CN112300789B - Ratio type fluorescent probe, preparation method and application thereof, and detection method - Google Patents
Ratio type fluorescent probe, preparation method and application thereof, and detection method Download PDFInfo
- Publication number
- CN112300789B CN112300789B CN202011211937.5A CN202011211937A CN112300789B CN 112300789 B CN112300789 B CN 112300789B CN 202011211937 A CN202011211937 A CN 202011211937A CN 112300789 B CN112300789 B CN 112300789B
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- Prior art keywords
- terbium
- compound
- containing compound
- borate
- detection
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- 238000001514 detection method Methods 0.000 title claims abstract description 67
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 72
- -1 terbium-pyridine dicarboxylic acid compound Chemical class 0.000 claims abstract description 59
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 25
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 45
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 229910052771 Terbium Inorganic materials 0.000 claims description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 29
- 150000002500 ions Chemical class 0.000 claims description 28
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 26
- 239000000523 sample Substances 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 21
- 238000004090 dissolution Methods 0.000 claims description 18
- 229910001385 heavy metal Inorganic materials 0.000 claims description 17
- 230000005284 excitation Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001217 Terbium Chemical class 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001917 fluorescence detection Methods 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000005057 refrigeration Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 3
- UTHULKKJYXJZLV-UHFFFAOYSA-N (3-aminophenoxy)boronic acid Chemical group NC1=CC=CC(OB(O)O)=C1 UTHULKKJYXJZLV-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000035484 reaction time Effects 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- ZIKNLDSSGXLGAJ-UHFFFAOYSA-N pyridine-2,3-dicarboxylic acid terbium Chemical class [Tb].N1=C(C(=O)O)C(C(=O)O)=CC=C1 ZIKNLDSSGXLGAJ-UHFFFAOYSA-N 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000000575 pesticide Substances 0.000 description 13
- 241000282414 Homo sapiens Species 0.000 description 7
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- JMZFEHDNIAQMNB-UHFFFAOYSA-N m-aminophenylboronic acid Chemical compound NC1=CC=CC(B(O)O)=C1 JMZFEHDNIAQMNB-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 231100001234 toxic pollutant Toxicity 0.000 description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000005949 Malathion Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229960000453 malathion Drugs 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- DIRRKLFMHQUJCM-UHFFFAOYSA-N (2-aminophenyl)boronic acid Chemical compound NC1=CC=CC=C1B(O)O DIRRKLFMHQUJCM-UHFFFAOYSA-N 0.000 description 1
- ZSKXYSCQDWAUCM-UHFFFAOYSA-N 1-(chloromethyl)-2-dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCl ZSKXYSCQDWAUCM-UHFFFAOYSA-N 0.000 description 1
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- 102000012440 Acetylcholinesterase Human genes 0.000 description 1
- 108010022752 Acetylcholinesterase Proteins 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005561 Glufosinate Substances 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229940022698 acetylcholinesterase Drugs 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MYCZBBOLTYBTCX-UHFFFAOYSA-N cyclopenta-2,4-dien-1-amine;cyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.NC1=CC=C[CH-]1 MYCZBBOLTYBTCX-UHFFFAOYSA-N 0.000 description 1
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- 230000001419 dependent effect Effects 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 1
- 229950001327 dichlorvos Drugs 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- YKBZOVFACRVRJN-UHFFFAOYSA-N dinotefuran Chemical compound [O-][N+](=O)\N=C(/NC)NCC1CCOC1 YKBZOVFACRVRJN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- 239000012982 microporous membrane Substances 0.000 description 1
- KRTSDMXIXPKRQR-AATRIKPKSA-N monocrotophos Chemical compound CNC(=O)\C=C(/C)OP(=O)(OC)OC KRTSDMXIXPKRQR-AATRIKPKSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical group CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical group COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 239000013595 supernatant sample Substances 0.000 description 1
- UFPWIQQSPQSOKM-UHFFFAOYSA-H terbium(3+);trisulfate Chemical compound [Tb+3].[Tb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O UFPWIQQSPQSOKM-UHFFFAOYSA-H 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000003260 vortexing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Immunology (AREA)
- Optics & Photonics (AREA)
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Abstract
The invention relates to the field of environment detection, in particular to a ratio type fluorescent probe, a preparation method and application thereof and a detection method. The ratio-type fluorescent probe comprises a terbium-pyridine dicarboxylic acid compound and borate modified carbon quantum dots, wherein the carbon quantum dots are bonded with the terbium-pyridine dicarboxylic acid compound through borate. The ratio type fluorescent probe can detect various pollutants at the same time, particularly nickel ions and nitrophenol at the same time, and is accurate in detection and not easy to be interfered by environment and samples.
Description
Technical Field
The invention relates to the field of environment detection, in particular to a ratio type fluorescent probe, a preparation method and application thereof and a detection method.
Background
Toxic pollutants are currently attracting much attention, which severely threatens human health, especially pesticides and heavy metal ions. In modern agriculture, pesticides are used to protect crops from pests. However, due to incorrect application and handling, low concentrations of pesticides are contained from water, fruits, natural plants, which can pose serious hazards to human health, especially to children's acetylcholinesterase. Heavy metal ions are considered as the most toxic inorganic pollutants, and can accumulate from the food chain like pesticides, severely threatening the health of humans. Nickel (Ni) is an indispensable element for human beings, and low concentration of nickel can meet the demands of animals and plants, but when high level of nickel ions or salts thereof exist in the animals and plants, the nickel ions or salts thereof can poison and cause cancer. The pesticide and nickel ions threaten the top of the human food chain, and form a great threat to human beings, and a simple, convenient, rapid and accurate pesticide and heavy metal ion analysis method is urgently needed to be developed.
