CN103194212B - Ratio-dependent florescent probe for identifying Zn<2+> and S<2-> in relayed manner as well as synthesis method and application of ratio-dependent florescent probe - Google Patents
Ratio-dependent florescent probe for identifying Zn<2+> and S<2-> in relayed manner as well as synthesis method and application of ratio-dependent florescent probe Download PDFInfo
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- CN103194212B CN103194212B CN201310107444.0A CN201310107444A CN103194212B CN 103194212 B CN103194212 B CN 103194212B CN 201310107444 A CN201310107444 A CN 201310107444A CN 103194212 B CN103194212 B CN 103194212B
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- 239000000523 sample Substances 0.000 title abstract description 27
- 230000001419 dependent effect Effects 0.000 title abstract 6
- 238000001308 synthesis method Methods 0.000 title 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 33
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000012544 monitoring process Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000007850 fluorescent dye Substances 0.000 claims description 57
- 238000001556 precipitation Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 3
- -1 2-pyridylmethylene Chemical group 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 51
- 230000000694 effects Effects 0.000 description 22
- 238000002189 fluorescence spectrum Methods 0.000 description 21
- 238000010586 diagram Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000001514 detection method Methods 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 7
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 6
- 239000007995 HEPES buffer Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 4
- 229910020366 ClO 4 Inorganic materials 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 3
- FFFHZYDWPBMWHY-VKHMYHEASA-N L-homocysteine Chemical compound OC(=O)[C@@H](N)CCS FFFHZYDWPBMWHY-VKHMYHEASA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 3
- 229960003180 glutathione Drugs 0.000 description 3
- 235000003969 glutathione Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004641 brain development Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
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- 229940125904 compound 1 Drugs 0.000 description 1
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- 229940126214 compound 3 Drugs 0.000 description 1
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- 210000000981 epithelium Anatomy 0.000 description 1
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- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention relates to a ratio-dependent florescent probe for identifying Zn<2+> and S<2-> in a relayed manner. The ratio-dependent florescent probe has a structure formula described in the specification. The ratio-dependent florescent probe is synthesized by adopting the specific steps of: with DMF (Dimethyl Formamide) as a solvent, stirring raw materials, namely N-(2-(1H-benzimidazoly)phenyl)-2-chloroacetamide and bis-(pyridylmethylene) amine, according to a molar ratio of 1: 2-1: 4 at room temperature for reaction for 7-10 hours to obtain a solution; and adding distilled water to the solution, adjusting pH of the solution to 6-7 by using diluted hydrochloric acid, filtering to collect generated precipitate, and recrystallizing by using acetonitrile to obtain the florescent probe N-(2-(1H-benzimidazoly)phenyl)-2-bis(2-pyridylmethylene) acetamide. The ratio-dependent florescent probe has the advantages of favorable sensitivity, strong antijamming capability and friendliness to environment in the process of carrying out monitoring analysis and tracing on Zn<2+> and S<2-> in a water environment system and a biological cell system.
Description
Technical field
The present invention relates to a kind of relay identification Zn
2+and S
2-ratiometric fluorescent probe and synthetic method and application.
Background technology
Zine ion is the transition metal ion of human body relaying iron ion the second enrichment afterwards.Zinc is being played the part of very important role in human body grows, and it is the main component of tens of kinds of enzymes in human body, is the requisite trace element of human brain development; Meanwhile, zinc promotes lymphopoiesis and movable effect in addition, to maintaining epithelium and mucosal tissue normally and preventing that bacterium, poisoning intrusion from also having played very important effect.Therefore, the detection of zine ion all has great significance to bio-science and medical science.
Negative sulfidion is mainly to exist with the form of inorganic sulphide, in living things system environment, when negative sulfidion content overproof, can affect respiratory system, suppresses to breathe.Therefore, the negative sulfidion of Identification and determination mensuration has great importance.
At present, for after identifying zine ion and mainly adopting probe molecule in conjunction with zine ion, show as at original transmitting site that fluorescence strengthens or the fluorescent probe of quencher.But this class fluorescent probe is easily subject to the impact of concentration and probe concentration, excitation wavelength and testing environment, to the interference that causes of measurement result, prohibited data detection is true.And because zinc element and cadmium element are positioned at same main group, chemical property is similar, the interference that existed by cadmium element.
In the fluorescent probe design of the negative sulfidion of identification is synthetic, by fluorescent probe and metal ion (as Cu
2+or Hg
2+) complex compound that forms, the method identification S based on metal ion displacement
2-but these methods are all to show as fluorescence at original transmitting site to strengthen or quencher, and have used environmentally harmful cupric ion or mercury ion.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of have good sensitivity, stronger immunity from interference, environment amenable relay identification Zn
2+and S
2-ratiometric fluorescent probe and synthetic method and application.
