolvent selected from dichloromethane, ethyl alcohol, methanol,
Or mixtures thereof acetone, 1,4- dioxane, glycerine, ethyl acetate, acetic acid；
2) compound i and compound H2N-R1In molar ratio 1:1-1:5 reactions, prepare compound iii；
Reaction temperature be 0-150 DEG C, the reaction time be 1-16 hour, reaction dissolvent selected from dichloromethane, ethyl alcohol, methanol,
Or mixtures thereof acetone, 1,4- dioxane, glycerine, ethyl acetate, acetic acid；
3) compound i and compound ii respectively with compound iv and iv-1 in molar ratio 1:1-1:5 reactions, prepare compound
V and vi；
Reaction temperature be 0-150 DEG C, the reaction time be 1-16 hour, reaction dissolvent selected from dichloromethane, ethyl alcohol, methanol,
Or mixtures thereof acetone, 1,4- dioxane, glycerine, ethyl acetate, acetic acid；
4) compound iii, v or vi respectively with Ca (NO3)2.4H2O and (NH4)2HPO4According to molar ratio 1:1:10-1:1.5:
50 reactions prepare compounds of formula I：
First, compound iii, v and vi respectively with Ca (NO3)2.4H2O reacts, and reaction dissolvent is selected from dichloromethane, anhydrous
Or mixtures thereof ethyl alcohol, methanol, acetone, 1,4- dioxane, glycerine, ethyl acetate, acetic acid；It is stirred to react time 3-6h；
Then, (the NH of 10mL 0.1-5.0mol/L is added dropwise with the speed of 0.1-10mL/min into said mixture4)2HPO4After being added dropwise, 36-120h is reacted at 20-100 DEG C, and keeps in reaction process PH between 8.0-10 for solution.
The composite nano materials of organic naphthalene and inorganic phosphate of the present invention can " first fluorescence " identification heavy metal；And
Based on material to heavy metal adsorption so that most of heavy metal in material adherent cell；Also, have according in material
Machine is with inorganic part to the difference of heavy metal adsorption so that Materials Inorganic partial competitive adsorbs the huge sum of money in organic moiety
Belong to, and reach change in fluorescence, realizes that " rear fluorescence " identification heavy metal adsorption drains situation.In addition, the present invention's is of the present invention
Organic naphthalene and inorganic phosphate composite nano materials have good biocompatibility and outstanding permeability of cell membrane.
Also there is lower bio-toxicity, phototoxicity, photobleaching simultaneously.Its spectral region and the spectral region of biological sample have enough
Big difference, can be to avoid the generation of archebiosis fluorescence.
Based on this, the present invention further provides the composite nano materials of above-mentioned organic naphthalene and inorganic phosphate heavy metal from
Son identification, absorption and the application in removing.The heavy metal ion is the heavy metal ion in cell.Including but not limited to lead
(Pb), cadmium (Cd), chromium (Cr), mercury (Hg), copper (Cu), golden (Au), silver-colored (Ag) and cobalt (Co).This applies the object of preferred pin pair
For the heavy metal in cell or tumor tissues.
Description of the drawings
17 width of attached drawing of the present invention：
Attached drawing 1 is materials A1Transmission electron microscope photo
Attached drawing 2 is materials A1XRD spectrum test map
Attached drawing 3 is materials A1Water-soluble detection test result.
Attached drawing 4 is materials A2Transmission electron microscope photo
Attached drawing 5 is materials A2XRD spectrum test map
Attached drawing 6 is materials A3Transmission electron microscope photo
Attached drawing 7 is materials A3XRD spectrum test map
Attached drawing 8 is materials A4Transmission electron microscope photo
Attached drawing 9 is materials A4XRD spectrum test map
Attached drawing 10 is materials A1To the identification of living cells heavy metal Cd, adsorb and clear the result of experiment
Attached drawing 11 is materials A2To the identification of living cells heavy metal Pb, adsorb and clear the result of experiment
Attached drawing 12 is materials A3To the identification of living cells heavy metal Cu, adsorb and clear the result of experiment
Attached drawing 13 is materials A4To the identification of living cells heavy metal Pt, adsorb and clear the result of experiment
Attached drawing 14 is atomic absorption spectrography (AAS) detection materials A1The result of experiment is cleared to living cells heavy metal
Attached drawing 15 is atomic absorption spectrography (AAS) detection materials A2The result of experiment is cleared to living cells heavy metal
Attached drawing 16 is atomic absorption spectrography (AAS) detection materials A3The result of experiment is cleared to living cells heavy metal
Attached drawing 17 is atomic absorption spectrography (AAS) detection materials A4The result of experiment is cleared to living cells heavy metal
Specific implementation mode
Unless otherwise stated, term used herein has following meanings.
Term " alkyl " used herein includes straight chained alkyl, branched alkyl and naphthenic base.Such as refer to specific alkyl name
Claim, such as " propyl ", " isopropyl " or " cyclopropyl ", refers in particular to the direct-connected alkyl of specific carbon atom number purpose, branched alkyl and naphthenic base.
Such as the description of general form, such as " C1-8Alkyl " includes then all groups that carbon atom number is met the requirements, " C1-8Alkyl " include but
It is not limited to C1-6Alkyl, C1-5Alkyl, methyl, ethyl, n-propyl, isopropyl, tertiary butyl, cyclopropyl, cyclobutyl, methylcyclopropyl groups
Deng.Similar rule is also suitable the other groups used in this manual.
Present invention firstly provides a kind of composite nano materials of organic naphthalene and inorganic phosphate, the structure with general formula I：
In general formula I：The X is selected from X1、X2And X3, by a dotted line key be connected respectively with rest part in general formula I, wherein
The dotted line key is chemical bond：
Wherein, R2And R3Arbitrarily replace in respective cyclic compound structure, the R1、R2And R3It selects each independently
From：-(CH2)pCOOH、-(CH2)pOH、-(CH2OCH2)pCOOH、-(CH2OCH2)pOH、-CH[(CH2)pCOOH]2、-NH(CH2)pCOOH、-CH[(CH2)pOH]2、-CH[(CH2O CH2)pCOOH]2、-CH[(CH2OCH2)pOH]2, wherein p is the integer of 1-8.
