CN103194212A - 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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- CN103194212A CN103194212A CN2013101074440A CN201310107444A CN103194212A CN 103194212 A CN103194212 A CN 103194212A CN 2013101074440 A CN2013101074440 A CN 2013101074440A CN 201310107444 A CN201310107444 A CN 201310107444A CN 103194212 A CN103194212 A CN 103194212A
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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 35
- 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 17
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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
- 238000004458 analytical method Methods 0.000 claims abstract description 3
- 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
- SDMNYPICHWANBA-UHFFFAOYSA-N n-(pyridin-2-ylmethylideneamino)acetamide Chemical compound CC(=O)NN=CC1=CC=CC=N1 SDMNYPICHWANBA-UHFFFAOYSA-N 0.000 claims description 18
- 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 6
- 230000035945 sensitivity Effects 0.000 abstract description 3
- -1 2-pyridylmethylene Chemical group 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 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 12
- 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
- 230000003139 buffering effect Effects 0.000 description 5
- 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
- 238000005303 weighing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 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
- 230000036039 immunity Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 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
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-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
- 230000000536 complexating effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 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
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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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-Ratio type fluorescent probe and synthetic method and application.
Background technology
Zine ion is the transition metal ion of human body relaying iron ion second enrichment afterwards.Zinc is being played the part of very important role in human body grows, it is the main component of tens of kinds of enzymes in the human body, is the requisite trace element of human brain development; Simultaneously, zinc promotes lymphopoiesis and movable effect in addition, to keeping epithelium and mucosal tissue normally and preventing that bacterium, poisoning intrusion from also having played important effect.Therefore, detection of zinc ions all has great significance to bio-science and medical science.
Negative sulfidion mainly is that the form with inorganic sulphide exists, and in the living things system environment, during negative sulfidion content overproof, can influence respiratory system, suppresses to breathe.Therefore, the negative sulfidion of discriminating and quantitative assay has great importance.
At present, after being used for the identification 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 subjected to the influence of concentration and probe concentration, excitation wavelength and testing environment easily, and 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, is subjected to the interference of cadmium element existence in recognition process easily at zine ion.
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, based on metal ion method of replacement identification S
2-But these methods all are 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 provides a kind of have good sensitivity, stronger immunity from interference, environment amenable relay identification Zn
2+And S
2-Ratio type fluorescent probe and synthetic method and application.
Technical solution of the present invention is:
A kind of relay identification Zn
2+And S
2-Ratio type 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 ratio type fluorescent probe, its reaction formula is:
Its concrete synthesis step is as follows:
Be solvent with DMF, 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 reaction 7h～10h; Add distilled water, regulate pH=6～7 with dilute hydrochloric acid, filter, collect the precipitation that generates, use the acetonitrile recrystallization, obtain fluorescent probe
N-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide.
A kind of relay identification Zn
2+And S
2-Ratio type fluorescent probe Zn in water environment system, biomass cells system
2+And S
2-Monitoring analysis and the application in the spike.
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 it is simple that product separates purification process;
(2) this fluorescent probe can relay identification Zn
2+And S
2-, by the regulation and control that the excited state molecule inner proton of probe molecule is shifted, i.e. Zn
2+After the probe complexing, suppressed excited state molecule inner proton transfer process, when adding S
2-After, S
2-With 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 ratio type fluorescent probe, has the self-checkign n. effect, can avoid the influence of some external factor, detects object ion more accurately, to Zn
2+And S
2-Mensuration have good sensitivity and stronger immunity from interference.
Description of 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 the effect;
Fig. 6 is fluorescent probe of the present invention and Cd
2+Fluorescence emission spectrum variation diagram before and after the effect;
Fig. 7 is fluorescent probe of the present invention and Cu
2+Fluorescence emission spectrum variation diagram before and after the effect;
Fig. 8 is fluorescent probe of the present invention and Co
2+Fluorescence emission spectrum variation diagram before and after the effect;
Fig. 9 is fluorescent probe of the present invention and Ni
2+Fluorescence emission spectrum variation diagram before and after the effect;
Figure 10 is fluorescent probe of the present invention and Hg
2+Fluorescence emission spectrum variation diagram before and after the effect;
Figure 11 is fluorescent probe of the present invention and Ag
+Fluorescence emission spectrum variation diagram before and after the 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 the effect;
Figure 13 is fluorescent probe of the present invention and Fe
2+Fluorescence emission spectrum variation diagram before and after the effect;
Figure 14 is fluorescent probe of the present invention and Pb
2+Fluorescence emission spectrum variation diagram before and after the effect;
Figure 15 is that fluorescent probe of the present invention is to Zn
2+The detection figure that anti-other metal ion disturbs during identification;
Figure 16 is fluorescent probe-Zn of the present invention
2+With other negatively charged ion and contain 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-Ion identification resists other negatively charged ion and contains the detection figure of the amino acid interference 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 the 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 the 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 the 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 the effect.