Technical solution of the present invention is:
A kind of relay identification Zn
2+and S
2-ratiometric fluorescent probe, this fluorescent probe is the derivative of 2-(2'-aminophenyl) benzoglyoxaline, structural formula is as follows:
A kind of relay identification Zn
2+and S
2-the synthetic method of Ratiometric fluorescent probe, its reaction formula is:
Its concrete synthesis step is as follows:
Taking DMF as solvent, raw material
nthe mol ratio of-(2-(1H-benzimidazolyl-) phenyl)-2-chlor(o)acetamide and two-(pyridine methylene) amine is 1:2～1:4, stirring at room temperature reaction 7h～10h; Add distilled water, regulate pH=6～7 with dilute hydrochloric acid, filter, collect the precipitation generating, use acetonitrile recrystallization, obtain fluorescent probe
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide.
A kind of relay identification Zn
2+and S
2-ratiometric fluorescent probe Zn in water environment system, biomass cells system
2+and S
2-monitoring analysis and spike in application.
Beneficial effect of the present invention:
(1) needed raw material
n-(2-(1H-benzimidazolyl-) phenyl)-2-chlor(o)acetamide, can pass through the preparation of 2-(2'-aminophenyl) benzoglyoxaline, and raw material is easy to get; The building-up reactions of fluorescent probe only needs a step, and product separation purification process is simple;
(2) this fluorescent probe energy relay identification Zn
2+and S
2-, the regulation and control of shifting by the excited state molecule inner proton to probe molecule, i.e. Zn
2+after probe complexing, suppress excited state molecule inner proton transfer process, when adding S
2-after, S
2-by Zn
2+from complex compound, capture out, the excited state molecule inner proton transfer process of probe is restored, thereby reached the multifunction of fluorescent probe molecule; And, use Zn
2+complex compound detects S
2-, environmentally friendly;
(3) this fluorescent probe belongs to Ratiometric fluorescent probe, has self-checkign n. effect, can avoid the impact of some external factor, detects more accurately object ion, to Zn
2+and S
2-mensuration there is good sensitivity and stronger immunity from interference.
Brief description of the drawings
Fig. 1 is fluorescent probe of the present invention
1h NMR spectrogram;
Fig. 2 is fluorescent probe of the present invention
13c NMR spectrogram;
Fig. 3 is the mass spectrogram of fluorescent probe of the present invention;
Fig. 4 is the fluorescence emission spectrogram of fluorescent probe of the present invention;
Fig. 5 is fluorescent probe of the present invention and Zn
2+fluorescence emission spectrum variation diagram before and after effect;
Fig. 6 is fluorescent probe of the present invention and Cd
2+fluorescence emission spectrum variation diagram before and after effect;
Fig. 7 is fluorescent probe of the present invention and Cu
2+fluorescence emission spectrum variation diagram before and after effect;
Fig. 8 is fluorescent probe of the present invention and Co
2+fluorescence emission spectrum variation diagram before and after effect;
Fig. 9 is fluorescent probe of the present invention and Ni
2+fluorescence emission spectrum variation diagram before and after effect;
Figure 10 is fluorescent probe of the present invention and Hg
2+fluorescence emission spectrum variation diagram before and after effect;
Figure 11 is fluorescent probe of the present invention and Ag
+fluorescence emission spectrum variation diagram before and after effect;
Figure 12 be fluorescent probe of the present invention respectively with Ba
2+, Mg
2+, K
+, Al
3+, Fe
3+, Na
+, Sr
2+, Cr
3+, Mn
2+fluorescence emission spectrum variation diagram before and after effect;
Figure 13 is fluorescent probe of the present invention and Fe
2+fluorescence emission spectrum variation diagram before and after effect;
Figure 14 is fluorescent probe of the present invention and Pb
2+fluorescence emission spectrum variation diagram before and after effect;
Figure 15 is that fluorescent probe of the present invention is to Zn
2+the detection figure of anti-other metal ion disturbance when identification;
Figure 16 is fluorescent probe-Zn of the present invention
2+with other negatively charged ion and containing the fluorescence emission spectrum variation diagram before and after the amino acid effect of sulfydryl;
Figure 17 is fluorescent probe-Zn of the present invention
2+to S
2-anti-other negatively charged ion of ion identification and the detection figure disturbing containing the amino acid of sulfydryl;
Figure 18 is the Zn of fluorescent probe of the present invention and 0 μ mol/L～10 μ mol/L
2+fluorescence emission spectrum variation diagram after effect;
Figure 19 is fluorescent probe-Zn of the present invention
2+s with 0 μ mol/L～200 μ mol/L
2-fluorescence emission spectrum variation diagram after effect;
Figure 20 be fluorescent probe of the present invention in actual water sample with the Zn of 0 μ mol/L～6 μ mol/L
2+fluorescence emission spectrum variation diagram after effect;
Figure 21 is fluorescent probe-Zn of the present invention
2+in actual water sample with the Zn of 0 μ mol/L～500 μ mol/L
2+fluorescence emission spectrum variation diagram after effect.