In specific implementation mode, R1、R2And R3It is each independently selected from-(CH2)pCOOH、-(CH2)pOH and-NH (CH2)pCOOH.It is further preferable that the R1Selected from-(CH2)pCOOH or-(CH2)pOH；The R2Selected from-NH (CH2)pCOOH；Institute
The R stated3Selected from-(CH2)pCOOH。
In general formula I, the L is selected from：-NH(CH2)qCH3、-NH(CH2)qNH2、-NH(CH2)qOH、-NH(CH2)qCOOH、-N[(CH2)qCH3]2、-N[(CH2)qNH2]2、-N[(CH2)qOH]2、-N[(CH2)qCOOH]2, a- crown ether-b, azepine
A- crown ethers-b；It is preferably selected from-N [(CH2)qCH3]2、-N[(CH2)qNH2]2、-N[(CH2)qOH]2、-N[(CH2)qCOOH]2, a- hat
A- crown ethers-the b of ether-b, azepine；L particularly preferably-N [(CH2)qOH]2, a- crown ether-b or azepine a- crown ethers-b.Wherein, q is 1-
8 integer, the preferably integer of 1-4.A is the integer of 1-20, and b is the integer of 1-8；In preferred scheme, a>7 and a=b+1.
In general formula I, the M is inorganic phosphate salt material, it passes through the R of X section in wave key and general formula1,R2Or R3
It is connected, the wave key is chemical bond, hydrogen bond or electrostatic force；M can be with multiple I-M groups with respectively independent in general formula
Connection type be connected, the numbers of I-M groups is n, and the n is the integer of 1-8, the I-M groups be general formula I except M with
Outer remainder.
In specific implementation mode, the M is selected from hydroxyapatite (HAP), calcium octahate phosphate (Ocp), calcium monohydrogen phosphate
(DCP), calcium dihydrogen phosphate (MCP) or tricalcium phosphate (TCP).M preferably is selected from hydroxyapatite (HAP), calcium monohydrogen phosphate (DCP) or phosphorus
Acid dihydride calcium (MCP).
Each preferred feature described above can be combined with each other, and gained technical solution should be included in this hair completely
Bright addressed range.
The example of the combination of preferred feature one of is for specific embodiment of the present invention, organic naphthalene and
The composite nano materials of inorganic phosphate are selected from compound A1-A4：
On the other hand, the present invention provides the systems of organic naphthalene of aforementioned present invention and the composite nano materials of inorganic phosphate
Preparation Method includes the following steps：
1) bromo- 1, the 8- naphthalenes glycosides of 4-, 4- bromines acenaphthenequinone respectively with L-H in molar ratio 1:1-1:6 reactions, prepare compound i and change
Close object ii；
In specific implementation mode, the reaction temperature of the step 1) is 0-200 DEG C, preferably 25-180 DEG C, more preferable 50-
180 DEG C, most preferably 60-150 DEG C；The reaction time is 1-36 hours, preferably 1-23 hours, 1-22 hours more preferable, most
It is preferred that 1-20 hours；The reaction dissolvent is selected from dichloromethane, ethyl alcohol, methanol, acetone, 1,4- dioxane, glycerine, second
Or mixtures thereof acetoacetic ester, acetic acid, more preferable dichloromethane, ethyl alcohol, methanol, Isosorbide-5-Nitrae-dioxane, glycerine, ethyl acetate,
Or mixtures thereof acetic acid, or mixtures thereof most preferred ethanol, methanol, glycerine, ethyl acetate, acetic acid.
2) compound i and compound H2N-R1In molar ratio 1:1-1:5 reactions, prepare compound iii；
In specific implementation mode, the reaction temperature of the step 2) is 0-150 DEG C, preferably 0-140 DEG C, more preferable 25-140
DEG C, most preferably 60-140 DEG C；The reaction time is 1-16 hours, preferably 1-15 hours, 1-13 hours more preferable, most preferably
1-12 hours；The reaction dissolvent is selected from dichloromethane, ethyl alcohol, methanol, acetone, 1,4- dioxane, glycerine, acetic acid second
Or mixtures thereof ester, acetic acid, preferably dichloromethane, ethyl alcohol, methanol, Isosorbide-5-Nitrae-dioxane, glycerine, ethyl acetate, acetic acid or
Its mixture, or mixtures thereof more preferable ethyl alcohol, methanol, glycerine, ethyl acetate, acetic acid.
3) compound i and compound ii respectively with compound iv and iv-1 in molar ratio 1:1-1:5 reactions, prepare compound
V and vi；
In specific implementation mode, the reaction temperature of the step 3) is 0-150 DEG C, preferably 25-150 DEG C, more preferable 50-
150 DEG C, most preferably 60-150 DEG C；The reaction time is 1-16 hours, preferably 1-13 hours, 1-12 hours more preferable, most
It is preferred that 1-10 hours；The reaction dissolvent is dichloromethane, ethyl alcohol, methanol, acetone, 1,4- dioxane, glycerine, acetic acid
Or mixtures thereof ethyl ester, acetic acid, preferably dichloromethane, ethyl alcohol, methanol, Isosorbide-5-Nitrae-dioxane, glycerine, ethyl acetate, acetic acid
Or mixtures thereof, or mixtures thereof more preferable ethyl alcohol, methanol, glycerine, ethyl acetate, acetic acid.
4) compound iii, v or vi respectively with Ca (NO3)2.4H2O (four water-calcium nitrate) and (NH4)2HPO4(phosphoric acid hydrogen two
Ammonium) according to molar ratio 1:1:10-1:1.5:50 reactions prepare compounds of formula I：
In specific implementation mode, first, compound iii, v or vi respectively with Ca (NO3)2.4H2O and (NH4)2HPO4Reaction
Molar ratio preferably 1:1:15-1:1.5:45, more preferable 1:1:15-1:1.5:43, most preferably 1:1:15-1:1.5:40.
Secondly, compound iii, v and vi respectively with Ca (NO3)2.4H2O reacts：Preferred 25-100 DEG C of reaction temperature, it is more excellent
Select 30-90 DEG C, most preferably 40-80 DEG C；It is stirred to react time 3-6h, preferably 3-5.5h, more preferable 3-5h, most preferably 3-4.5h；
Reaction dissolvent be selected from dichloromethane, absolute ethyl alcohol, methanol, acetone, 1,4- dioxane, glycerine, ethyl acetate, acetic acid or its
Mixture.