Embodiment
(1) synthetic relay identification Zn
2+And S
2-The reaction formula of ratio type fluorescent probe:
(2) synthetic relay identification Zn
2+And S
2-The concrete steps of ratio type fluorescent probe:
Take by weighing 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-the dimethyl formamide (DMF), at room temperature, stirring reaction 7h adds 100ml distilled water, regulates pH value to 6 with dilute hydrochloric acid, filters and collects the precipitation that produces, and uses the acetonitrile recrystallization, obtains fluorescent probe
N-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide (compound 1), yield is 56%.
Take by weighing the intermediate of 300mg
NTwo-(pyridine methylene) amine of-(2-(1H-benzimidazolyl-) phenyl)-2-chlor(o)acetamide and raw material 630mg, be dissolved among the DMF of 20ml, at room temperature, stirring reaction 9h, add 150ml distilled water, regulate pH value to 7 with dilute hydrochloric acid, filter and collect the precipitation that produces, use the acetonitrile recrystallization, obtain fluorescent probe
N-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide, yield is 68%.
Embodiment 3
Take by weighing the intermediate of 300mg
NTwo-(pyridine methylene) amine of-(2-(1H-benzimidazolyl-) phenyl)-2-chlor(o)acetamide and raw material 835mg, be dissolved among the DMF of 20ml, at room temperature, stirring reaction 10h, add 150ml distilled water, regulate pH value to 7 with dilute hydrochloric acid, filter and collect the precipitation that produces, use the acetonitrile recrystallization, obtain fluorescent probe
N-(2-(1H-benzimidazolyl-) phenyl)-2-two (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-two (2-pyridyl-methylene amino) ethanamide:
Fusing point: 177 ℃～179 ℃;
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.(such as Fig. 3).
Fluorescent probe
N-(2-(1H-benzimidazolyl-) phenyl)-2-two (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-two (2-pyridyl-methylene amino) ethanamide (fluorescent probe) cushions (v/v=2:8, pH=7.4) solution, the fluorescence emission spectrum of this fluorescent probe adds the metal ion (Ni of 10 μ mol/L respectively as shown in Figure 4
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 behind the 15min changes, as Fig. 5～shown in Figure 14.
As shown in Figure 4, fluorescent probe has emission peak at the 500nm place; As shown in Figure 5, add Zn
2+Behind the ion, probe solution fades away at the emission peak at 500nm place, simultaneously, has occurred a new emission peak again at the 424nm place, and strengthens gradually; As shown in Figure 6, add Cd
2+Behind the ion, probe solution is at a small amount of blue shift of 500nm place emission peak; By Fig. 7～Figure 14 as can be known, 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, the emission peak of probe solution at the 500nm place do not have obvious displacement; Therefore, fluorescent probe
N-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide is to Zn
2+And Cd
2+Good selectivity and separating capacity are arranged.
Fluorescent probe
N-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide to Zn
2+Detect with the selectivity of other metal ion:
10 μ mol/L
N(v/v=2:8, pH=7.4) solution add other metal ion (Ni of 10 μ mol/L to the acetonitrile of-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide (fluorescent probe)/HEPES buffering 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 behind the 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+Almost not influence of fluorescence identification.
Fluorescent probe
NThe relay identification S of-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide
2-Selectivity detect:
10 μ mol/L
N-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide and Zn
2+Title complex (fluorescent probe-Zn that the effect back forms
2+) acetonitrile/HEPES buffering (v/v=2:8, pH=7.4) solution add (F behind the negatively charged ion of 500 μ mol/L respectively
-, 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-), detected fluorescence pattern changing conditions (as shown in figure 16) behind the 15min; As seen from Figure 16, has only 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-two (2-pyridyl-methylene amino) ethanamide and Zn
2+Title complex (fluorescent probe-Zn that the effect back forms
2+) acetonitrile/HEPES buffering (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 behind the 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-Almost not influence of selectivity.
10 μ mol/L
N(v/v=2:8, pH=7.4) solution add the Zn of 0 μ mol/L～10 μ mol/L to the acetonitrile of-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide (fluorescent probe)/HEPES buffering
2+, the fluorescence pattern changing conditions (as shown in figure 18) that tests out; As seen from Figure 18, along with Zn
2+The continuous adding of amount, the emission peak fluorescence intensity at 500nm place constantly weakens, and new emission peak occurs at the 424nm place, and fluorescence intensity constantly strengthens, at the Zn that adds 10 μ mol/L
2+In time, reach capacity.