Embodiment
Embodiment 1
(1) synthetic relay identification Zn
2+and S
2-the reaction formula of Ratiometric fluorescent probe:
(2) synthetic relay identification Zn
2+and S
2-the concrete steps of Ratiometric fluorescent probe:
Take the intermediate of 300mg
ntwo-(pyridine methylene) amine (compound 3) of-(2-(1H-benzimidazolyl-) phenyl)-2-chlor(o)acetamide (compound 2) and raw material 418mg, are dissolved in 20ml's
n,Nin-dimethyl formamide (DMF), at room temperature, stirring reaction 7h, adds 100ml distilled water, by dilute hydrochloric acid adjusting pH value to 6, filters and collects the precipitation producing, and uses acetonitrile recrystallization, obtains fluorescent probe
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide (compound 1), yield is 56%.
Embodiment 2
Take the intermediate of 300mg
ntwo-(pyridine methylene) amine of-(2-(1H-benzimidazolyl-) phenyl)-2-chlor(o)acetamide and raw material 630mg, be dissolved in the DMF of 20ml, at room temperature, stirring reaction 9h, add 150ml distilled water, by dilute hydrochloric acid adjusting pH value to 7, filter and collect the precipitation producing, use acetonitrile recrystallization, obtain fluorescent probe
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide, yield is 68%.
Embodiment 3
Take the intermediate of 300mg
ntwo-(pyridine methylene) amine of-(2-(1H-benzimidazolyl-) phenyl)-2-chlor(o)acetamide and raw material 835mg, be dissolved in the DMF of 20ml, at room temperature, stirring reaction 10h, add 150ml distilled water, by dilute hydrochloric acid adjusting pH value to 7, filter and collect the precipitation producing, use acetonitrile recrystallization, obtain fluorescent probe
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide, yield is 72%.
The fluorescent probe of embodiment 1～embodiment 3
nthe master data of-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide:
Fusing point: 177 DEG C～179 DEG C;
1h NMR (400 MHz, DMSO-
d 6)
δ13.20 (s, 1H), 13.09 (s, 1H), 8.72 (d,
j=8.4 Hz, 1H), 8.41 (d,
j=4.3 Hz, 2H), 8.04 (d,
j=7.8 Hz, 1H), 7.75 (d,
j=7.8 Hz, 2H), 7.57 (s, 2H), 7.47-7.31 (m, 3H), 7.32-7.04 (m, 5H), 4.13-3.84 (m, 4H), 3.39 (S, 2H). (as Fig. 1).
13c NMR (100 MHz, DMSO-
d 6).
δ170.47,158.25,150.95,149.24,138.09,136.74,130.89,128.22,123.51,123.43,122.74,120.74,116.90,60.53,58.79. (as Fig. 2).
The calculated value C of high resolution mass spectrum (electron spray(ES), holotype)
27h
24n
6oNa [
1+ Na]
+, 471.1909, measured value 471.1908.(is as Fig. 3).
Fluorescent probe
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide to Zn
2+and Cd
2+selectivity detect:
10 μ mol/L
nacetonitrile/the HEPES of-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide (fluorescent probe) cushions (v/v=2:8, pH=7.4) solution, the fluorescence emission spectrum of this fluorescent probe as shown in Figure 4, adds respectively the metal ion (Ni of 10 μ mol/L
2+, Hg
2+, Ba
2+, Mg
2+, K
+, Al
3+, Mn
2+, Pb
2+, Na
+, Sr
2+, Co
2+, Cr
3+, Ag
+, Fe
2+, Fe
3+, Cu
2+, Zn
2+, Cd
2+), the fluorescence emission spectrum that detects solution after 15min changes, as shown in Fig. 5～Figure 14.