Traditional pesticide analysis methods include gas chromatography, micelle electro-dynamic chromatography, and other methods. Also, conventional methods for detecting heavy metal ions, such as FAAS flame ions, ICP-MS, and ICP-OES, all require complex and cumbersome experimental procedures. The above analysis methods not only do not have the ability to detect in situ, but also require a large number of pretreatment steps, require a large amount of solvent and time consumption, and are experienced by skilled technicians. Recently, many rapid detection strategies with high sensitivity have been developed to detect pesticides and heavy metal ions, including chemiluminescent sensors, immunoassays, electrochemical sensors, and enzyme-based biosensors. These quick-check methods still have some drawbacks in use, such as insufficient environmental adaptability or high storage requirements. In addition, these strategies rarely allow simultaneous detection of pesticides and heavy metal ions. In this work, carbon quantum dots (CDs) as signaling probes construct novel fluorescence analysis techniques in an effort to overcome the above-described deficiencies.
Fluorescent nanoprobes with single signals have been developed and their green, simple and inexpensive properties have led to their use in various fields. In the detection of toxic pollutants, single signal detection of carbon quantum dots is susceptible to environmental influences during detection, although many advances have been made, increasing the generation of false positive results. Thus, ratio-type fluorescent nanoprobes comprising dual or multiple signals may be of interest as reference and detection signals. Compared with the existing detection method of nickel ions, chinese patent application No. 201510368783.3 discloses a detection reagent and a detection method of nickel ions, wherein the detection reagent is prepared from boric acid, dimethylglyoxime, N-diethyl p-phenylenediamine, sulfanilic acid, potassium chloride, an oxidant, a masking agent, sodium hydroxide, distilled water and the like, and the content of nickel ions is calculated by utilizing the absorbance difference of ultraviolet spectrum under 470 nm. The preparation method is complex, the adopted synthetic substrates are more, and the method is a single signal output mode of ultraviolet detection. In China patent application No. 201410626111.3, detection of nitrophenol by using an electrochemical method is reported, the preparation of a compound is carried out by stirring N, N-dimethylformamide solution of a single-wall carbon nano tube, 0.5M hydrochloric acid solution, N-dimethylformamide solution of aminoferrocene and sodium nitrite overnight at 0 ℃ under the protection of argon, and after the product is repeatedly washed for three times by the N, N-dimethylformamide, the product is dispersed in the N, N-dimethylformamide. The modification process of the compound applied to the electrode has high operation requirement and has great influence on the repeatability of electrode detection. The N, N-dimethylformamide system is easy to pollute the environment and is more easy to cause harm to human bodies.
These substances or methods are used to detect a single contaminant in an environment, are not capable of detecting multiple substances simultaneously, and single signal probes have the disadvantage of being susceptible to sample and environmental interference.
Disclosure of Invention
The invention provides a ratio type fluorescent probe, a preparation method and application thereof and a detection method, wherein the ratio type fluorescent probe can detect various pollutants at the same time, particularly nickel ions and nitrophenol can be detected at the same time, and the detection is accurate and is not easy to be interfered by environment and samples.
The invention is realized in the following way:
the embodiment of the invention provides a ratio-type fluorescent probe which comprises a terbium-pyridine dicarboxylic acid compound and borate modified carbon quantum dots, wherein the carbon quantum dots are bonded with the terbium-pyridine dicarboxylic acid compound through borate.
The embodiment of the invention also provides a preparation method of the ratio type fluorescent probe, which comprises the step of bonding the carbon quantum dots modified by the borate with the terbium-pyridine dicarboxylic acid compound.
Further, in a preferred embodiment of the present invention, the bonding process includes: carrying out hydrothermal reaction on a borate-containing compound, and then carrying out reaction on the borate-containing compound, the alkali, the terbium-containing compound and the pyridine dicarboxylic acid compound to form the ratio type fluorescent probe;
preferably, the molar ratio of the borate-containing compound, the base, the terbium-containing compound, and the dipicolinic acid-based compound is 6 to 323:500:1-3:2-10.
Further, in a preferred embodiment of the present invention, the steps prior to performing the hydrothermal reaction include: dissolving the borate-containing compound and then adjusting the pH to 4-10, preferably 4-6, more preferably 4,5 or 6, most preferably 5;
preferably, the dissolution is carried out by ultrasonic dissolution for 5-15 minutes, preferably 10 minutes;
preferably, the concentration of the solution formed after dissolution is 0.1-5mg/mL, preferably 0.5-3mg/mL, more preferably 0.8-1.2mg/mL, preferably 1mg/mL, 1.5mg/mL or 2mg/mL, most preferably 1mg/mL;
preferably, the acid used for adjusting the pH is an inorganic acid, preferably at least one of hydrochloric acid, sulfuric acid and nitric acid;
preferably, the borate-containing compound comprises 3-aminophenylboronic acid.
Further, in a preferred embodiment of the present invention, the temperature of the hydrothermal reaction is 160-200deg.C, preferably 170-190 deg.C, preferably 175-185 deg.C, preferably 180 deg.C;
the time of the hydrothermal reaction is 5 to 7 hours, preferably 5.5 to 6.5 hours, more preferably 6 hours.
