CN104132920B - A kind of fluorescent quenching measures the method for Ag+ or F- - Google Patents
A kind of fluorescent quenching measures the method for Ag+ or F- Download PDFInfo
- Publication number
- CN104132920B CN104132920B CN201410384727.4A CN201410384727A CN104132920B CN 104132920 B CN104132920 B CN 104132920B CN 201410384727 A CN201410384727 A CN 201410384727A CN 104132920 B CN104132920 B CN 104132920B
- Authority
- CN
- China
- Prior art keywords
- reagent
- concentration
- solution
- mol
- detection
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
One fluorescent quenching of the present invention measures Ag+Or F‑Method, belong to technical field of analytical chemistry.Establishing a kind of with 1,2 O, O'(1,1,3,3 tetra isopropyl two silica ethers) 3,4 two (7 nitro 42,1,3 benzofuran amino) thia cup [4] aromatic hydrocarbons is fluorometric reagent s2, quantitative determines Trace Ag+Or F‑.Reagent s2 is at oxolane (THF)/H2O(v/v=4:1), in the buffer solution of pH7 ~ 8, with 476nm as fluorescence exciting wavelength, measure the fluorescence intensity at 530nm, measure Ag+Content；Reagent s2 is in THF solvent, with 470nm as fluorescence exciting wavelength, measures the fluorescence intensity at 524nm, measures F‑Content.Measure Ag+、F‑The detection range of linearity is two orders of magnitude, detection limit as little as 10‑9mol·L‑1.The chemical structural formula of reagent s2 is:
Description
Technical field
The invention belongs to analytical chemistry field.A kind of fluorescence quenching method detects special metal ion or the method for anion and reagent.
Background technology:On the basis of fluorescent probe is built upon molecular recognition and fluorescent technique combination, by the specific receptor selective binding to object, by corresponding fluorescence signal transmission mechanism, identification information is converted to the fluorescence signal being prone to detect, thus realizes detection on a molecular scale.Utilizing Fluorescence Increasing or quencher realization is the main method that fluorescent probe is applied to the detection of specific target molecules, ion.Highly sensitive and high selectivity due to fluorescence analysis, real-time in-situ detects, equipment is simple, and it is provided that abundant spectral information, in the fields such as analytical chemistry, biochemistry, environmental science, medicine and pharmacology, the aspect such as various ion detection, DNA and protein molecular marker, cell imaging, immunoassay plays an important role.
Silver has good antibacterial activity, thus is widely used in many commodity and medical supplies, but Ag+Ion can make internal sulfur-bearing enzyme inactivate, it is also possible to metabolites various with amine, imidazoles etc. are combined and cause various disease, Ag+And the harm producing human health that is widely present of heavy metal ion becomes problem of concern.The silver nanoparticle ion of widespread adoption can generate the oxygen that activity is the highest in recent years, and in suppression environment, the growth of beneficial bacteria, disturbs bacteriological aftergrowth, make the biotic environment of nature be destroyed.In recent years, fluorescence analysis is passed through, it is achieved quick, high sensitivity detection Ag+Chemical sensor receive much concern.Although Ag+Belong to typical heavy atom ion, and be frequently subjected to Cu2+And Hg2+Isoionic interference, but use fluorescence spectrum analysing method detection Ag+Probe design the most still achieving progress.Wang Wei et al. is by modifying the fluorescence signal reporter group with naphthalene nucleus and S at cup [4] aromatic hydrocarbons main body lower edge2O2Recognition site, has synthesized fluorescent probe molecule, shows that probe molecule is to Ag by researchs such as fluorescence emission spectrums+There is Selective recognition performance.Yoon and spring et al. reports naphthalimide derivative class Ag+Fluorescent probe, in the solution system of second eyeball/water (50/50, v/v, pH 7.4), this probe is to Ag+Selectively enhancement effect of fluorescence, has higher binding constant (Ka=1.24 × 105M-1) and relatively low detection limit (1.0 × 10-8M).Therefore, life, environment and medical science are all had great importance by the detection method setting up silver ion fast and efficiently.
Anion Recognition is the most constantly coming into one's own, and medicine and catalytic field of many uses, and the most numerous waste liquid containing anion also can be to environment.F-Ion, as the anion of volume minimum, is distributed widely in nature, and closely related with the refinement of the uranium of nerve gas, Drinking Water, nuclear weapon, dental caries preventing and treating, osteoporotic clinical diagnosis etc..Owing to the optical signal of the optical pickocffs such as fluorescence is prone to detection, highly sensitive, easy to use.Therefore, searching can high Selective recognition F-Fluorescent optical sensor be always the direction that chemists make great efforts.The design such as Liu Qingjian has synthesized novel F based on phenanthro-imidazoles-Probe.This probe can high selectivity, highly sensitive identification F-, fluorescence intensity acutely declines and other ions are (such as Cl-、Br-、I-) its fluorescence Spectra is only had faint reduction.A series of detectable all high selectivity of energy, the highly sensitive response F that Yu-Chen Lin et al. synthesizes with acridone condensed-nuclei aromatics for parent-、AcO-、H2PO4 -, the photo display solution fluorescence under uviol lamp all there occurs different color changes.Due to anion important function in life sciences and chemical process, the fluorescent probe of design synthesis of selective bonded anionic, have a wide range of applications at the aspect such as diagnosis of disease, environmental reconstruction.
Summary of the invention: present invention aims to, with fluorescent method, utilize a kind of fluorometric reagent detection by quantitative Trace Ag+Or F-Ion concentration, sets up a kind of high selectivity and highly sensitive fluorescence quenching spectrum analyzes method.