As shown in Figure 4, fluorescent probe has emission peak at 500nm place; As shown in Figure 5, add Zn
2+after ion, probe solution fades away at the emission peak at 500nm place, meanwhile, has occurred again a new emission peak at 424nm place, and strengthens gradually; As shown in Figure 6, add Cd
2+after ion, probe solution is at a small amount of blue shift of 500nm place emission peak; From Fig. 7～Figure 14, add Ni
2+, Hg
2+, Ba
2+, Mg
2+, K
+, Al
3+, Mn
2+, Pb
2+, Na
+, Sr
2+, Co
2+, Cr
3+, Ag
+, Fe
2+, Fe
3+, Cu
2+after, probe solution at the emission peak at 500nm place without obvious displacement; Therefore, fluorescent probe
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide is to Zn
2+and Cd
2+there are good selectivity and separating capacity.
Fluorescent probe
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide to Zn
2+detect with the selectivity of other metal ion:
10 μ mol/L
nacetonitrile/the HEPES of-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide (fluorescent probe) cushions (v/v=2:8, pH=7.4) solution adds other metal ion (Ni of 10 μ mol/L simultaneously
2+, Hg
2+, Ba
2+, Mg
2+, K
+, Al
3+, Mn
2+, Pb
2+, Na
+, Sr
2+, Co
2+, Cr
3+, Ag
+, Fe
2+, Fe
3+, Cu
2+, Cd
2+) and Zn
2+, the fluorescence spectrum that detects solution after 15min changes, and calculates
f 424nm/
f 500nmnumerical value (as shown in figure 15); As seen from Figure 15, other metal ion (Ni
2+, Hg
2+, Ba
2+, Mg
2+, K
+, Al
3+, Mn
2+, Pb
2+, Na
+, Sr
2+, Co
2+, Cr
3+, Ag
+, Fe
2+, Fe
3+, Cu
2+, Cd
2+) to Zn
2+fluorescence identification almost do not affect.
Fluorescent probe
nthe relay identification S of-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide
2-selectivity detect:
10 μ mol/L
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide and Zn
2+title complex (fluorescent probe-the Zn forming after effect
2+) acetonitrile/HEPES cushion (v/v=2:8, pH=7.4) solution, add respectively (F after the negatively charged ion of 500 μ mol/L
-, Cl
-, Br
-, I
-, SCN
-, PO
4 3-, S
2o
3 2-, S
2o
8 2-, H
2pO
4 -, HPO
4 2-, NO
2 -, NO
3 -, C
2o
4 2-, AcO
-, ClO
4 -, SO
4 2-, P
2o
7 4-, HSO
4 -, CO
3 2-, HCO
3 -, halfcystine, homocysteine, reduced glutathion, S
2-), the fluorescence pattern changing conditions (as shown in figure 16) detecting after 15min; As seen from Figure 16, only has S
2-can make fluorescent probe-Zn
2+fluorescence returns to the state of fluorescent probe self, and this fluorescent probe-Zn is described
2+system is to S
2-high selectivity.
10 μ mol/L
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide and Zn
2+title complex (fluorescent probe-the Zn forming after effect
2+) acetonitrile/HEPES cushion (v/v=2:8, pH=7.4) solution, add the negatively charged ion (F of 200 μ mol/L simultaneously
-, Cl
-, Br
-, I
-, SCN
-, PO
4 3-, S
2o
3 2-, S
2o
8 2-, H
2pO
4 -, HPO
4 2-, NO
2 -, NO
3 -, AcO
-, ClO
4 -, C
2o
4 2-, SO
4 2-, P
2o
7 4-, HSO
4 -, CO
3 2-, HCO
3 -, halfcystine, homocysteine, reduced glutathion) and S
2-, the fluorescence spectrum that detects solution after 15min changes, and calculates
f 424nm/
f 500nmnumerical value (Fig. 2 as shown in figure 17), as seen from Figure 17, other negatively charged ion (F
-, Cl
-, Br
-, I
-, SCN
-, PO
4 3-, S
2o
3 2-, S
2o
8 2-, H
2pO
4 -, HPO
4 2-, NO
2 -, NO
3 -, AcO
-, ClO
4 -, C
2o
4 2-, SO
4 2-, P
2o
7 4-, HSO
4 -, CO
3 2-, HCO
3 -, halfcystine, homocysteine, reduced glutathion) and to S
2-selectivity almost do not affect.
10 μ mol/L
nacetonitrile/the HEPES of-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide (fluorescent probe) cushions (v/v=2:8, pH=7.4) solution, adds the Zn of 0 μ mol/L～10 μ mol/L
2+, the fluorescence pattern changing conditions (as shown in figure 18) testing out; As seen from Figure 18, along with Zn
2+constantly the adding of amount, the emission peak fluorescence intensity at 500nm place constantly weakens, and occurs new emission peak at 424nm place, and fluorescence intensity constantly strengthens, at the Zn that adds 10 μ mol/L
2+in time, reaches capacity.