Then, (the NH of 10mL 0.1-5.0mol/L is added dropwise with the speed of 0.1-10mL/min into said mixture4)2HPO4After being added dropwise, 36-120h is reacted at 20-100 DEG C, and keeps in reaction process PH between 8.0-10 for solution.Its
In, (NH4)2HPO4Rate of addition preferred 0.1-5mL/min, more preferable 0.1mL-3mL/min, most preferably 0.1mL-2mL/min；
(NH4)2HPO4Solution concentration preferred 0.1-3.0mol/L, more preferable 0.1mol/L-2.0mol/L, most preferably 0.1mol/L-
1.0mol/L.The reaction time is 36-110 hours preferred, 40-100 hours more preferable, most preferably 50-90 hours.
It is total with nuclear-magnetism to using organic naphthalene prepared by the synthetic method of the present invention and inorganic phosphate composite nano materials
Spectrogram, mass spectrum, infrared spectrum, XRD difraction spectrums, power spectrum, scanning electron microscope, transmission electron microscope etc. shake to confirm its structure.
The composite nano materials of organic naphthalene and inorganic phosphate of the present invention have following advantages：
Answering for organic naphthalene and inorganic phosphate can be improved with the fluorogen of heavy metal proportion change in fluorescence by introducing
Close the fluorescence feedback capability that nano material identifies heavy metal in living cells and tissue and remove situation；
With multi-pore channel structure, it is easy to it applied to the absorption of heavy metal in biological sample and clears ability；
Side effect is small, and raw material is easy to get, simple in structure, easily prepared；
In consideration of it, the composite nano materials of organic naphthalene of the present invention and inorganic phosphate can be used for a huge sum of money in living cells
Belong to label, adsorb and clear.In addition to being directly used in living cells heavy metal label, absorption and clear in the form of described herein
The composition of fortune, the composite nano materials of organic naphthalene and inorganic phosphate containing the present invention can be used for a huge sum of money in living cells
Belong to label, adsorb and clear.Should include a effective amount of organic naphthalene provided by the present invention and inorganic phosphate in the composition
One of composite nano materials of salt.Furthermore it is also possible to be incubated required other components, such as solvent, pH comprising biological sample
Conditioning agent etc..These components are all that one's own profession is known in the art.Above-mentioned composition can exist as an aqueous solution, or can be with
The other suitable forms for being formulated as solution with water before use exist.
The present invention also provides in the composite nano materials living cells of organic naphthalene and inorganic phosphate for using aforementioned present invention
The method that heavy metal marks, adsorbs and clear, this method includes making the composite nano materials of organic naphthalene and inorganic phosphate
The step of being contacted with biological sample.Term " contact " used herein may include contacting in solution or solid phase.
Following non-limiting embodiments can make those skilled in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Embodiment 1
The composite nano materials A of organic naphthalene and inorganic phosphate1(abbreviation materials A1), synthetic route is as follows：
(1) compound A1- 1 synthesis
The bromo- 1,8- naphthalenes glycosides of 20mmol4- and 70mmol diethanolamines are added to the round-bottomed flask containing 10ml ethanol solutions
In, nitrogen protection.Reaction stops after being heated to reflux sustained response 16h.Mixture pours into ice water, Precipitation, filters yellow
Color solid powder crude product, compound A1- 1, yield 90%.
(2) compound A1- 2 synthesis
By 20mmol compounds A1- 1 and 30mmol aminovaleric acids are added in the round-bottomed flask of 20ml acetums, nitrogen
Protection.Stop after 125 DEG C of reflux sustained response 12h of reaction heating.Decompression steams solvent, and pillar layer separation obtains yellow solid powder
Compound A1- 2, yield 72%.
(3) materials A1Synthesis
0.002g A are added in flask1- 2, with 30ml absolute ethyl alcohols, solution is stirred to without undissolved C22H43O4N2
.Beaker is taken again, by 2.36g Ca (NO3)2.4H2O and the dissolving of 20ml absolute ethyl alcohol mixed solutions are complete, and two kinds of solution are mixed
Close it is uniform, be placed on magnetic stirring apparatus stir 3 hours it is spare.
By 0.79g (NH4)2HPO4(i.e. diammonium hydrogen phosphate) is dissolved in 10ml water, and it is molten that above-mentioned mixing is slowly dropped to after dissolving
In liquid.Under the conditions of condensing reflux, mixed solution reacts 72 hours in 40 DEG C of oil bath heatings.At interval of 2 hours with dense ammonia in reaction
Water adjusts PH=9.0.After reaction, cooling is stood, there is the generation of light yellow solid sediment.Solution is removed, deionization is added
Water washs the sediment of bottom repeatedly, until solution clear, stands after removing extra solution, precipitates natural air drying about 15
It.The light yellow powder product of short texture is obtained, it is primary with water cleaning, it is dried up in air and obtains the material of even compact
A1。
(4) materials A1Characterization
To A1Middle organic molecule A1The characterization of -2 parts:1H NMR (400MHz, DMSO) δ 10.89 (s, 1H) 8.40 (d, J=
8.3Hz, 1H), 8.35 (d, J=7.2Hz, 1H), 8.29 (d, J=8.3Hz, 1H), 7.76 (d, J=6.9Hz, 1H), 7.27 (d,
J=6.9Hz, 1H), 4.30 (m, 4H), 3.75 (m, 4H), 3.60 (s, 2H), 3.20 (m, 2H), 2.35 (m, 2H), 1.56-1.52
(m,4H).
To A1Characterization:1H NMR (400MHz, DMSO) δ 8.40 (d, J=8.3Hz, 1H), 8.35 (d, J=7.2Hz,
1H), 8.29 (d, J=8.3Hz, 1H), 7.76 (d, J=6.9Hz, 1H), 7.27 (d, J=6.9Hz, 1H), 4.30 (m, 4H),
3.75(m,4H),3.60(s,2H),3.20(m,2H),2.35(m,2H),1.56-1.52(m,4H).