One fluorescent quenching of the present invention measures Ag+Or F-Method, be to be 1,2-O, O'(1,1 with chemical name, 3,3-tetra isopropyl two silica ethers)-3,4-bis-(7-nitro-4-2,1,3-benzofuran amino) thia cup [4] aromatic hydrocarbons, be abbreviated as reagents2, as detection Trace Ag+Or F-Fluorescent quenching agent, in different solvent mediums, quantitative determine Trace Ag+Or F-Ion, reagents2Molecular formula be C68H86N8O11S4Si2, chemical structural formula is:
Concrete grammar is (1) reagents2At oxolane (THF)/H2O(v/v=4:1), in hydroxyethyl piperazine second sulfacid (HEPES)-NaOH buffer solution (pH 7 ~ 8), measure Ag+Time, with 476nm as fluorescence exciting wavelength, measure the fluorescence intensity at 530nm, the reduction of fluorescence intensity and Ag in the range of finite concentration+Concentration is linear, quantitative determines Ag+Content；(2) reagents2In THF solvent, measure F-Time, with 470nm as fluorescence exciting wavelength, measure the fluorescence intensity at 524nm, the reduction of fluorescence intensity and F in the range of finite concentration-Concentration is linear, quantitative determines F-Content.
Above-mentioned a kind of fluorescence quenching method measures Ag+Or F-Method: (1) measure Ag+During ion, other coexisting ion includes: Li+, Na+, K+, Ca2+, Mg2+, Sr2+, Ba2+, Cd2+, Zn2+, Cr3+, Co2+, Ni2+, Pb2+, Cu2+, Fe3+, Al3+One of, at concentration and Ag+Time quite, except Al3+Outward, above-mentioned ion-pairing agents2Detection Ag+Fluorescence intensity affect error within 5%；(2) F is measured-During ion, other coexisting ion includes: Cl-, Br-, I-, NO3 -, HSO4 -, ClO4 -, PF6 -, AcO-, H2PO4 -One of, at concentration and F-Time quite, to reagents2Detection F-Fluorescence intensity affect error within 5%.
Above-mentioned a kind of fluorescence quenching method measures Ag+Or F-Method: (1) reagents2Detection Trace Ag+Concentration, detection the range of linearity be 1.0 × 10-7~7.0×10-5mol·L-1, detection limit as little as 10-9 mol·L-1；(2) reagents2Detection trace F-Concentration, detection the range of linearity be 1.0 × 10-7~7.5×10-5mol·L-1, detection limit as little as 10-9mol·L-1。
The compound method of various reagent is:
(1) reagents2Solution: weigh the reagent of 13.7mgs2, to dissolve with THF, be configured to 100mL solution, concentration is 100 μm ol L-1；
(2) Ag+Standard solution: weigh silver perchlorate 41.5mg, dissolves with distilled water, is configured to 100mL solution, Ag+Concentration is 2.00 × 10-3 mol·L-1；As required with distilled water stepwise dilution to suitable concentration；
(3) F-Standard solution: weigh the trihydrate ([CH of 63.1mg tetrabutyl ammonium fluoride3(CH2)3]4NF·3H2O) dissolve with THF, be configured to 100 mL solution, F-Concentration is 2.00 × 10-3 mol·L-1, as required with THF stepwise dilution to suitable concentration；
(4) preparation of other metal ion solution and Ag+Standard solution compound method is identical；The preparation of other anion solutions and F-Standard solution compound method is identical；
(6) HEPES-NaOH buffer preparation: be 0.01 mol L by concentration-1Hydroxyethyl piperazine second sulfacid (HEPES) and appropriate NaOH preparation, regulate pH 7 ~ 8；
When volumetric flask change in volume, various solution additions to change the most accordingly；Agents useful for same is analytical pure, and distilled water is redistilled water.
Above-mentioned a kind of fluorescent quenching measures Ag+Or F-Method be 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers)-3,4-bis-(7-nitro-4-2,1,3-benzofuran amino) thia cup [4] aromatic hydrocarbons, be abbreviated as reagents2, it is that the present inventor synthesizes as fluorometric reagent.