Further, in a preferred embodiment of the present invention, after the hydrothermal reaction, the reaction with the terbium-containing compound and the dipicolinic acid-based compound is preceded by: post-treating the reaction system after the hydrothermal reaction;
preferably, the post-treatment comprises: after cooling the reaction system, centrifugation was performed to form a supernatant.
Further, in a preferred embodiment of the present invention, the step of reacting with the terbium-containing compound and the dipicolinic acid-based compound comprises: and uniformly mixing the supernatant, the alkali, the terbium-containing compound and the pyridine dicarboxylic acid compound, and then refrigerating.
Further, in a preferred embodiment of the present invention, the base is selected from any one of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium bicarbonate and ammonia water, preferably sodium hydroxide;
preferably, the alkali is added in the form of an alkali solution, and the concentration of the alkali solution is 0.3-0.7mol/L, preferably 0.4mol/L, 0.5mol/L or 0.6mol/L;
preferably, the terbium-containing compound is a terbium salt, preferably terbium chloride;
preferably, the terbium-containing compound is added in the form of a terbium-containing compound solution having a concentration of 0.05-0.15mmol/L, preferably 0.8mmol/L, 0.1mmol/L or 0.12mmol/L;
preferably, the dipicolinic acid compound is dipicolinic acid;
preferably, the dipicolinic acid compound is added in the form of dipicolinic acid compound solution, and the concentration of the dipicolinic acid compound solution is 0.1-0.5mmol/L, preferably 0.3mmol/L;
preferably, the temperature of refrigeration is 0-4 ℃.
The embodiment of the invention also provides an application of the ratio type fluorescent probe in detecting organic matters and/or heavy metal ions;
preferably, the organic matter is nitrophenol, and the heavy metal ion is nickel ion;
preferably, the detection comprises a sewage detection;
preferably, the ratio-type fluorescent probe is applied to the simultaneous detection of nitrophenol and nickel ions.
The embodiment of the invention also provides a detection method, which utilizes the ratio-type fluorescent probe to detect organic matters and/or heavy metal ions; preferably, the ratio-type fluorescent probe is mixed with a sample to be detected, and then fluorescent detection is carried out; preferably, the excitation wavelength used for fluorescence detection is 273nm.
The beneficial effects of the invention are as follows: according to the invention, the carbon quantum dots are modified by utilizing the borate, and the carbon quantum dots are bonded with the terbium-pyridine dicarboxylic acid compound, so that the ratio type fluorescent probe can detect various pollutants at the same time, particularly nickel ions and nitrophenol can be detected at the same time, the detection result is accurate, the interference of the environment and a sample is not easy, and the generation of false positive detection results is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the results provided in Experimental example 1 of the present invention;
FIG. 2 is a graph showing the results of exciting borate modified carbon quantum dots at different excitation wavelengths provided in Experimental example 2 of the present invention;
FIG. 3 is a representation provided in Experimental example 2 of the present invention;
FIG. 4 is a graph showing the results provided in Experimental example 3 of the present invention;
FIG. 5 is a graph showing the results of detection of the presence of p-NP at various concentrations as provided in Experimental example 4 of the present invention;
FIG. 6 is a graph showing the results of detection of the presence of Ni ions at different concentrations provided in Experimental example 4 of the present invention;
FIG. 7 is a graph showing the results provided in Experimental example 5 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides a ratio-type fluorescent probe which comprises a terbium-pyridine dicarboxylic acid compound and borate modified carbon quantum dots, wherein the carbon quantum dots are bonded with the terbium-pyridine dicarboxylic acid compound through borate. The carbon quantum dot is modified by utilizing the borate, and the carbon quantum dot is bonded with the terbium-pyridine dicarboxylic acid compound, so that the ratio type fluorescent probe can detect various pollutants at the same time, particularly nickel ions and nitrophenol can be detected at the same time, the detection result is accurate, the interference of the environment and a sample is not easy, and the generation of false positive detection results is reduced.
The embodiment also provides a preparation method of the ratio type fluorescent probe, which comprises the following steps:
mixing borate-containing compound with water for dissolution, and dissolving with ultrasound for 5-15 min, preferably 10min, to promote dissolution; for example, the value may be a range formed between any two values such as 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, and 10 minutes, or any value within the range. The concentration of the solution formed after dissolution is 0.1-5mg/mL, preferably 0.5-3mg/mL, more preferably 0.8-1.2mg/mL, preferably 1mg/mL, 1.5mg/mL or 2mg/mL, most preferably 1mg/mL; for example, the amount may be 0.1mg/mL, 0.2mg/mL, 0.3mg/mL, 0.5mg/mL, 0.8mg/mL, 1mg/mL, 1.2mg/mL, 1.5mg/mL, 1.7mg/mL, 2mg/mL, 2.5mg/mL, 3mg/mL, 3.5mg/mL, 4mg/mL, 4.5mg/mL, 5mg/mL, or any value within a range between any two values.
The borate-containing compound includes 3-aminophenylboronic acid. It should be noted that, although the embodiment of the present invention only provides the 3-aminophenylboronic acid to form the carbon quantum dot modified by boric acid, other borate-containing compounds in the prior art, which can react with water to form the boric acid modified carbon quantum dot, are also within the scope of the present invention, such as 4-aminophenylboronic acid, 2-aminophenylboronic acid.