By A1With A1- 21H NMR test result comparative analyses, analysis shows that：A1Peaks OH in -2 disappear, at this moment due to
A1- 2 are connected to form A with inorganic phosphate composite nano materials by chemical bond1。
Resulting materials A1Transmission electron microscope photo such as Fig. 1.As can be seen, A1For porous nanometer material.
Resulting materials A1XRD spectrum testing result it is as shown in Fig. 2.As a result it shows：A1For hydroxyapatite porous nano
Material.
Embodiment 2：Materials A1Water-soluble detection experiment
Use the materials A of above-mentioned synthesis1Be added to the water, measure various concentration (0.27,0.65,0.86,1.1,1.5,
2.0,3.0mg/mL) A1Absorbance under the maximum absorption wavelength of aqueous solution.Test result is Fig. 3, display：Work as materials A1It is a concentration of
When 2.0mg/mL, absorbance value does not shift, i.e. materials A1Solubility in water is 2.0mg/mL.
The present embodiment instrument is 8453 ultraviolet specrophotometers of Agilent respectively.
Embodiment 3
The composite nano materials A of organic naphthalene and inorganic phosphate2(abbreviation materials A2), synthetic route is as follows：
(1) compound A2- 1 synthesis
The bromo- 1,8- naphthalenes glycosides of 20mmol4- and 70mmol diethanolamines are added to the round-bottomed flask containing 10ml ethanol solutions
In, nitrogen protection.Reaction stops after being heated to reflux sustained response 16h.Mixture pours into ice water, Precipitation, filters yellow
Color solid powder crude product, compound A2- 1, yield 90%.
(2) compound A2- 2 synthesis
20mmol compound A1-1 and 30mmol compounds B is added in the round-bottomed flask of 20ml acetums, nitrogen
Protection.Stop after 125 DEG C of reflux sustained response 12h of reaction heating.Decompression steams solvent, and pillar layer separation obtains yellow solid powder
Compound A2- 2, yield 72%.
(3) materials A2Synthesis
0.005g A are added in flask2- 2 with 30ml absolute ethyl alcohols, solution is stirred to without undissolved C22H43O4N2
.Beaker is being taken, by 2.36g Ca (NO3)2.4H2O and the dissolving of 20ml absolute ethyl alcohol mixed solutions are complete, and two kinds of solution are mixed
Close it is uniform, be placed on magnetic stirring apparatus stir 3 hours it is spare.
By 0.79g (NH4)2HPO4It is dissolved in 10ml water, is slowly dropped to after dissolving in above-mentioned solution.By mixed solution 30
DEG C oil bath condensing reflux heating reaction 72 hours.PH was adjusted at interval of 1 hour in reaction, dipping concentrated ammonia liquor with pipette tips adjusts PH=
10.After reaction, the solution above sediment is drawn, the solid that deionized water rinses bottom repeatedly is added, it is extra to be sucked out
Solution will precipitation stand.A is added2- 2 solution, ultrasound draw supernatant liquor, and deionized water is cleaned repeatedly.Natural air drying needs 15
It or so.The light yellow powder product of short texture is obtained after air-drying, it is primary with water cleaning, it dries up in air and is uniformly caused
Close materials A2。
(4) materials A2Characterization
To A2Middle organic molecule A2The characterization of -2 parts:1H NMR (400MHz, DMSO) δ 10.89 (s, 1H) 8.40 (d, J=
8.3Hz, 1H), 8.35 (d, J=7.2Hz, 1H), 8.29 (d, J=8.3Hz, 1H), 7.76 (d, J=6.9Hz, 1H), 7.40 (d,
J=6.3Hz, 1H), 7.27 (d, J=6.9Hz, 1H), 6.87 (d, J=6.8Hz, 1H), 6.47 (d, J=6.8Hz, 1H), 4.30
(m,4H),3.75(m,4H),3.60(s,2H),3.20(m,2H),2.35(m,2H),1.56-1.52(m,4H).
To A2Characterization:1H NMR (400MHz, DMSO) δ 11.09 (s, 1H) 8.40 (d, J=8.3Hz, 1H), 8.35 (d, J
=7.2Hz, 1H), 8.29 (d, J=8.3Hz, 1H), 7.76 (d, J=6.9Hz, 1H), 7.40 (d, J=6.3Hz, 1H), 7.27
(d, J=6.9Hz, 1H), 6.87 (d, J=6.8Hz, 1H), 6.47 (d, J=6.8Hz, 1H), 4.30 (m, 4H), 3.75 (m,
4H),3.60(s,2H),3.20(m,2H),2.35(m,2H),1.56-1.52(m,4H).
By A2With A2- 21H NMR test result comparative analyses, analysis shows that：A2The peaks OH in -2 are in A2In still have display,
But to 11.09ppm, this illustrates A for chemical shift2- 2 are connected to form A with inorganic phosphate composite nano materials by hydrogen bond2。
Resulting materials A2Transmission electron microscope photo such as attached drawing 4.As can be seen, materials A2For nano material.
Resulting materials A2XRD spectrum testing result it is as shown in Fig. 5.As a result it shows：A2For hydroxyapatite porous nano
Material.
Embodiment 4
The composite nano materials A of organic naphthalene and inorganic phosphate3(abbreviation materials A3), synthetic route is as follows：
(1) compound A3- 1 synthesis
20mmol 5- bromines acenaphthenequinones and 18 crown ether of 70mmol azepines are added to the round-bottomed flask containing 10ml ethanol solutions
In, nitrogen protection.Reaction stops after being heated to reflux sustained response 16h.Mixture pours into ice water, Precipitation, filters yellow
Color solid powder crude product, compound A3- 1, yield 50%.
(2) compound A3- 2 synthesis
By 20mmol compounds A3- 1 and 30mmol compounds B1It is added in the round-bottomed flask of 20ml acetums, nitrogen
Protection.Stop after 125 DEG C of reflux sustained response 12h of reaction heating.Decompression steams solvent, and pillar layer separation obtains yellow solid powder
Compound A3- 2, yield 65%.