Reagents2Synthetic route be:
The first step, by raw material thia cup [4] aromatic hydrocarbons and 1,3-bis-chloro-1,1,3,3-tetra isopropyl two silicon ethers react in DMF (DMF) solution, intermediate feed 1 is i.e. obtained through eluting, 2-O, O'(1,1,3,3-tetra isopropyl two silica ethers) thia cup [4] aromatic hydrocarbons；
Second step is to control configuration, the intermediate feed 1,2-O that will obtain in the first step, O'(1,1,3,3-tetra isopropyl two silica ether) thia cup [4] aromatic hydrocarbons and bromoacetonitrile react in oxolane (THF) solution, obtain intermediate feed 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers)-3,4-bis-(cyanogen methoxyl group) thia cup [4] aromatic hydrocarbons；
3rd step, in oxolane (THF) solution, with diborane (B2H6) reduction 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ether)-3, cyano group in 4-bis-(cyanogen methoxyl group) thia cup [4] aromatic hydrocarbons, obtain intermediate 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers)-3,4-bis-(amino ethoxy) thia cup [4]；
4th step, intermediate 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers)-3,4-bis-(ammonia ethyoxyl) thia cup [4] aromatic hydrocarbons and 4-chloro-7-nitro benzo-2,1,3-4-oxadiazole is at chloroform (CHCl3) in solution reaction obtain compound 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers)-3,4-bis-(7-nitro-4-2,1,3-benzofuran amino) thia cup [4] aromatic hydrocarbons, i.e. reagents2, synthetic route is as follows:
Prepare reagents2The process conditions of each step are:
The first step, intermediate feed 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers) synthesis of thia cup [4] aromatic hydrocarbons
At N2In there-necked flask under Bao Hu, add thia cup [4] aromatic hydrocarbons, imidazoles, it is dried DMF(N, dinethylformamide), stir, then room temperature dropping is containing 1, 3-bis-chloro-1, 1, 3, the dry DMF solution of 3-tetra isopropyl two silicon ether, it it is thia cup [4] aromatic hydrocarbons according to mol ratio: imidazoles: 1, 3-bis-chloro-1, 1, 3, 3-tetra isopropyl two silicon ether=1:3 ~ 3.5:1 ~ 1.5 add, white solid is had to separate out, after dropping, after continuing reaction 11h, solution is cooled to 0 DEG C, add the hydrochloric acid of 2M, continue reaction 0.5h, separate out a large amount of precipitation, filter, washing, dichloromethane and recrystallizing methanol obtain white intermediate feed；
Reaction temperature: room temperature
Response time: 11.5h
Reaction dissolvent: DMF
Second step, intermediate feed 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers)-3,4-bis-(cyanogen methoxyl group) thia cup [4] aromatic hydrocarbons synthesizes
At N2In there-necked flask under Bao Hu, add 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers) thia cup [4] aromatic hydrocarbons, cesium carbonate, cesium iodide and anhydrous THF, back flow reaction 1h, solution is gradually become buff by colourless；Temperature is reduced to 20 DEG C, in bottle, add bromoacetonitrile, be 1,2-O according to mol ratio, O'(1,1,3,3-tetra isopropyl two silica ether) thia cup [4] aromatic hydrocarbons: cesium carbonate: cesium iodide: bromoacetonitrile=1:5.5 ~ 6.5:5.5 ~ 6.5:5.5 ~ 6.5, heat up, back flow reaction 12h, solution colour continues to deepen, finally close to black；Cooling, adds the hydrochloric acid of 2M, after extracting with chloroform, then washs it with saturated aqueous common salt, and colourless magnesium sulfate is dried, and filters, is spin-dried for, and silica gel column chromatography obtains intermediate feed；
Reaction temperature: backflow
Response time: 13h
Reaction dissolvent: anhydrous THF
Eluant: n-hexane/ethyl acetate (v/v, 9/1)
3rd step, intermediate 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers)-3,4-bis-(amino ethoxy) thia cup [4] synthesizes
At N2In there-necked flask under Bao Hu, add 1,2-O; O'(1,1,3; 3-tetra isopropyl two silica ether)-3; 4-bis-(cyanogen methoxyl group) thia cup [4] aromatic hydrocarbons, adds the THF solution of diborane by dry THF, according to mol ratio 1 after dissolving; 2-O; O'(1,1,3; 3-tetra isopropyl two silica ether)-3; 4-bis-(cyanogen methoxyl group) thia cup [4] aromatic hydrocarbons: diborane=1:5.5 ~ 6.5, back flow reaction 72h, adds water to bubble-free and produces; it is spin-dried for solvent; chloroform extracts, and anhydrous sodium sulfate is dried, and silica gel column chromatography purification obtains white intermediate；
Reaction temperature: backflow
Response time: 72h
Reaction dissolvent: anhydrous THF
Eluant: chloroform/triethylamine (v/v, 80/1)
4th step, 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ether)-3,4-bis-(7-nitro-4-2,1,3-benzofuran amino) thia cup [4] aromatic hydrocarbons synthesizes
At N2In there-necked flask under Bao Hu, add intermediate 1,2-O; O'(1,1,3; 3-tetra isopropyl two silica ether)-3,4-bis-(amino ethoxy) thia cup [4], 4-chloro-7-nitro benzo-2; 1; 3-4-oxadiazole, potassium carbonate, it is dried chloroform; according to mol ratio 1; 2-O, O'(1,1; 3; 3-tetra isopropyl two silica ether)-3,4-bis-(amino ethoxy) thia cup [4]: 4-chloro-7-nitro benzo-2,1; 3-4-oxadiazole: potassium carbonate=1:2 ~ 3:2.5 ~ 3.5, reflux 24h.After reaction terminates, filtering precipitation, after vacuum rotary steam removes solvent, silica gel column chromatography purification obtains red 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ether)-3,4-bis-(7-nitro-4-2,1,3-benzofuran amino) thia cup [4] aromatic hydrocarbons；
Reaction temperature: backflow
Response time: 24h
Reaction dissolvent: chloroform
Eluant: chloroform；N-hexane/ethyl acetate (v/v, 4/1)
Key technology in patent of the present invention is to control THF/H2O mixed solvent ratio and certain pH value, just can make reagents2Become and can detect Ag+Ion can detect again F-Multifunction fluorescent probe reagent.Although the mode using fluorescent quenching realizes the detection of ion, but the range of linearity of detection reaches 1.0 × 10-7~7.0×10-5mol·L-1, detection limit as little as 10-9mol·L-1, the interference of coexisting ion is little, and identifies have reversibility (illustrating 9 see accompanying drawing and accompanying drawing), and can realize Ag under neutral water soluble medium member+Detection；F-Detection is not included AcO-The interference of ion, unique properties, it is easy that analytical performance is better than the Fluorescence Increasing type probe reagent much reported, operation and control method.
Accompanying drawing explanation:
Fig. 1 reagents2THF/H2O solution fluorescence spectrum in the presence of different metal ion.