The pH of the solution is then adjusted to 4-10, preferably 4-6, more preferably 4,5 or 6, most preferably 5; for example, a range value formed between any two values of 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and 10, or any value within the range, may be selected. The inventor finds that by controlling the pH of the solution containing the borate compound, the carbon quantum dots formed by the subsequent hydrothermal reaction can be ensured to emit a plurality of high-intensity fluorescent signals under the excitation of 273nm, so that the finally formed ratio type fluorescent probe can detect a plurality of toxic pollutants simultaneously, and meanwhile, the accuracy of detection is ensured, and the environmental interference resistance is strong.
Wherein the acid used for adjusting the pH is an inorganic acid, preferably at least one of hydrochloric acid, sulfuric acid and nitric acid.
Then carrying out a hydrothermal reaction, specifically, adding the solution with the pH adjusted into a reaction tank prepared from polytetrafluoroethylene, sealing, and carrying out the reaction, wherein the temperature of the hydrothermal reaction is 160-200 ℃, preferably 170-190 ℃, preferably 175-185 ℃, preferably 180 ℃; for example, the temperature may be 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃ or any value within a range between any two values. The time of the hydrothermal reaction is 5 to 7 hours, preferably 5.5 to 6.5 hours, more preferably 6 hours, for example, 5 hours, 5.2 hours, 5.5 hours, 6.7 hours, 6.5 hours, and 7 hours, or any value within the range between any two values. By adopting the hydrothermal reaction condition, the hydrothermal reaction can be ensured, and then the formation of carbon quantum dots is facilitated, and then the performance of the ratio-type fluorescent probe is ensured.
After the hydrothermal reaction is finished, the reaction system is centrifuged to form a supernatant. The centrifugation time is 5-15 minutes, and can be selected from the range value formed between any two values of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15min, or any value in the range, preferably 10min; the rotational speed of the centrifugation is 4000rpm; and the insoluble substances and other impurities can be removed by centrifugation, so that the carbon quantum dots modified by the required borate in the formed supernatant can be ensured.
And uniformly mixing the supernatant, the alkali, the terbium-containing compound and the pyridine dicarboxylic acid compound to form a terbium-pyridine dicarboxylic acid compound and connecting the carbon quantum dots with the terbium-pyridine dicarboxylic acid compound through borate.
The molar ratio of the borate-containing compound to the alkali to the terbium-containing compound to the dipicolinic acid compound is 6-323:500:1-3:2-10, preferably 65:500:2:6. the use of the molar ratio ensures the formation and performance of the ratio-type fluorescent probe, and can simultaneously detect a plurality of harmful substances, in particular heavy metal ions and organic substances, for example nickel ions and nitrophenol. And the detection is not easily affected by the environment and the sample, so that the detection result is improved.
Wherein the alkali is selected from any one of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium bicarbonate and ammonia water, and preferably sodium hydroxide; although some alkaline substances are used in the examples of the present invention, other compounds that are alkaline in aqueous solution in the prior art are also within the scope of the examples of the present invention, for example, sodium alkoxides such as sodium ethoxide and sodium methoxide, or carbonates such as sodium carbonate and potassium carbonate.
The alkali may be directly mixed with the supernatant liquid, or the alkali may be dissolved in water and then mixed with the supernatant liquid, and when the alkali is added in the form of an alkali solution, the concentration of the alkali solution may be, for example, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, or any value within a range between any two values. Preferably 0.4mol/L, 0.5mol/L or 0.6mol/L.
The terbium-containing compound is a terbium salt, preferably terbium chloride; other terbium salts in the prior art, such as terbium sulfate, which are capable of bonding with carbon quantum dots and dipicolinic compounds are also within the scope of the present invention.
The terbium-containing compound may be directly mixed with the supernatant, or the terbium salt may be dissolved in water and then mixed with the supernatant. When the terbium-containing compound solution is added in the form of 0.05 to 0.15mmol/L, the terbium-containing compound solution may be, for example, 0.05mmol/L, 0.06mmol/L, 0.07mmol/L, 0.08mmol/L, 0.09mmol/L, 0.1mmol/L, 0.11mmol/L, 0.12mmol/L, 0.13mmol/L, 0.14mmol/L, or any value in the range between any two values of the range. Preferably 0.08mmol/L, 0.1mmol/L or 0.12mmol/L.
The pyridine dicarboxylic acid compound is pyridine dicarboxylic acid; the dipicolinic acid compound may be directly mixed with the supernatant, or the dipicolinic acid compound may be dissolved to form a dipicolinic acid compound solution. When the dipicolinic acid compound is added in the form of a solution, the concentration of the dipicolinic acid compound solution may be, for example, 0.1mmol/L, 0.15mmol/L, 0.2mmol/L, 0.25mmol/L, 0.3mmol/L, 0.35mmol/L, 0.4mmol/L, and 0.5mmol/L, or any value within the range formed between any two values thereof. Preferably 0.3mmol/L.
Can directly be used for detecting after the misce bene, also can refrigerate it, when needing to use, take out again, refrigerate it can effectively prevent ratio type fluorescent probe rotten, then guarantee the accuracy of testing result. Wherein, the refrigerating temperature is 0-4 ℃, and the adoption of the refrigerating temperature is favorable for ensuring the performance of the ratio type fluorescent probe.