(3) materials A3Synthesis
0.002g A are added in flask3- 2 with 30ml absolute ethyl alcohols, solution is stirred to without undissolved C22H43O4N2
.Beaker is being taken, by 2.36gCa (NO3)2.4H2O and the dissolving of 20ml absolute ethyl alcohol mixed solutions are complete, and two kinds of solution are mixed
Close it is uniform, be placed on magnetic stirring apparatus stir 3 hours it is spare.
By 0.79g (NH4)2HPO4It is dissolved in 10ml water, is slowly dropped to after dissolving in above-mentioned solution.By mixed solution 40
DEG C oil bath condensing reflux heating reaction 72 hours.PH was adjusted at interval of 2 hours in reaction, dipping concentrated ammonia liquor with pipette tips adjusts PH=
9.0.After reaction, cooling is stood, has light yellow solid in the solution.By above sediment solution draw, addition go from
Sub- water rinses the solid of bottom repeatedly, until solution colour above is as clear as crystal, extra solution is sucked out and stands precipitation, from
So air-drying needs 15 days or so.The light yellow powder product of short texture is obtained after air-drying, it is primary with water cleaning, it is dried up in air
Obtain the materials A of even compact3。
To A3Middle organic molecule A3The characterization of -2 parts:1H NMR (400MHz, DMSO) δ 10.90 (s, 1H) 7.95 (d, J=
8.3Hz, 1H), 7.88 (d, J=7.2Hz, 1H), 7.80 (d, J=8.3Hz, 1H), 7.76 (d, J=6.9Hz, 1H), 7.62 (d,
J=7.2Hz, 1H), 7.55-7.57 (m, 2H), 6.90 (d, J=6.9Hz, 1H), 5.50-5.30 (m, 18H), 2.85 (m, 2H),
2.56(m,2H).
To A3Characterization:1H NMR (400MHz, DMSO) δ 7.95 (d, J=8.3Hz, 1H), 7.88 (d, J=7.2Hz,
1H), 7.80 (d, J=8.3Hz, 1H), 7.76 (d, J=6.9Hz, 1H), 7.62 (d, J=7.2Hz, 1H), 7.55-7.57 (m,
2H), 6.90 (d, J=6.9Hz, 1H), 5.50-5.30 (m, 18H), 2.85 (m, 2H), 2.56 (m, 2H)
By A3With A3- 21H NMR test result comparative analyses, analysis shows that：A3The peaks OH in -2 are in A3Middle disappearance, this says
Bright A3- 2 are connected to form composite A with inorganic phosphate composite nano materials by chemical bond3。
Resulting materials A3Transmission electron microscope photo such as Fig. 6.As can be seen, A3For porous nanometer material.
Resulting materials A3XRD spectrum testing result it is as shown in Fig. 7.As a result it shows：A3For hydroxyapatite porous nano
Material.
Embodiment 5
The composite nano materials A of organic naphthalene and inorganic phosphate4(abbreviation materials A4), synthetic route is as follows：
(1) compound A4- 1 synthesis
The bromo- 1,8- naphthalenes glycosides of 20mmol 4- and 18 crown ether of 70mmol azepines are added to the round bottom containing 10ml ethanol solutions
In flask, nitrogen protection.Reaction stops after being heated to reflux sustained response 16h.Mixture pours into ice water, Precipitation, filters
Obtain yellow solid powder crude product, compound A4- 1, yield 45%.
(2) compound A4- 2 synthesis
By 20mmol compounds A4- 1 and 30mmol amino enanthol is added in the round-bottomed flask of 20ml acetums, nitrogen
Protection.Stop after 125 DEG C of reflux sustained response 12h of reaction heating.Decompression steams solvent, and pillar layer separation obtains yellow solid powder
Compound A4- 2, yield 65%.
(3) materials A4Synthesis
0.002g A are added in flask4- 2 with 30ml absolute ethyl alcohols, solution is stirred to without undissolved C22H43O4N2
.Beaker is being taken, by 2.36g Ca (NO3)2.4H2O and the dissolving of 20ml absolute ethyl alcohol mixed solutions are complete, and two kinds of solution are mixed
Close it is uniform, be placed on magnetic stirring apparatus stir 3 hours it is spare.
By 0.79g (NH4)2HPO4It is dissolved in 10ml water, is slowly dropped to after dissolving in above-mentioned solution.By mixed solution 30
DEG C oil bath condensing reflux heating reaction 72 hours.PH was adjusted at interval of 1 hour in reaction, dipping concentrated ammonia liquor with pipette tips adjusts PH=
10.After reaction, the solution above sediment is drawn, the solid that deionized water rinses bottom repeatedly is added, it is extra to be sucked out
Solution will precipitation stand.A is added4- 2 solution, ultrasound draw supernatant liquor, and deionized water is cleaned repeatedly.Natural air drying needs 15
It or so.The light yellow powder product of short texture is obtained after air-drying, it is primary with water cleaning, it dries up in air and is uniformly caused
Close materials A4。
To A4Middle organic molecule A4The characterization of -2 parts:1H NMR (400MHz, DMSO) δ 8.40 (d, J=8.3Hz, 1H),
8.35 (d, J=7.2Hz, 1H), 8.29 (d, J=8.3Hz, 1H), 7.76 (d, J=6.9Hz, 1H), 7.40 (d, J=6.3Hz,
1H),5.50(m,18H),3.55(s,1H),3.50(m,2H),3.20(m,2H),1.66-1.63(m,6H),1.23-1.25(m,
4H).
To A4Characterization:1H NMR (400MHz, DMSO) δ 8.40 (d, J=8.3Hz, 1H), 8.35 (d, J=7.2Hz,
1H), 8.29 (d, J=8.3Hz, 1H), 7.76 (d, J=6.9Hz, 1H), 7.40 (d, J=6.3Hz, 1H), 5.50 (m, 18H),
4.70(s,1H),3.50(m,2H),3.20(m,2H),1.66-1.63(m,6H),1.23-1.25(m,4H).
By A4With A4- 21H NMR test result comparative analyses, analysis shows that：A4The peaks OH in -2 are in A4In still have display,
But to 4.70ppm, this illustrates A for chemical shift4- 2 are connected to form materials A with inorganic phosphate composite nano materials by hydrogen bond4。
Resulting materials A4Transmission electron microscope photo such as Fig. 8.As can be seen, A4For nanometer sheet.