Concentration is 1.00 × 10-5 mol·L-1Reagents2THF/H2O(4/1, v/v, pH 7 ~ 8) solution, it is not added with metal ion respectively or adds 2.00 × 10-3mol·L-1Metal ion Ag+, Li+, Na+, K+, Ca2+, Mg2+, Sr2+, Ba2+, Cd2+, Al3+, Zn2+, Cr3+, Co2+, Ni2+, Pb2+, Cu2+, Fe3+After fluorescence spectrum.Ag+Addition make reagents2Fluorescence at 530nm significantly reduces, and transmitted wave length occurs that the green fluorescence of the photo display solution under red shift, uviol lamp disappears.And the addition of other above-mentioned Experiment Metal ions changes reagent hardlys2Fluorescence intensity.Excitation wavelength and the transmitting wavelength of test are respectively 476nm/530nm.
Fig. 2 coexistent metallic ion is to reagents2Fluorometric assay Ag+Impact.
It is 1.00 × 10 in concentration-5 mol·L-1Reagents2THF/H2O(4/1, v/v, pH 7 ~ 8) in solution, measure addition 2.00 × 10-3mol·L-1Ag+Rear reagents2In wavelength fluorescence intensity at 530nm.Measure again respectively tos2-Ag+One of other metal ions following adding isodose in mixed solution: Li+, Na+, K+, Ca2+, Mg2+, Sr2+, Ba2+, Cd2+, Zn2+, Cr3+, Co2+, Ni2+, Pb2+, Cu2+, Fe3+, Al3+After the change of fluorescence intensity level.Black bar representss2In be separately added into the fluorescence intensity of different metal ion.Red bar representss2-Ag+Mixed solution is separately added into fluorescence intensity change after above-mentioned metal ion again.Except Al3+Addition can makes2-Ag+Fluorescence recover outside, coexisting to reagent of other common metal ions2Detection Ag+Fluorescence intensity affect error within 5%.
The Ag of Fig. 3 variable concentrations+To reagents2Fluorescence titration spectrogram.
It is 1.00 × 10 in concentration-5 mol·L-1Reagents2THF/H2O(4/1, v/v, pH 7 ~ 8) solution is separately added into variable concentrations Ag+To reagents2In solution, along with Ag+Addition, the fluorescent spectrum curve recorded respectively.Emission peak at 530nm is gradually lowered, and launches wavelength gradually red shift.The excitation wavelength of test is 476nm.
Fig. 4 reagents2Fluorescent spectrometry detection Ag+Calibration curve.
Vertical coordinate is the fluorescence intensity level at a length of 530nm of transmitted wave, and abscissa is Ag+Concentration.Excitation wavelength is 476nm.Ag+The concentration range of linearity of response is 1.0 × 10-7 ~7.0×10-5mol·L-1。
Fig. 5 reagents2THF solution fluorescence spectrum in the presence of different anions.
Concentration is 1.00 × 10-5 mol·L-1Reagents2THF solution, be not added with respectively anion or add 2.00 × 10-3 mol·L-1Anion F-, Cl-, Br-, I-, NO3 -, HSO4 -, ClO4 -, PF6 -, AcO-, H2PO4 -After fluorescence spectrum.Except F-Addition make reagents2Fluorescence significantly reduces, AcO-Addition also make fluorescence significantly reduce, and the addition of other above-mentioned experiment aniones changes reagent hardlys2Fluorescence intensity.Maximum excitation and transmitting wavelength are respectively 470 nm and 524 nm.
Fig. 6 counter anion is to reagents2Fluorometric assay F-Impact.
It is 1.00 × 10 in concentration-5 mol·L-1Reagents2THF solution in, add 2.00 × 10-3 mol·L-1F-Rear fluorescence significantly reduces.Measure again respectively tos2-F-One of other following aniones adding isodose in mixed solution: Cl-, Br-, I-, NO3 -, HSO4 -, ClO4 -, PF6 -, AcO-, H2PO4 -After fluorescence intensity change.Black bar represents at reagents2Solution is separately added into the fluorescence intensity of different anions.Red bar representss2-F-Mixed solution is separately added into the fluorescence intensity change after other counter anions above-mentioned.Show reagents2Detection F-Fluorescence intensity do not included AcO-In the impact that interior other aniones above-mentioned coexist.Maximum excitation and transmitting wavelength are respectively 470nm and 524nm.
The F of Fig. 7 variable concentrations-To reagents2Fluorescence method spectra for titration figure.
It is 1.00 × 10 in concentration-5 mol·L-1Reagents2THF solution in be separately added into variable concentrations F-To reagents2In solution, along with F-Addition, the fluorescent spectrum curve recorded respectively.Emission peak at 524nm is gradually lowered.The excitation wavelength of test is 470nm.
Fig. 8 reagents2Spectrographic method detection F-Calibration curve.
Vertical coordinate is the fluorescence intensity at a length of 524nm of transmitted wave, and abscissa is F-Concentration.Excitation wavelength is 470nm.F-The concentration range of linearity of response is 1.0 × 10-7 ~7.5×10-5mol·L-1。
Fig. 9 reagents2Identify Ag+Reversibility.
With I-For competing reagent, at reagents2The Ag of middle addition 5 times amount+Rear fluorescent quenching, at reagents2-Ag+Complex solution adds relative to 5 times of reagents2The I of amount-, the fluorescence spectrum of system with do not add Ag+Time reagents2Fluorescence spectrum close, show I-Addition captures2-Ag+Ag in coordination compound+, define Ag+-I-Coordination compound；And then the Ag of 10 times is added+(relative to reagents2After), fluorescence emission spectrum reduces again at 530 nm, close to being initially added Ag+Time intensity.Show the Ag of excess+With reagent free in solutions2Re-forms2-Ag+Coordination compound, also explanation recognition reaction is reversible process.