The embodiment of the invention also provides an application of the ratio type fluorescent probe in detecting organic matters and/or heavy metal ions, wherein the organic matters are nitrophenol, and the heavy metal ions are nickel ions; the detection comprises sewage detection; that is, the ratio-type fluorescent probe can be applied to detecting nitrophenol and nickel ions respectively or simultaneously, the detection result is accurate, and the influence of factors such as environment on the detection result can be reduced.
The embodiment of the invention also provides a detection method, which comprises the steps of detecting organic matters and/or heavy metal ions by using the ratio-type fluorescent probe; specifically, mixing the ratio-type fluorescent probe with a sample to be detected, and then performing fluorescent detection; preferably, the excitation wavelength used for fluorescence detection is 273nm.
The invention provides a ratio-type fluorescent probe, a preparation method and application thereof and a detection method thereof, which are specifically described below with reference to specific examples.
Example 1
The embodiment provides a preparation method of a ratio type fluorescent probe, which comprises the following steps:
10mg of APBA (3-aminophenylboric acid) is mixed with water to prepare 10mL of solution with the concentration of 1mg/mL, and the solution is subjected to ultrasonic treatment for 10 minutes to be fully dissolved to obtain uniform and transparent light yellow solution; the pH was adjusted to 5 by adding 6mol/L HCl. The above solution was added to a Polytetrafluoroethylene (PTFE) reaction vessel (20 mL) and heated at 180℃for 6 hours. And secondly, cooling to room temperature (25 ℃) and transferring the reaction solution into a 50mL centrifuge tube, centrifuging at 4000rpm for 10 minutes to remove insoluble substances, filtering the centrifuged solution by using a 0.22 mu m filter membrane to obtain filtrate, and transferring the filtrate into a new 50mL centrifuge tube (the borate modified carbon quantum dots are synthesized in the place, namely CDs). 1mL NaOH (0.5 mol/L) and 20mL TbCl were added to the above centrifugation 3 (0.1 mmol/L) and 20mL of dipicolinic acid (DPA) (0.3 mmol/L), vortexing for 5 minutes, mixing well, and storing at 4 ℃ to obtain the ratio type fluorescent probe, which is marked as CDs@Tb-DPA.
Example 2-example 4
Examples 2 to 4 each provide a preparation method of a ratio-type fluorescent probe, which is basically identical to the preparation method of a ratio-type fluorescent probe provided in example 1, except that the operating conditions are different, specifically as follows:
example 2: the ultrasonic time is 15 minutes, the concentration of the solution formed after dissolution is 5mg/mL, the pH is regulated to 10 by sulfuric acid (6 mol/L), the temperature of the hydrothermal reaction is 200 ℃, the time is 7, the base is sodium hydroxide, the refrigerating temperature is 4 ℃, and the molar ratio of the borate-containing compound, the base, the terbium-containing compound and the dipicolinic acid compound is 323:500:3:10.
example 3: the ultrasonic time is 15 minutes, the concentration of the solution formed after dissolution is 1mg/mL, the pH is regulated to 6 by nitric acid (6 mol/L), the temperature of the hydrothermal reaction is 200 ℃, the time is 7 hours, the base is sodium bicarbonate, the refrigeration temperature is 4 ℃, and the molar ratio of the borate-containing compound, the base, the terbium-containing compound and the dipicolinate compound is 65:500:2:6.
example 4: the ultrasonic time is 5 minutes, the concentration of the solution formed after dissolution is 0.1mg/mL, the pH is regulated to 4 by hydrochloric acid (6 mol/L), the temperature of the hydrothermal reaction is 160 ℃, the time is 5 hours, the base is potassium hydroxide, the refrigeration temperature is 0 ℃, and the molar ratio of the borate-containing compound, the base, the terbium-containing compound and the dipicolinic acid compound is 6:500:1:2.
comparative example 1: the nanoprobe was prepared by the method of reference study (MaiLuoet al, fluorescentand visual detection method methyl-paraloxonbyusingboron-and nitrogen-dopedcarboots, microchemical journal154 (2020) 104547): 1g of Citric Acid (CA) and 130mg of 3-aminophenylboronic acid (APBA) were dissolved in 10mL of dimethylformamide DMF. The mixture was heated in a Polytetrafluoroethylene (PTFE) autoclave (20 mL) at 200℃for 6 hours. After cooling to room temperature a brown solution was obtained, which was then dried in a vacuum oven to remove DMF 6h at 80 ℃. The precipitate was washed 3 times with deionized water to remove impurities. Finally, the resulting boron, nitrogen doped carbon quantum dots were dissolved with 33.3mL of 2.5g/L NaOH solution in 66.7mL DMF and stored at 4℃for later use.
The specific results of the probes prepared in comparative example 1 and comparative example 1 with respect to the difference in wavelength of excitation light/emission light are shown in Table 1.
TABLE 1 difference between excitation light/emission light wavelength
As is clear from Table 1, the probe in comparative example 1 has an excitation light-dependent characteristic, and the maximum fluorescence emission spectrum changes with a change in the excitation light wavelength. The fluorescent probe prepared in example 1 of the present invention has the characteristic of independent excitation light, and the maximum emission wavelength is continuously 420nm when the excitation wavelength is changed from 210nm to 300 nm. Meanwhile, the complex formed by the fluorescent carbon quantum dots, terbium (Tb) ions and dipicolinic acid (DPA) prepared in the research can emit a plurality of high-intensity fluorescent signals under 273nm excitation, and the fluorescent carbon quantum dots have the advantages of high accuracy, strong environment interference resistance and the like in pollutant detection.