Resulting materials A4XRD spectrum testing result it is as shown in Fig. 9.As a result it shows：Materials A4It is porous for hydroxyapatite
Nano material.
Embodiment 6：Materials A1To the identification of living cells heavy metal Cd, adsorb and clear experiment
With the materials A of final concentration of 2.0mg/mL1It is incubated HepG2 cells respectively, wherein heavy metal is added in experimental group
Cd, at 37 DEG C, 5%CO2It is incubated 30 minutes.PBS concussion rinsings 5min × 3, add cell culture medium, laser co-focusing at
Picture.Representative area is chosen, is observed with dry mirror (40 ×), in triplicate.The network of Cd metal ions is then added in experimental group
Mixture reduces the content of Cd ions.Then shake rinsing 5min × 3 with PBS, add cell culture medium, laser co-focusing at
Picture.Representative area is chosen, is observed with dry mirror (40 ×), in triplicate.
Experimental result such as Figure 10, surface：Materials A1With the reduction of heavy metal amount in HepG2 cells, relative comparison group,
A, b are control group, c and d groups are that heavy metal Cd group is added, and fluorescence signal weakens (c) at wherein 550nm, and fluorescence is believed at 470nm
Number enhancing (d).This is mainly due to materials As1Materials A caused by adsorbing metal ions Cd1In molecular moiety A1- 2 pairs of metals from
The recognition reaction of sub- Cd.Opposite c and d groups, e and f groups are the complexing agent group of addition heavy metal Cd and Cd metal ions, wherein
Fluorescence signal enhancing (e) at 550nm, and fluorescence signal weakens (f) at 470nm.Comprehensive three groups of experimental contrast analysis, it can be deduced that
Materials A1It can effectively identify, adsorb and clear heavy metal Cd, wherein materials A1Middle A1- 2 parts mainly identify heavy metal Cd
Effect, what composite material rest part played the role of is to adsorb and clear heavy metal Cd.
Embodiment 7：Materials A2To the identification of living cells heavy metal Pb, adsorb and clear experiment
With the A of final concentration of 2.0mg/mL2It is incubated HepG2 cells respectively, wherein heavy metal Pb is added in experimental group,
37 DEG C, 5%CO2It is incubated 30 minutes.PBS concussion rinsings 5min × 3, add cell culture medium, laser confocal imaging.It chooses
Representative area is observed, in triplicate with dry mirror (40 ×).The complexing agent of Pb metal ions, drop are then added in experimental group
The content of low Pb ions.Rinsing 5min × 3 then are shaken with PBS, add cell culture medium, laser confocal imaging.It chooses
Representative area is observed, in triplicate with dry mirror (40 ×).
Experimental result such as attached drawing 11, shows：Materials A2With the reduction of heavy metal amount, opposite a and b in HepG2 cells
Group, c and d groups are that heavy metal Pb group is added, and fluorescence signal weakens (c) at wherein 550nm, and fluorescence signal enhances at 470nm
(d).This is mainly due to materials As2Materials A caused by adsorbing metal ions Pb2In molecular moiety A2- 2 couples of metal ion Pb's
Recognition reaction.Opposite c and d groups, e and f groups are that the complexing agent group of heavy metal Pb and Pb metal ions is added, glimmering at wherein 550nm
Optical signal enhances (e), and fluorescence signal weakens (f) at 470nm.Comprehensive three groups of experimental contrast analysis, it can be deduced that materials A2It can
Effectively to identify, adsorb and clear heavy metal Pb, wherein materials A2Middle A2- 2 parts mainly identify heavy metal Pb effect, multiple
What condensation material rest part played the role of is to adsorb and clear heavy metal Pb.
Embodiment 8：Materials A3The experiment that living cells heavy metal Cu is identified, adsorbs and clears
With the A of final concentration of 2.0mg/mL3It is incubated HepG2 cells respectively, wherein heavy metal Cu is added in experimental group,
37 DEG C, 5%CO2It is incubated 30 minutes.PBS concussion rinsings 5min × 3, add cell culture medium, laser confocal imaging.It chooses
Representative area is observed, in triplicate with dry mirror (40 ×).The complexing agent of Cu metal ions, drop are then added in experimental group
The content of low Cu ions.Rinsing 5min × 3 then are shaken with PBS, add cell culture medium, laser confocal imaging.It chooses
Representative area is observed, in triplicate with dry mirror (40 ×).
Experimental result such as Figure 12, shows：Materials A3With the reduction of heavy metal amount, relative comparison group in HepG2 cells
(a and b), c and d groups are that heavy metal Cu group is added, and fluorescence signal weakens (c) at wherein 550nm, and fluorescence signal increases at 470nm
By force (d).This is mainly due to materials As3Materials A caused by adsorbing metal ions Cu3In molecular moiety A3- 2 couples of metal ion Cu
Recognition reaction.Opposite c and d groups, e and f groups are that the complexing agent group of heavy metal Cu and Cu metal ions is added, at wherein 550nm
Fluorescence signal enhances (e), and fluorescence signal weakens (f) at 470nm.Comprehensive three groups of experimental contrast analysis, it can be deduced that materials A3
It can effectively identify, adsorb and clear heavy metal Cu, wherein materials A3Middle A3- 2 parts mainly identify heavy metal Cu effect,
What composite material rest part played the role of is to adsorb and clear heavy metal Cu
Embodiment 9：Materials A4The experiment that living cells heavy metal Pt is identified, adsorbs and clears
With the A of final concentration of 2.0mg/mL4It is incubated HepG2 cells respectively, wherein heavy metal Pt is added in experimental group,
37 DEG C, 5%CO2It is incubated 30 minutes.PBS concussion rinsings 5min × 3, add cell culture medium, laser confocal imaging.It chooses
Representative area is observed, in triplicate with dry mirror (40 ×).The complexing agent of Pt metal ions, drop are then added in experimental group
The content of low Pt ions.Rinsing 5min × 3 then are shaken with PBS, add cell culture medium, laser confocal imaging.It chooses
Representative area is observed, in triplicate with dry mirror (40 ×).