10 μ mol/L
N-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide and Zn
2+Title complex (fluorescent probe-Zn that the effect back forms
2+) acetonitrile/HEPES buffering (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) that tests out; As seen from Figure 19, along with S
2-The continuous 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, reach capacity.
The processing of actual water sample and detection:
(1) with the processing of actual water sample
Get river and lake water water sample, use dichloromethane extraction earlier, remove organism wherein; Take from water sample, heated and boiled 15min filters the back and cools off standby to remove chlorine wherein.
(2) Zn in the actual water sample
2+Detection
Prepare the aqueous solution of 10 μ mol/L fluorescent probes with the actual water sample after handling, add
NThe Zn of-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide (fluorescent probe) 0 μ mol/L～6 μ mol/L
2+, the fluorescence emission spectrum that detects solution behind the 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 the detected water sample is described
2+Concentration in 1 μ mol/L ~ 6 μ mol/L scopes the time, can realize Zn
2+Detection by quantitative.
(3) S in the actual water sample
2-Detection:
Prepare 10 μ mol/L with the actual water sample after handling
N-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide and Zn
2+Title complex (fluorescent probe-Zn that the effect back forms
2+) the aqueous solution, add the S of 0 μ mol/L～550 μ mol/L
2-, the fluorescence emission spectrum that detects solution behind the 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 the scope, the fluorescence intensity at 424nm place is linear, and S in the detected water sample is described
2-Concentration in 0 ~ 500 μ mol/L scope the time, can realize S
2-Detection by quantitative.
Claims (3)
1. Zn is identified in a relay
2+And S
2-Ratio type fluorescent probe, this fluorescent probe is the derivative of 2-(2'-aminophenyl) benzoglyoxaline, it is characterized in that: structural formula is as follows:
。
2. Zn is identified in a kind of relay as claimed in claim 1
2+And S
2-The synthetic method of ratio type fluorescent probe, it is characterized in that: reaction formula is:
Concrete synthesis step is as follows:
Be solvent with DMF, 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 reaction 7h～10h; Add distilled water, regulate pH=6～7 with dilute hydrochloric acid, filter, collect the precipitation that generates, use the acetonitrile recrystallization, obtain fluorescent probe
N-(2-(1H-benzimidazolyl-) phenyl)-2-two (2-pyridyl-methylene amino) ethanamide.
3. Zn is identified in a kind of relay as claimed in claim 1
2+And S
2-Ratio type fluorescent probe Zn in water environment system, biomass cells system
2+And S
2-Monitoring analysis and the application in the spike.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263354A (en) * | 2014-09-06 | 2015-01-07 | 渤海大学 | Relay-type multifunctional fluorescent probe, and preparation method and application thereof |
| CN105482808A (en) * | 2015-11-27 | 2016-04-13 | 中南林业科技大学 | Preparation method and use of fluorescent probe for detecting S<2-> in drinking water |
| CN107991273A (en) * | 2017-09-11 | 2018-05-04 | 齐齐哈尔大学 | A kind of imdazole derivatives class mercury ion and sulphion relay fluoroscopic examination and application method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000059888A1 (en) * | 1999-04-02 | 2000-10-12 | Neurogen Corporation | N-benzimidazolylmethyl- and n-indolylmethyl-benzamides and their use as crf modulators |
| 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 |
-
2013
- 2013-03-30 CN CN201310107444.0A patent/CN103194212B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000059888A1 (en) * | 1999-04-02 | 2000-10-12 | Neurogen Corporation | N-benzimidazolylmethyl- and n-indolylmethyl-benzamides and their use as crf modulators |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 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》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263354A (en) * | 2014-09-06 | 2015-01-07 | 渤海大学 | Relay-type multifunctional fluorescent probe, and preparation method and application thereof |
| CN104263354B (en) * | 2014-09-06 | 2016-08-24 | 渤海大学 | A kind of relay type Multifunction fluorescent probe, Its Preparation Method And Use |
| CN105482808A (en) * | 2015-11-27 | 2016-04-13 | 中南林业科技大学 | Preparation method and use of fluorescent probe for detecting S<2-> in drinking water |
| 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 |
| CN107991273A (en) * | 2017-09-11 | 2018-05-04 | 齐齐哈尔大学 | A kind of imdazole derivatives class mercury ion and sulphion relay fluoroscopic examination and application method |
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| CN103194212B (en) | 2014-09-17 |
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