Experimental example 1
The preparation method of the boric acid modified carbon quantum dot according to the method of example 1 is different only in pH, and then the fluorescence intensity of the carbon quantum dot is detected, see fig. 1.
As can be seen from fig. 1, at ph=5, the carbon quantum dot having the highest fluorescence intensity was synthesized.
Experimental example 2
(1) The borate modified carbon quantum dots prepared in the examples were excited with different excitation wavelengths, and the detection results are shown in fig. 2.
From FIG. 2, it can be seen that the maximum emission wavelength of CDs remains at 420nm when excited from 210nm to 290 nm. The results indicate that CDs are concentrated on narrower sizes or fewer surface defects.
(2) The CDs, CDs@Tb and CDs@Tb-DPA prepared in example 1 were characterized, and the results are shown in FIG. 3.
Wherein A in FIG. 3 is the fluorescence emission spectrum of CDs@Tb-DPA; b in FIG. 3 is CDs, CDs@Tb and CDs@Tb-DPA ultraviolet absorption spectrum and CDs@Tb-DPA fluorescence emission map; c in FIG. 3 is the FT-IR chart of CDs, CDs@Tb and CDs@Tb-DPA; figure 3D is the XRD pattern of CDs; e in FIG. 3 is a TEM electron microscope image of CDs, inner image: TEM high resolution electron microscope image of CDs; f in FIG. 3 is the particle size distribution of CDs.
As shown in fig. 3 a, 273nm was chosen for excitation in order to achieve equal fluorescence intensities between 420 and 546 nm. As shown in the ultraviolet-visible spectrum (B in FIG. 3), the maximum absorption peak of CDs@Tb-DPA is 273nm. Under 273nm excitation, CDs@Tb-DPA exhibited four characteristic FL peaks at 494, 546, 586 and 624nm (B in FIG. 3) due to the 5D4→7F6, 5D4→7F5, 5D4→ 7F4,5D4 →7F3 transitions, respectively.
To verify the CDs@Tb-DPA structure, the complex formation process was studied using FT-IR. As shown in FIG. 3C, after Tb (III) and DPA are added to CDs, the spectra are 890, 950, 1464, 3350, 3450 and 3650cm -1 A significant change in the vicinity occurred, which is responsible for the formation of cd@tb-DPA.
As shown in fig. 3D, two peaks (27.8 ° and 41.3 °) were found in the XRD pattern of CDs, which may be attributed to graphitic carbons (002) and (100). The CDs produced were polycrystalline nanoparticles (as shown by E in TEM image 3) showing good solubility in water. After the distribution size and lattice spacing of CDs were counted (F in FIG. 3), the average particle size and lattice distance were 2.8nm and 0.20nm, respectively. As shown in FIGS. 3E-F, the CDs size distribution was centered at 2 to 3nm, accounting for 57%.
Experimental example 3 establishment of ratio detection System
The method comprises the following steps: from the prepared CDs@Tb-DPA ratio probe solution of example 1, 250. Mu.L was removed and added to a 2mL centrifuge tube. Pure water was filled into a centrifuge tube to make the volume of the detection system 1mL. After being fully and evenly mixed, the mixture is transferred into a cuvette of 3mL and is placed into a fluorescence spectrophotometer for detection. Fluorescence probes were excited using 273nm and the fluorescence intensity values of the emitted light at 420nm and 546nm were recorded.
The results are shown in FIG. 4, wherein A in FIG. 4 is the efficiency of pH at 298K (25 ℃) for fluorescence detection of 40. Mu. M p-NP; b in fig. 4 is the efficiency of fluorescence ratio detection of 40 μ M p-NP at ph=10, different temperatures; in fig. 4C is the fluorescent quantitative detection of 0, 10, 40 and 70 μ M p-NP at ph=10 and 298K; in FIG. 4D is the UV-vis spectrum and fluorescence spectrum of CDs@Tb-DPA in the presence of 0, 40 μ M p-NP or 15 μM Ni (ii) ions.
As shown in FIG. 4, pH 10, 298K (25 degrees) and 0 minutes were set as the optimal conditions.
Experimental example 4 drawing a Linear Standard Curve
The method comprises the following steps:
mu.L of the prepared CDs@Tb-DPA ratio probe solution of example 1 was removed and added to a 2mL centrifuge tube together with contaminants at the corresponding concentrations. The remaining volume was filled with 1mL of purified water and thoroughly mixed. The detection parameters were identical to those in experimental example 3. The Quenching Rate (QR) was calculated by substituting the values obtained for fluorescence intensity at 420nm and 546nm into the following formula. Standard curves were plotted using QR and corresponding concentrations. And drawing the linear regression equations of the related p-nitrophenol and nickel ions by using the formula (1) and the formula (2) respectively. The calculation formula is as follows:
s, B, I420 and I546 in the calculation formula represent fluorescence intensity values of the pollutant sample, the blank sample and CDs@Tb-DPA at 420 and 546nm respectively.
The detection results are shown in FIG. 5 and FIG. 6, wherein A in FIG. 5 is the fluorescence emission spectrum of CDs@Tb-DPA in the presence of p-NP at different concentrations; in FIG. 5, B is a graph showing the linear relationship between the concentration of p-NP and the change in fluorescence intensity of CDs@Tb-DPA. FIG. 6A is a fluorescence emission spectrum of CDs@Tb-DPA in the presence of Ni ions of different concentrations; in FIG. 6, B is a graph showing the linear relationship between Ni ion concentration and CDs@Tb-DPA fluorescence intensity.