Figure 10 synthesizes detection Ag in lake water sample+Fluorescence spectrum.
In sample liquid, different amounts of Ag is added successively by standard addition method+The fluorescence spectrum figure that standard solution records.
Detailed description of the invention
Embodiment one:
In the present invention, the compound method of reagent is:
(1) reagents2The preparation of solution: weigh the reagent of 13.7mgs2, dissolve with THF, be configured to 100mL solution,s2Concentration is 1.00 × 10-4 mol·L-1；
(2) Ag+Standard solution: weigh analytical pure silver perchlorate 41.5mg, uses second distillation water dissolution, and is configured to 100mL solution, Ag+Concentration is 2.00 × 10-3 mol·L-1；As required with redistilled water stepwise dilution to suitable concentration；
(3) F-Standard solution: weigh 63.1mg 4-butyl ammonium fluoride trihydrate ([CH3(CH2)3]4NF·3H2O) dissolve with THF, be configured to 100 mL solution, F-Concentration is 2.00 × 10-3 mol·L-1；As required with THF stepwise dilution to suitable concentration；
(4) preparation of other coexistent metallic ion solution: take perchlorate or the nitrate of analytically pure various metal, uses second distillation water dissolution, and to be configured to concentration be 2.00 × 10-3 mol·L-1Second distillation aqueous solution；
(5) preparation of other counter anion solution: take the 4-butyl ammonium of analytically pure various anion, dissolves with THF, and to be configured to concentration is 2.00 × 10-3 mol·L-1THF solution；
(6) HEPES-NaOH buffer preparation: by concentration be 0.01 mol/L hydroxyethyl piperazine second sulfacid (HEPES) and appropriate NaOH prepares, and regulates pH 7 ~ 8.
Reagent used by the inventive method is analytical reagent, and water is redistilled water.
Spectrofluorophotometer model used by the present invention is Cary Eclipse spectrofluorophotometer, and VARIAN company of the U.S. produces.
Embodiment two: to Ag+Ion detection
Reagent is added in 10.0 mL volumetric flaskss2THF storing solution (1.00 × 10-4 mol·L-1, 1mL), metal ion Ag+(2.00 × 10-3 mol·L-1, 1 mL), HEPES-NaOH buffer (1.00 × 10-3Mol/L, 1.0 mL), use THF/H2O(4/1, v/v) solvent dilution to scale, shake up, pH 7 ~ 8, move into 1cm quartz colorimetric utensil carry out fluorescence spectrometry.
Arranging fluorescence exciting wavelength is 476nm, to reagents2(1.00 × 10-5 mol·L-1) THF/H2O(4/1, v/v, pH 7 ~ 8) solution carries out fluorescence spectrum test, reagents2Fluorescent emission is had at 530 nm wavelength.Add Ag+(2.00 × 10-4 mol·L-1After), reagents2Solution fluorescence intensity at 530nm significantly reduces (quencher rate 75%), and the green fluorescence of the photo display solution under transmitting red shift of wavelength to 569nm, uviol lamp disappears.Under the same terms, at reagents2Solution is separately added into Li+, Na+, K+, Ca2+, Mg2+, Sr2+, Ba2+, Cd2+, Al3+, Zn2+, Cr3+, Co2+, Ni2+, Pb2+, Cu2+, Fe3+After metal ion, change reagent hardlys2Fluorescence spectrum and intensity.Reagents2Only to Ag+Selective fluoroscopic examination response performance, selects the fluorescence intensity at 530nm wavelength to carry out quantitative determining (accompanying drawing 1).
Identical with above-mentioned test condition, reagents2Detection Ag+Fluorescence intensity at 530nm wavelength is present in respectively as coexisting ion at above-mentioned metal ions2-Ag+In mixed solution, as the Ag of coexistent metallic ion concentration Yu test+When ion is suitable, except Al3+Addition can makes2-Ag+Fluorescence recover outside, other metal ions coexist to reagents2Detection Ag+Fluorescence intensity affect error all within 5% (accompanying drawing 2).
Under above-mentioned test strip, measure Ag respectively+Concentration changes and reagents2Fluorescence spectrum change at 530nm, it is thus achieved that the fluorescence titration curve of spectrum (accompanying drawing 3) and fluorescence method calibration curve (accompanying drawing 4).By the slope of calibration curve and the standard deviation of 10 blank values of mensuration, measure and be calculated reagents2Detection Ag+The concentration range of linearity and detection limit be listed in table 1.
Table 1 reagents2Detection Ag+The analytical parameters of ion
| Calibration curve range of linearity mol L-1 | Correlation coefficient | Detection limit mol L-1 |
| 1.0×10-7~7.0×10-5 | 0.9924(n=10) | 7.42×10-9 |
Embodiment three: to F-Ion detection
Reagent is added in 10mL volumetric flasks2THF storing solution (1.00 × 10-4 mol·L-1, 1mL), anion F-(2.00 × 10-3 mol·L-1, 1mL).With THF solvent dilution to scale, shaking up, the quartz colorimetric utensil moving into 1cm carries out fluorescence spectrometry.