Experimental result such as attached drawing 13, shows：Materials A4With the reduction of heavy metal amount, relative comparison in HepG2 cells
Group (a and b), c and d groups are that heavy metal Pt groups are added, and fluorescence signal weakens (c) at wherein 550nm, and fluorescence signal at 470nm
Enhance (d).This is mainly due to materials As4Materials A caused by adsorbing metal ions Pt4In molecular moiety A4- 2 pairs of metal ions
The recognition reaction of Pt.Opposite c and d groups, e and f groups are that the complexing agent group of heavy metal Pt and Pt metal ion, wherein 550nm is added
Locate fluorescence signal enhancing (e), and fluorescence signal weakens (f) at 470nm.Comprehensive three groups of experimental contrast analysis, it can be deduced that material
A4It can effectively identify, adsorb and clear heavy metal Pt, wherein materials A4Middle A4- 2 parts mainly identify that heavy metal Pt makees
With what composite material rest part played the role of is to adsorb and clear heavy metal Pt.
Embodiment 10：Atomic absorption spectrography (AAS) detects materials A1Experiment is cleared to living cells heavy metal
Selection HepG2 cells are research object.Be separately added into experimental group and control group heavy metal Pt, Cu, Pb, Cd,
Cr, Co, Hg, Ag ion, at 37 DEG C, 5%CO2It is incubated 30 minutes.Control group PBS concussion rinsings 5min × 3, vitellophag are ground
Mill pretreatment, obtains the heavy metal in control group.Experimental group is with the A of final concentration of 2.0mg/mL1It is incubated 30min, PBS shakes respectively
Rinsing 5min × 3, vitellophag are swung, grinding pretreatment obtains the heavy metal in control group.Then by the control group of acquisition and reality
The metal tested in group is measured with atomic absorption spectrophotometer respectively.As shown in Fig. 14, in figure 1-8 indicate respectively be added Pt,
The test result of Cu, Pb, Cd, Cr, Co, Hg, Ag8 metal ion species.As it can be seen that materials A1Heavy metal in processed experimental group
Ion concentration is substantially reduced.Prove A1It is adsorbable and clear heavy metal Pt, Cu, Pb, Cd, Cr, Co, Hg, Ag ion.It is golden in figure
The sequence for belonging to ion is (1) Pt, (2) Cu, (3) Pb, (4) Cd, (5) Cr, (6) Co, (7) Hg, (8) Ag.
Embodiment 11：Atomic absorption spectrography (AAS) detects materials A2Experiment is cleared to living cells heavy metal
Selection HepG2 cells are research object.Be separately added into experimental group and control group heavy metal Pt, Cu, Pb, Cd,
Cr, Co, Hg, Ag ion, at 37 DEG C, 5%CO2It is incubated 30 minutes.Control group PBS concussion rinsings 5min × 3, vitellophag are ground
Mill pretreatment, obtains the heavy metal in control group.Experimental group is with the A of final concentration of 2.0mg/mL2It is incubated 30min, PBS shakes respectively
Rinsing 5min × 3, vitellophag are swung, grinding pretreatment obtains the heavy metal in control group.Then by the control group of acquisition and reality
The metal tested in group is measured with atomic absorption spectrophotometer respectively.As shown in Fig. 15, in figure 1-8 indicate respectively be added Pt,
The test result of Cu, Pb, Cd, Cr, Co, Hg, Ag8 metal ion species.As it can be seen that materials A2Heavy metal in processed experimental group
Ion concentration is substantially reduced.Prove A2It is adsorbable and clear heavy metal Pt, Cu, Pb, Cd, Cr, Co, Hg, Ag ion.It is golden in figure
The sequence for belonging to ion is (1) Pt, (2) Cu, (3) Pb, (4) Cd, (5) Cr, (6) Co, (7) Hg, (8) Ag.
Embodiment 12：Atomic absorption spectrography (AAS) detects materials A3Experiment is cleared to living cells heavy metal
Selection HepG2 cells are research object.Be separately added into experimental group and control group heavy metal Pt, Cu, Pb, Cd,
Cr, Co, Hg, Ag ion, at 37 DEG C, 5%CO2It is incubated 30 minutes.Control group PBS concussion rinsings 5min × 3, vitellophag are ground
Mill pretreatment, obtains the heavy metal in control group.Experimental group is with the A of final concentration of 2.0mg/mL3It is incubated 30min, PBS shakes respectively
Rinsing 5min × 3, vitellophag are swung, grinding pretreatment obtains the heavy metal in control group.Then by the control group of acquisition and reality
The metal tested in group is measured with atomic absorption spectrophotometer respectively.As shown in Fig. 16, in figure 1-8 indicate respectively be added Pt,
The test result of Cu, Pb, Cd, Cr, Co, Hg, Ag8 metal ion species.As it can be seen that materials A3Heavy metal in processed experimental group
Ion concentration is substantially reduced.Prove A3It is adsorbable and clear heavy metal Pt, Cu, Pb, Cd, Cr, Co, Hg, Ag ion.It is golden in figure
The sequence for belonging to ion is (1) Pt, (2) Cu, (3) Pb, (4) Cd, (5) Cr, (6) Co, (7) Hg, (8) Ag.