Under optimal conditions, as shown in FIGS. 5 and 6, the CDs@Tb-DPA of the ratio detection exhibited good linearity with p-NP and Ni ion concentrations. On the other hand, as the concentration of p-NP increased from 1.25 to 80. Mu.M, the fluorescence intensity of the detection signal (420 nm) was gradually decreased (FIG. 5). The CDs@Tb-DPA fluorescence quenching rate showed a strong linear trend (with two linear ranges) in the p-NP range from 1.25 to 80. Mu.M. As shown in fig. 5B, the first linear range (y= -0.01055 x+0.9775, r2= 0.9912) is from 1.25 to 30 μm, the second linear range is from 30 to 80 μm, and the linear (y= -0.006173 x+0.8395, r2= 0.9934). As shown in fig. 6B, cds@tb-DPA (detection signal 546 nm) shows a better linear relationship for nickel ions (0.01-8 μm) (y= -0.07302 x+0.9390, r2= 0.9926).
Experimental example 5 Selective experiments on CDs@Tb-DPA
By testing nineteen pesticides and metal ions, the selectivity of CDs@Tb-DPA prepared in example 1 to an object to be tested is verified, and the specific operation method comprises the following steps: different pesticides and metal ions are used for replacing the p-nitrophenol and nickel ions in equal quantity and are added into the ratio type probe. Specific probe configurations and quench rate calculations were made with reference to the method in Experimental example 4.
The detection results are shown in FIG. 7, wherein A in FIG. 7 is the selective detection result of CDs@Tb-DPA in the presence of 80. Mu.M of different pesticide contaminants; FIG. 7B is a graph of fluorescence spectra of CDs@Tb-DPA in the presence of 80. Mu.M of different pesticide contaminants; FIG. 7C shows the selective detection results of CDs@Tb-DPA in the presence of 10. Mu.M of different metal ions; in FIG. 7D is a graph of fluorescence spectra of CDs@Tb-DPA in the presence of 10. Mu.M of different metal ions.
As can be seen from FIG. 7, CDs@Tb-DPA has a very high selectivity for p-NP and nickel ions. In one aspect, A and B in FIG. 7 represent that CDs@Tb-DPA is unable to detect dinotefuran, malathion, diazinon, dichlorvos, malathion, monocrotophos, parathion methyl, parathion ethyl, methyl glufosinate and benfofos. On the other hand, potassium ion K is used + Zn ions of zinc 2+ Chromium ion Cr 2+ Antimony ions Sb 2+ Mn ions of Mn 2+ Silver ion Ag 2+ Gold ion Au 2+ Ca ion Ca 2+ And Na ion Na + To test the selectivity for metal ions. As shown in FIGS. 7C and D, only nickel ions can precisely quench the fluorescence intensity of CDs@Tb-DPA at 480 to 650 nm. The result shows that CDs@Tb-DPA has strong anti-interference capability and can be used for detecting complex samples.
Experimental example 6 detection in real samples
Methyl Paraoxone (MP) is a representative organophosphorus pesticide, is extremely common in water and plants, and constitutes a great threat to human safety. MP is treated by strong alkali solution, and the MP is effectively degraded into p-nitrophenol (p-NP) in equal molar ratio, so that the fluorescent probe can be used for quantitatively detecting.
1. Sample source
Tap water and lake water samples were collected from universities of australia. 10mL of water was centrifuged at 4000rpm for 10 minutes. After centrifugation, the sample was filtered through a 0.22 μm microporous membrane.
2. Detection flow
For Ni (II) ions and the treated MP, i.e., p-NP, samples, fluorescence detection was performed by adding 750. Mu.L of the supernatant samples containing both contaminants to a 2mL centrifuge tube containing 250. Mu.L of CDs@Tb-DPA prepared in example 1.
3. Results
The CDs@Tb-DPA detection system has strong selectivity and anti-interference capability, and the MP and Ni (II) ion content in tap water and lake water is tested by using a sample recovery rate experiment. Verification by ICP-MS and GC-MS indicated that MP and nickel ions were absent from the actual samples. After simple pretreatment of the actual sample (refer to the method of experimental example 5), the recovery rate was measured, and the detection results are shown in tables 2 and 3.
TABLE 2 recovery results of Nickel ions Ni (II) in Natural Water and lake Water samples
TABLE 3 recovery results of MP in Natural Water and lake Water samples
From tables 2 and 3, the recovery rate was between 90.00% and 109.00%. The results show that the established method has high selectivity, good repeatability and interference resistance, and the results represent that the true sample has good recovery rate and high method accuracy.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (40)
1. A ratio-type fluorescent probe is characterized by comprising a terbium-pyridine dicarboxylic acid compound and borate modified carbon quantum dots, wherein the carbon quantum dots are bonded with the terbium-pyridine dicarboxylic acid compound through borate,
the bonding process comprises the following steps: carrying out hydrothermal reaction on a borate-containing compound, and then carrying out reaction on the borate-containing compound, the alkali, the terbium-containing compound and the pyridine dicarboxylic acid compound to form the ratio type fluorescent probe;
the molar ratio of the borate-containing compound to the alkali to the terbium-containing compound to the dipicolinic acid compound is 6-323:500:1-3:2-10;
the steps before the hydrothermal reaction are carried out include: dissolving the compound containing borate, and then adjusting the pH value to 5-6;
the compound containing borate is 3-aminophenylboric acid;
the dipicolinic acid compound is dipicolinic acid.