Arranging excitation wavelength is 470nm, in THF solution, reagents2(concentration is 1.00 × 10-5 mol·L-1) launch 524 nm wavelength hyperfluorescences, under 365nm uviol lamp, observe strong green fluorescence.Add F-(concentration is 2.00 × 10-4 mol·L-1After), reagents2The fluorescence intensity of solution significantly reduces (quencher 99%), except F-There was added outside significant fluorescent quenching signal, AcO-Addition also make the obvious quencher of fluorescence, other test anion Cl-, Br-, I-, NO3 -, HSO4 -, ClO4 -, PF6 -, H2PO4 -To reagents2Solution all responds without obvious signal, shows reagents2Only to F-、AcO-Selective fluorescent quenching detection response performance (accompanying drawing 5).
Under above-mentioned fluorescence method test condition, reagents2Detection F-Fluorescence intensity experiment anion be present in respectively as coexisting ions2-F-In mixed solution, when coexisting ion includes AcO-F in interior concentration Yu test-When ion is suitable, to detection F-Fluorescence intensity impact relative deviation all within 5% (accompanying drawing 6).
Under the test conditions above, F is measured respectively-Concentration changes and reagents2Fluorescence spectrum change at 530nm, it is thus achieved that the fluorescence titration curve of spectrum (accompanying drawing 7) and calibration curve (accompanying drawing 8).By the slope of calibration trace and the standard deviation of 10 blank values of mensuration, measure and be calculated detection F-The range of linearity of ion concentration and detection limit are listed in table 2.
Table 2 reagents2Detection F-The analytical parameters of ion
| Calibration trace range of linearity mol L-1 | Correlation coefficient | Detection limit mol L-1 |
| 1.0×10-7~7.5×10-5 | 0.9972(n=11) | 4.70×10-9 |
Embodiment four: reagents2-Ag+The reversible character of coordination compound
With I-For competing reagent, at reagents2(1.00 × 10-5 mol·L-1The Ag of 5 times amount is added in)+(relative to reagents2) afterwards fluorescence significantly reduce (quencher rate 74%), at reagents2-Ag+Mixture solution adds relative to 5 times of reagents2The I of amount-, the fluorescence intensity of system strengthens, and does not adds Ag+Time reagents2Fluorescence spectrum close, for the 97% of original fluorescence intensity, show I-Addition captures2-Ag+Ag in coordination compound+, define Ag+-I-Coordination compound；And then the Ag of 10 times is added+(relative to reagents2After), fluorescence emission spectrum reduces again at 530 nm, close to being initially added Ag+Time intensity (Fig. 9).Show the Ag of excess+With reagent free in solutions2Re-form reagents2-Ag+Coordination compound, illustrates to be identified as reversible process.
Embodiment five: Ag in synthesis lake water sample+Content detection
1. lake water sample pre-treatments: take lake water sample 2.0 L, boils 10 minutes, cooling, stands and places 12 hours, filters, and detects water sample pH value.Concentrating is 10mL, cools down standby.
2. detection: pipette lake water sample processed for 1mL in 10mL volumetric flask, add 1 mL reagents2(1.00 × 10-5 mol·L-1, THF), 1 mL HEPES-NaOH, be sequentially added into 0,0.1,0.3,0.5mL Ag+(1.00 × 10-4 mol·L-1), use THF/H2O(4:1, v/v) mixed solvent constant volume, pH 7 ~ 8.Measure the fluorescence intensity at 530nm wavelength and carry out quantitative analysis, parallel assay 3 times.
It is calculated measurement result the most according to the method described above and is shown in Table 3.
。
Claims (5)
1. a fluorescent quenching measures Ag+Or F-Method, it is characterized in that with chemical name be 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers)-3,4-bis-(7-nitro-4-2,1,3-benzofuran amino) thia cup [4] aromatic hydrocarbons, be abbreviated as reagents2, as detection Trace Ag+Or F-Fluorescent quenching agent, in different solvent mediums, quantitative determine Trace Ag+Or F-Ion, reagents2Molecular formula be C68H86N8O11S4Si2, chemical structural formula is:
Concrete grammar is (1) reagents2Oxolane (THF)/H at v/v=4:12In hydroxyethyl piperazine second sulfacid (the HEPES)-NaOH buffer solution of O, pH 7 ~ 8, measure Ag+Time, with 476nm as fluorescence exciting wavelength, measure the fluorescence intensity at 530nm, the reduction of fluorescence intensity and Ag in the range of finite concentration+Concentration is linear, quantitative determines Ag+Content；(2) reagents2In THF solvent, measure F-Time, with 470nm as fluorescence exciting wavelength, measure the fluorescence intensity at 524nm, the reduction of fluorescence intensity and F in the range of finite concentration-Concentration is linear, quantitative determines F-Content.
A kind of fluorescent quenching the most according to claim 1 measures Ag+Or F-Method, it is characterized in that (1) measure Ag+During ion, other coexisting ion includes: Li+, Na+, K+, Ca2+, Mg2+, Sr2+, Ba2+, Cd2+, Zn2+, Cr3+, Co2+, Ni2+, Pb2+, Cu2+, Fe3+, Al3+One of, at concentration and Ag+Time quite, except Al3+Outward, above-mentioned ion-pairing agents2Detection Ag+Fluorescence intensity affect error within 5%；(2) F is measured-During ion, other coexisting ion includes: Cl-, Br-, I-, NO3 -, HSO4 -, ClO4 -, PF6 -, AcO-, H2PO4 -One of, at concentration and F-Time quite, to reagents2Detection F-Fluorescence intensity affect error within 5%.