Embodiment 13：Atomic absorption spectrography (AAS) detects materials A4Experiment is cleared to living cells heavy metal
Selection HepG2 cells are research object.Be separately added into experimental group and control group heavy metal Pt, Cu, Pb, Cd,
Cr, Co, Hg, Ag ion, at 37 DEG C, 5%CO2It is incubated 30 minutes.Control group PBS concussion rinsings 5min × 3, vitellophag are ground
Mill pretreatment, obtains the heavy metal in control group.Experimental group is with the A of final concentration of 2.0mg/mL4It is incubated 30min, PBS shakes respectively
Rinsing 5min × 3, vitellophag are swung, grinding pretreatment obtains the heavy metal in control group.Then by the control group of acquisition and reality
The metal tested in group is measured with atomic absorption spectrophotometer respectively.As shown in Fig. 17, in figure 1-8 indicate respectively be added Pt,
The test result of Cu, Pb, Cd, Cr, Co, Hg, Ag8 metal ion species.As it can be seen that materials A4Heavy metal in processed experimental group
Ion concentration is substantially reduced.Prove A4It is adsorbable and clear heavy metal Pt, Cu, Pb, Cd, Cr, Co, Hg, Ag ion.It is golden in figure
The sequence for belonging to ion is (1) Pt, (2) Cu, (3) Pb, (4) Cd, (5) Cr, (6) Co, (7) Hg, (8) Ag.The above content is combinations
Specific preferred embodiment is made for the present invention to be further described, and it cannot be said that the specific implementation of the present invention is only limited to
In these explanations.For those of ordinary skill in the art to which the present invention belongs, in the premise for not departing from present inventive concept
Under, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to protection scope of the present invention.It is as fluorescent dye
A kind of purposes of noval chemical compound of the present invention is, and it cannot be said that the compound of the present invention is only used for fluorescent dye, belonging to the present invention
For the those of ordinary skill of technical field, in the identical mechanism of action for being used as fluorescent dye based on the considerations of the compounds of this invention
Under, several simple inferences can also be made, the other application purposes of the compound of the present invention is obtained, all shall be regarded as belonging to this hair
Bright protection domain.
Claims (10)
1. the composite nano materials of organic naphthalene and inorganic phosphate, the structure with general formula I：
In general formula I：
The X is selected from X1、X2And X3：
R1、R2And R3It is each independently selected from：-(CH2)pCOOH、-(CH2)pOH、-(CH2OCH2)pCOOH、-(CH2OCH2)pOH、-
CH[(CH2)pCOOH]2、-NH(CH2)pCOOH、-CH[(CH2)pOH]2、-CH[(CH2O CH2)pCOOH]2、-CH[(CH2OCH2)pOH]2, wherein p is the integer of 1-8；
The L is selected from：-NH(CH2)qCH3、-NH(CH2)qNH2、-NH(CH2)qOH、-NH(CH2)qCOOH、-N[(CH2)qCH3
]2、-N[(CH2)qNH2]2、-N[(CH2)qOH]2、-N[(CH2)qCOOH]2, a- crown ether-b, the a- crown ether-b, wherein q of azepine be
The integer of 1-8, a are the integers of 1-20, and b is the integer of 1-8；
The M is inorganic phosphate salt material；
The n is the integer of 1-8.
2. the composite nano materials of organic naphthalene and inorganic phosphate according to claim 1, which is characterized in that the R1、
R2And R3It is each independently selected from-(CH2)pCOOH、-(CH2)pOH and-NH (CH2)pCOOH。
3. the composite nano materials of organic naphthalene and inorganic phosphate according to claim 1, which is characterized in that the L
Selected from N [(CH2)qCH3]2、-N[(CH2)qNH2]2、-N[(CH2)qOH]2、-N[(CH2)qCOOH]2, a- crown ethers-b, azepine a- hat
Ether-b.
4. the composite nano materials of organic naphthalene and inorganic phosphate according to claim 1, which is characterized in that the M
Selected from hydroxyapatite, calcium octahate phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate or tricalcium phosphate.
5. the composite nano materials of organic naphthalene and inorganic phosphate according to claim 1, which is characterized in that the M
Selected from hydroxyapatite, calcium monohydrogen phosphate or calcium dihydrogen phosphate.
6. the composite nano materials of organic naphthalene and inorganic phosphate according to claim 1 are selected from A1-A4：
7. the preparation method of the composite nano materials of organic naphthalene described in claim 1 and inorganic phosphate, includes the following steps：
1) bromo- 1, the 8- naphthalenes glycosides of 4-, 4- bromines acenaphthenequinone respectively with L-H in molar ratio 1:1-1:6 reactions, prepare compound i and compound
ii；
Reaction temperature be 0-200 DEG C, the reaction time be 1-36 hour, reaction dissolvent selected from dichloromethane, ethyl alcohol, methanol, acetone,
Or mixtures thereof 1,4- dioxane, glycerine, ethyl acetate, acetic acid；
2) compound i and compound H2N-R1 in molar ratio 1:1-1:5 reactions, prepare compound iii；
Reaction temperature be 0-150 DEG C, the reaction time be 1-16 hour, reaction dissolvent selected from dichloromethane, ethyl alcohol, methanol, acetone,
Or mixtures thereof 1,4- dioxane, glycerine, ethyl acetate, acetic acid；
3) compound i and compound iv in molar ratio 1:1-1:5 reactions, prepare compound v；
Compound ii and compound iv-1 in molar ratio 1:1-1:5 reactions, prepare compound vi；
Reaction temperature be 0-150 DEG C, the reaction time be 1-16 hour, reaction dissolvent selected from dichloromethane, ethyl alcohol, methanol, acetone,
Or mixtures thereof 1,4- dioxane, glycerine, ethyl acetate, acetic acid；
4) compound iii, v or vi respectively with Ca (NO3)2·4H2O and (NH4)2HPO4According to molar ratio 1:1:10-1:1.5:50
Reaction prepares compounds of formula I：
First, compound iii, v and vi respectively with Ca (NO3)2·4H2O reacts, and reaction dissolvent is selected from dichloromethane, anhydrous second
Or mixtures thereof alcohol, methanol, acetone, 1,4- dioxane, glycerine, ethyl acetate, acetic acid；It is stirred to react time 3-6h；
Then, (the NH of 10mL 0.1-5.0mol/L is added dropwise with the speed of 0.1-10mL/min into said mixture4)2HPO4It is molten
After being added dropwise, 36-120h is reacted at 20-100 DEG C, and keeps in reaction process pH between 8.0-10 for liquid.
8. the composite nano materials of the organic naphthalene and inorganic phosphate in claim 1-6 described in any claim are in heavy metal
Application in ion identification, absorption and removing.
9. application according to any one of claims 8, which is characterized in that the heavy metal ion is the heavy metal ion in cell.
10. application according to claim 8, which is characterized in that the heavy metal ion include lead, cadmium, chromium, mercury, copper,
Gold, silver and cobalt.
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| Multifunctional Mesoporous Silica Material Used for Detection and Adsorption of Cu2R in Aqueous Solution and Biological Applications in vitro and in vivo;Qingtao Meng，等;《Adv. Funct. Mater.》;20101231;第20卷;1903-1909 * |
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