10 μ mol/L
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide and Zn
2+title complex (fluorescent probe-the Zn forming after effect
2+) acetonitrile/HEPES cushion (v/v=2:8, pH=7.4) solution, add the S of 0 μ mol/L～200 μ mol/L
2-after, the fluorescence pattern changing conditions (as shown in figure 19) testing out; As seen from Figure 19, along with S
2-constantly the adding of amount, the emission peak fluorescence intensity at 500nm place constantly strengthens, and constantly weakens at the emission peak at 424nm place, at the S that adds 200 μ mol/L
2-in time, reaches capacity.
The processing of actual water sample and detection:
(1) by the processing of actual water sample
Get river and lake water water sample, first use dichloromethane extraction, remove organism wherein; Take from water sample, heated and boiled 15min is to remove chlorine wherein, cooling for subsequent use after filtering.
(2) Zn in actual water sample
2+detection
The aqueous solution of preparing 10 μ mol/L fluorescent probes by actual water sample after treatment, adds
nthe Zn of-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide (fluorescent probe) 0 μ mol/L～6 μ mol/L
2+, the fluorescence emission spectrum that detects solution after 15min changes (as shown in figure 20); As seen from Figure 20, at the Zn that adds 1 μ mol/L～6 μ mol/L
2+scope in, the fluorescence intensity at 424nm place is linear, and Zn in detected water sample is described
2+concentration within the scope of 1 μ mol/L ~ 6 μ mol/L time, can realize Zn
2+detection by quantitative.
(3) S in actual water sample
2-detection:
Prepare 10 μ mol/L by actual water sample after treatment
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide and Zn
2+title complex (fluorescent probe-the Zn forming after effect
2+) the aqueous solution, add the S of 0 μ mol/L～550 μ mol/L
2-, the fluorescence emission spectrum that detects solution after 15min changes (as shown in figure 21).As seen from Figure 21, at the S that adds 0 μ mol/L～500 μ mol/L
2-in scope, the fluorescence intensity at 424nm place is linear, and S in detected water sample is described
2-concentration within the scope of 0 ~ 500 μ mol/L time, can realize S
2-detection by quantitative.
Claims (3)
1. a relay identification Zn
2+and S
2-ratiometric fluorescent probe, this fluorescent probe is the derivative of 2-(2'-aminophenyl) benzoglyoxaline, it is characterized in that: structural formula is as follows:
。
2. a kind of relay identification Zn as claimed in claim 1
2+and S
2-the synthetic method of Ratiometric fluorescent probe, it is characterized in that: reaction formula is:
Concrete synthesis step is as follows:
Taking DMF as solvent, raw material
nthe mol ratio of-(2-(1H-benzimidazolyl-) phenyl)-2-chlor(o)acetamide and two-(pyridine methylene) amine is 1:2～1:4, stirring at room temperature reaction 7h～10h; Add distilled water, regulate pH=6～7 with dilute hydrochloric acid, filter, collect the precipitation generating, use acetonitrile recrystallization, obtain fluorescent probe
n-(2-(1H-benzimidazolyl-) phenyl)-2-bis-(2-pyridyl-methylene amino) ethanamide.
3. a kind of relay identification Zn as claimed in claim 1
2+and S
2-ratiometric fluorescent probe Zn in water environment system, biomass cells system
2+and S
2-monitoring analysis and spike in application.
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| CN105482808B (en) * | 2015-11-27 | 2017-05-31 | 中南林业科技大学 | S in detection food-borne water2‑Fluorescence probe preparation method and application |
| CN107991273B (en) * | 2017-09-11 | 2021-03-19 | 齐齐哈尔大学 | Hg based on imidazole derivative fluorescent probe2+And S2-Relay fluorescence detection method |
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| CN101440062A (en) * | 2007-11-23 | 2009-05-27 | 齐齐哈尔大学 | Synthesis of N-acyl-8-amino quinoline derivatives and use thereof as fluorescent molecular probe |
| CN102146077A (en) * | 2011-01-13 | 2011-08-10 | 上海大学 | Fluoreneimidazole derivatives and preparation method thereof |
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| CN102146077A (en) * | 2011-01-13 | 2011-08-10 | 上海大学 | Fluoreneimidazole derivatives and preparation method thereof |
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| 苯并咪唑类比率型荧光探针的合成及应用研究;齐海萍;《中国优秀硕士学位论文全文数据库》;20100915;1.3论文设想，及2-5章化合物的合成部分，第10-11页 * |
| 齐海萍.苯并咪唑类比率型荧光探针的合成及应用研究.《中国优秀硕士学位论文全文数据库》.2010, |
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