A kind of fluorescent quenching the most according to claim 1 measures Ag+Or F-Method, it is characterized in that (1) reagents2Detection Trace Ag+Concentration, detection the range of linearity be 1.0 × 10-7~7.0×10-5mol·L-1, detection limit as little as 10-9 mol·L-1；(2) reagents2Detection trace F-Concentration, detection the range of linearity be 1.0 × 10-7~7.5×10-5mol·L-1, detection limit as little as 10-9mol·L-1。
A kind of fluorescent quenching the most according to claim 1 measures Ag+Or F-Method, it is characterized in that the compound method of various reagent is:
(1) reagents2Solution: weigh the reagent of 13.7mgs2, to dissolve with THF, be configured to 100mL solution, concentration is 100 μm ol L-1；
(2) Ag+Standard solution: weigh silver perchlorate 41.5mg, dissolves with distilled water, is configured to 100mL solution, Ag+Concentration is 2.00 × 10-3 mol·L-1；As required with distilled water stepwise dilution to suitable concentration；
(3) F-Standard solution: weigh the trihydrate ([CH of 63.1mg tetrabutyl ammonium fluoride3(CH2)3]4NF·3H2O) dissolve with THF, be configured to 100 mL solution, F-Concentration is 2.00 × 10-3 mol·L-1, as required with THF stepwise dilution to suitable concentration；
(4) preparation of other metal ion solution and Ag+Standard solution compound method is identical；The preparation of other anion solutions and F-Standard solution compound method is identical；
(6) HEPES-NaOH buffer preparation: be 0.01 mol L by concentration-1Hydroxyethyl piperazine second sulfacid (HEPES) and appropriate NaOH preparation, regulate pH 7 ~ 8.
A kind of fluorescent quenching the most according to claim 4 measures Ag+Or F-Method, it is characterized in that, when volumetric flask change in volume, various solution additions to change the most accordingly；Agents useful for same is analytical pure, and distilled water is redistilled water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410384727.4A CN104132920B (en) | 2014-08-07 | 2014-08-07 | A kind of fluorescent quenching measures the method for Ag+ or F- |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410384727.4A CN104132920B (en) | 2014-08-07 | 2014-08-07 | A kind of fluorescent quenching measures the method for Ag+ or F- |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104132920A CN104132920A (en) | 2014-11-05 |
| CN104132920B true CN104132920B (en) | 2016-08-24 |
Family
ID=51805684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410384727.4A Active CN104132920B (en) | 2014-08-07 | 2014-08-07 | A kind of fluorescent quenching measures the method for Ag+ or F- |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104132920B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104833664B (en) * | 2015-03-25 | 2017-08-08 | 贵州大学 | A kind of living cells Rare Earth Ion La3+、Lu3+Fluorescence imaging method |
| CN105788530B (en) | 2016-05-18 | 2018-06-01 | 深圳市华星光电技术有限公司 | The threshold voltage circuit for detecting of OLED display |
| CN105884710B (en) * | 2016-06-08 | 2021-07-02 | 南开大学 | 1,3, 4-oxadiazole Cu based on calixarene2+Fluorescent probe and synthetic method thereof |
| CN109251331A (en) * | 2018-09-19 | 2019-01-22 | 天津工业大学 | A kind of Polyamine capsule dispersion liquid removing underwater gold category ion |
| CN109655436B (en) * | 2018-12-07 | 2021-03-30 | 武汉工程大学 | Column aromatic modified cyanide ion fluorescence detection test paper, and preparation method and detection method thereof |
| CN116120359A (en) * | 2023-02-27 | 2023-05-16 | 茅台学院 | Be used for detecting Zn 2+ Fluorescent probe of (2), preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982300A (en) * | 2005-12-13 | 2007-06-20 | 北京师范大学 | Calixarene aza-crown ether derivative, its preparation and use as metal ion fluorescent identification agent |
| EP1798270A1 (en) * | 2004-09-22 | 2007-06-20 | Japan Science and Technology Agency | Water-soluble fluorescent material and method for producing same |
| CN102276481A (en) * | 2011-04-29 | 2011-12-14 | 苏州大学 | Calixarene derivative and metal complex thereof, and preparation method and application of calixarene derivative and metal complex thereof |
| CN103342699A (en) * | 2013-07-16 | 2013-10-09 | 贵州大学 | Coumarin-thiacalix [4] arene fluorescent reagent as well as preparation method and application thereof |
-
2014
- 2014-08-07 CN CN201410384727.4A patent/CN104132920B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1798270A1 (en) * | 2004-09-22 | 2007-06-20 | Japan Science and Technology Agency | Water-soluble fluorescent material and method for producing same |
| CN1982300A (en) * | 2005-12-13 | 2007-06-20 | 北京师范大学 | Calixarene aza-crown ether derivative, its preparation and use as metal ion fluorescent identification agent |
| CN102276481A (en) * | 2011-04-29 | 2011-12-14 | 苏州大学 | Calixarene derivative and metal complex thereof, and preparation method and application of calixarene derivative and metal complex thereof |
| CN103342699A (en) * | 2013-07-16 | 2013-10-09 | 贵州大学 | Coumarin-thiacalix [4] arene fluorescent reagent as well as preparation method and application thereof |
Non-Patent Citations (12)
| Title |
|---|
| .《Sensors and Actuators B》.2012,第164卷(第1期),全文. * |
| A Molecular Keypad Lock Based on the Thiacalix[4]arene of 1,3-Alternate Conformation;Manoj Kumar et al;《American Chemical Society》;20090518;第11卷(第12期);全文 * |