2. A method of preparing a ratiometric fluorescent probe as claimed in claim 1, comprising bonding borate modified carbon quantum dots to terbium-pyridine dicarboxylic acid complexes.
3. The method of claim 2, wherein the step of performing the hydrothermal reaction comprises: the borate-containing compound was dissolved and then the pH was adjusted to 5.
4. The method of claim 2, wherein the step of performing the hydrothermal reaction comprises: the borate-containing compound was dissolved and then the pH was adjusted to 6.
5. The method according to claim 2, wherein the dissolution is carried out by ultrasonic dissolution for 5-15 minutes.
6. The method of claim 2, wherein the dissolution is performed by ultrasonic dissolution for 10 minutes.
7. The method of claim 2, wherein the concentration of the solution formed after dissolution is 0.1-5mg/mL.
8. The method of claim 2, wherein the concentration of the solution formed after dissolution is 0.5-3mg/mL.
9. The method of claim 2, wherein the concentration of the solution formed after dissolution is 0.8-1.2mg/mL.
10. The method of claim 2, wherein the concentration of the solution formed after dissolution is 1mg/mL, 1.5mg/mL or 2mg/mL.
11. The method of claim 2, wherein the concentration of the solution formed after dissolution is 1mg/mL.
12. The method according to claim 2, wherein the acid used for adjusting the pH is an inorganic acid.
13. The method according to claim 2, wherein the acid used for adjusting the pH is at least one of hydrochloric acid, sulfuric acid and nitric acid.
14. The preparation method according to claim 2, wherein the temperature of the hydrothermal reaction is 160-200 ℃.
15. The preparation method according to claim 2, wherein the temperature of the hydrothermal reaction is 170-190 ℃.
16. The process according to claim 2, wherein the hydrothermal reaction is carried out at a temperature of 175-185 ℃.
17. The method of claim 2, wherein the hydrothermal reaction is carried out at a temperature of 180 ℃.
18. The preparation method according to claim 2, wherein the hydrothermal reaction time is 5 to 7 hours.
19. The preparation method according to claim 2, wherein the hydrothermal reaction time is 5.5 to 6.5 hours.
20. The method of claim 2, wherein the hydrothermal reaction time is 6 hours.
21. The production method according to claim 2, characterized by comprising, after the hydrothermal reaction, before the reaction with the terbium-containing compound and the dipicolinic acid-based compound: and (3) carrying out post-treatment on the reaction system after the hydrothermal reaction.
22. The method of claim 21, wherein the post-treatment comprises: after cooling the reaction system, centrifugation was performed to form a supernatant.
23. The method according to claim 22, wherein the step of reacting with the terbium-containing compound and the dipicolinic acid-based compound comprises: and uniformly mixing the supernatant, the alkali, the terbium-containing compound and the pyridine dicarboxylic acid compound, and then refrigerating.
24. The method according to claim 23, wherein the base is selected from any one of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium bicarbonate, and aqueous ammonia.
25. The method of claim 23, wherein the base is sodium hydroxide.
26. The preparation method according to claim 23, wherein the alkali is added in the form of an alkali solution, and the concentration of the alkali solution is 0.3-0.7mol/L.
27. The method of claim 23, wherein the base is added in the form of an alkali solution having a concentration of 0.4mol/L, 0.5mol/L or 0.6mol/L.
28. The method of claim 23, wherein the terbium-containing compound is a terbium salt.
29. The method of claim 23, wherein the terbium-containing compound is terbium chloride.
30. The production method according to claim 23, wherein the terbium-containing compound is added in the form of a terbium-containing compound solution having a concentration of 0.05 to 0.15mmol/L.
31. The production method according to claim 23, wherein the terbium-containing compound is added in the form of a terbium-containing compound solution having a concentration of 0.8mmol/L, 0.1mmol/L or 0.12mmol/L.
32. The method according to claim 23, wherein the dipicolinic acid compound is added in the form of dipicolinic acid compound solution, and the concentration of the dipicolinic acid compound solution is 0.1-0.5mmol/L.
33. The method according to claim 23, wherein the dipicolinic acid compound is added in the form of a dipicolinic acid compound solution, and the dipicolinic acid compound solution has a concentration of 0.3mmol/L.
34. The method of claim 23, wherein the temperature of refrigeration is 0-4 ℃.
35. Use of the ratio-based fluorescent probe according to claim 1 for detecting organic matter and/or heavy metal ions; the organic matter is nitrophenol, and the heavy metal ions are nickel ions.
36. The use according to claim 35, wherein the detection is a sewage detection.
37. The use according to claim 35, wherein the ratio fluorescent probe according to claim 1 is used for simultaneous detection of nitrophenol and nickel ions.
38. A detection method, characterized in that it detects organic matter and/or heavy metal ions by using the ratio-type fluorescent probe according to claim 1; the organic matter is nitrophenol, and the heavy metal ions are nickel ions.
39. The method of claim 38, wherein the ratio-based fluorescent probe is mixed with the sample to be detected and then subjected to fluorescent detection.
40. The method of claim 39, wherein the fluorescence detection uses an excitation wavelength of 273nm.
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