| Heteroditopic thiacalix[4]arene receptor having ester and bipyridyl moieties for ions binding with positive/negative allosteric effect;Xin-Long Ni et al;《Journal of Molecular Structure》;20130823;第1046卷;全文 * |
| Molecular Taekwondo. 2. A New Calix[4]azacrown Bearing Two Different Binding Sites as a New Fluorescent Ionophore;Jong Seung Kim et al;《American Chemical Society》;20020712(第68期);全文 * |
| Optical Chemosensor for Ag+, Fe3+, and Cysteine: Information Processing at Molecular Level;Manoj Kumar et al;《American Chemical Society》;20101222;第13卷(第3期);全文 * |
| Pyrene-Armed Calix[4]azacrowns as New Fluorescent Ionophores: "Molecular Taekowndo" Process via Fluorescence Change;Jong Seung kim et al;《J.Org.Chem》;20020803;第67卷(第7期);全文 * |
| Synthesis and evaluation of a novel pyrenyl-appended triazole-based thiacalix[4]arene as a fluorescent sensor for Ag+ ion;Xin-Long Ni et al;《Tetrahedron》;20110506;第67卷(第18期);全文 * |
| Synthesis, Optical Resolution and Complexation Properties of Inherently Chiral Monoalkylated p-tert-Butyl-(1,2)-calix[4]crown Ethers;Francoise Arnaud-Neu et al;《J.Org.Chem》;19971231;第62卷(第23期);全文 * |
| Synthesis, structure and inclusion properties of cone-tris{[(50-methyl-2,20-bipyridyl)-5-yl] oxycarbonylmethoxy}hexahomotrioxacalix[3]arene;Xin-long Ni et al;《J Incl Phenom Macrocycl Chem》;20111031;第71卷(第1期);全文 * |
| Yu Fu et al.Use of a new thiacalix[4]arene derivative bearing two 4-chloro-7-nitrobenzofurazan groups as a colorimetric and fluorescent chemosensor for Ag+ and AcO− * |
| 基于杯[4]芳烃的银离子荧光探针的合成及性能;王炜等;《高等学校化学学报》;22121130;第33卷(第11期);全文 * |
| 新型呋咱阴离子探针的合成、晶体结构及性质研究;傅玉等;《无机化学学报》;20120830;第28卷(第8期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104132920A (en) | 2014-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104132920B (en) | A kind of fluorescent quenching measures the method for Ag+ or F- | |
| CN103952146B (en) | A kind of 1-(7-tonka bean camphor oxyethyl group)-4-(2-methyl-8-quinoline oxygen methyl)-1,2,3-triazoles ratio fluorescent or ratio uv-absorbing probe reagent and Synthesis and applications | |
| CN104101577B (en) | A kind of method that ratio absorption spectrophotometry determines Ag+ or F | |
| Khan et al. | Synthesis, characterization and applications of schiff base chemosensor for determination of Cr (III) ions | |
| CN107056704A (en) | A kind of hypochlorite ion's fluorescence probe of lysosome targeting and its application | |
| CN102746313A (en) | Rhodamine-B hydrazide derivative containing 1,2,4-triazole structural unit, preparation method and application thereof | |
| Li et al. | A rhodamine-benzimidazole based chemosensor for Fe 3+ and its application in living cells | |
| CN108178766A (en) | A kind of fluorescent probe molecule of recognizable iron ion and dihydrogen phosphate ions and its preparation method and application | |
| CN104788344B (en) | The one class difunctional fluorescent probe with anthracene as parent, preparation method and application | |
| Zhao et al. | A FRET-based ratiometric fluorescent probe for Hg2+ detection in aqueous solution and bioimaging in multiple samples | |
| Zhao et al. | Design, synthesis and applications of fluoride probe based on aromatization of isoquinolinium salts | |
| Ma et al. | An anthraquinone-based “turn-on” fluorescence probe for Hg2+ detection and its application in cell imaging | |
| CN108863961B (en) | Triazole anthraquinone derivative silver ion fluorescent probe and preparation method and application thereof | |
| CN104830312A (en) | Fluorescence-enhanced probe compound preparation method and trivalent chromium ion detection method | |
| Li et al. | A novel colorimetric chemosensor for Cu 2+ with high selectivity and sensitivity based on Rhodamine B | |
| CN113087651B (en) | Compound containing indole group and preparation method and application thereof | |
| CN109206351A (en) | A kind of near infrared fluorescent probe, preparation method and application for surveying palladium ion based on flower cyanines structure | |
| CN115261015B (en) | N is detected based on ICT principle 2 H 4 And Cu 2+ Double-channel fluorescent probe of (2), and preparation method and application thereof | |
| CN107739337A (en) | A kind of cadmium, aluminium, the preparation method of lead ion chelating agent | |
| Nakaya et al. | Sensitive fluorimetric flow injection analysis for fluoride ion with a novel reagent, 2′, 7′-dichlorofluorescein di-tert-butyldimethylsilyl ether | |
| CN110128328A (en) | A kind of fluorescence probe and preparation method thereof identifying molybdenum acid ion and recognition methods | |
| CN103012375B (en) | Pyridyl triazole methyl substituted acridine derivative, preparation method and application thereof | |
| CN105884787A (en) | Rhodamine 6G derivative and preparation method and application thereof | |
| CN112079861B (en) | Molecular probe for detecting fluorine ions through fluorescence quenching and preparation method thereof | |
| CN109370573A (en) | A kind of fluorescence probe, the preparation method and applications of dimercurion and temperature detection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201106 Address after: 531599 science and technology R & D service center of Tiandong County, Baise City, Guangxi Zhuang Autonomous Region Patentee after: Guangxi fine chemical products quality technology testing Co., Ltd Address before: 550025 Huaxi, Guiyang, Guizhou University (North) Technology Department Patentee before: Guizhou University |
|
| TR01 | Transfer of patent right |