CN104132920A - Method for measuring Ag<+> or F<-> through fluorescence quenching - Google Patents

Method for measuring Ag<+> or F<-> through fluorescence quenching Download PDF

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CN104132920A
CN104132920A CN201410384727.4A CN201410384727A CN104132920A CN 104132920 A CN104132920 A CN 104132920A CN 201410384727 A CN201410384727 A CN 201410384727A CN 104132920 A CN104132920 A CN 104132920A
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CN104132920B (en
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余梅
牟兰
曾晞
吴福勇
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Guangxi fine chemical products quality technology testing Co., Ltd
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Guizhou University
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Abstract

The invention discloses a method for measuring Ag<+> or F<-> through fluorescence quenching, and belongs to the technical field of analytical chemistry. The trace Ag<+> or F<-> is quantitatively measured by 1,2-O,O'(1,1,3,3-tetra-isopropyl-disiloxane)-3,4-di(7-nitro-4-2,1,3-benzofuran amino) thiacalix[4]arene serving as a fluorescent reagent s2. The reagent s2 measures the fluorescence intensity at 530nm in a tetrahydrofuran (THF)/H2O (v/v=4:1) buffering solution with the pH of 7 to 8 by taking 476nm as a fluorescence excitation wavelength so as to measure the Ag<+> content; in a THF solvent, the reagent s2 measures the fluorescence intensity at 524nm by taking 470nm as a fluorescence excitation wavelength so as to measure the F<-> content. The Ag<+> and the F<-> detection linear ranges are in two orders of magnitude; the detection limit is as low as 10<-9>mol*L<-1>. The chemical structural formula of the reagent s2 is shown in the specification.

Description

A kind of fluorescent quenching is measured the method for Ag+ or F-
Technical field
The invention belongs to analytical chemistry field.Specifically a kind of fluorescence quenching method detects method and the reagent of special metal ion or negative ion.
background technology:fluorescence probe is to be based upon on the basis of molecular recognition and fluorescent technique combination, selective binding by specific acceptor to object, by corresponding fluorescence signal transmission mechanism, identifying information is converted to the fluorescence signal that is easy to detection, thereby realizes the detection on molecular level.Utilizing fluorescence enhancing or quencher to realize the detection of specific target molecules, ion is the main method of fluorescence probe application.Due to the highly sensitive and high selectivity of fluorescence analysis, real-time in-situ detects, equipment is simple, and abundant spectral information can be provided, in the fields such as analytical chemistry, biological chemistry, 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, thereby is widely used in many commodity and medical supplies, but Ag +ion can make the sulfur-bearing enzyme deactivation in body, can also be combined with the various metabolic products such as amine, imidazoles and cause various diseases, Ag +and the harm that the extensive existence of heavy metal ion produces human health becomes the problem that people pay close attention to.The silver nanoparticle ion of widespread adoption can generate active very high oxygen in recent years, suppresses the growth of beneficial bacteria in environment, disturbs bacteriological aftergrowth, and natural coenocorrelation is destroyed.In recent years, by fluorescence analysis, realize quick, high sensitivity detection Ag +chemical sensor receive much concern.Although Ag +belong to typical heavy atom ion, and be usually subject to Cu 2+and Hg 2+isoionic interference, but adopt fluorescence spectrum analysing method to detect Ag +probe design still obtained progress in recent years.The people such as Wang Wei are by modifying fluorescence signal reporter group and the S with naphthalene nucleus at cup [4] aromatic hydrocarbons main body lower edge 2o 2recognition site, has synthesized fluorescent probe molecule, shows that by researchs such as fluorescence emission spectrums probe molecule is to Ag +there is selectivity recognition performance.The people such as Yoon and spring has reported naphthalimide derivative class Ag +fluorescence 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 × 10 5m -1) and lower detectability (1.0 × 10 -8m).Therefore, setting up the detection method of silver ion fast and efficiently all has great importance to life, environment and medical science.
Anion Recognition is constantly coming into one's own in recent years, and medicine and catalytic field of many uses, and numerous waste liquids that contain negative ion also can be to environment in commercial production.F -ion, as the negative ion of volume minimum, is distributed widely in occurring in nature, and closely related with the uranium refinement of nerve gas, Drinking Water, nuclear weapon, carious tooth control, osteoporotic clinical diagnosis etc.Because the light signal of the optical sensors such as fluorescence is easy to detect, highly sensitive, easy to use.Therefore, searching can high selectivity identification F -fluorescent optical sensor be the direction that chemists make great efforts always.The novel F based on phenanthro-imidazoles has been synthesized in the designs such as Liu Qingjian -probe.This probe energy high selectivity, highly sensitive identification F -, fluorescence intensity acutely decline and other ions (as Cl -, Br -, I -) its fluorescence Spectra is only had to faint reduction.All energy high selectivities of a series of detection reagent that the people such as Yu-Chen Lin are synthetic taking acridone condensed-nuclei aromatics as parent, highly sensitive response F -, AcO -, H 2pO 4 -, the photo under uviol lamp shows that different change color has all occurred solution fluorescence.Due to the vital role of negative ion in life science and chemical process, the fluorescence probe of design synthesis of selective bonding negative ion, has a wide range of applications at the aspect such as diagnosis of disease, environmental reconstruction.
Summary of the invention: the object of the invention is to use fluorescent method, utilize a kind of fluorescent reagent quantitatively to detect Trace Ag +or F -ion concentration, sets up a kind of high selectivity and highly sensitive fluorescent quenching spectroscopic analysis methods.
A kind of fluorescent quenching of the present invention is measured Ag +or F -method, be 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-coumarone amino) thia cup [4] aromatic hydrocarbons, is abbreviated as reagent s2, as detecting Trace Ag +or F -fluorescent quenching reagent, in different solvent mediums, quantitative measurement Trace Ag +or F -ion, reagent s2molecular formula be C 68h 86n 8o 11s 4si 2, chemical structural formula is:
Concrete grammar is (1) reagent s2at tetrahydrofuran (THF)/H 2o(v/v=4:1),, in hydroxyethyl piperazine second thiosulfonic acid (HEPES)-NaOH buffer solution (pH 7 ~ 8), measure Ag +time, taking 476nm as fluorescence exciting wavelength, measure the fluorescence intensity at 530nm place, the reduction of fluorescence intensity and Ag within the scope of finite concentration +concentration is linear, quantitative measurement Ag +content; (2) reagent s2in THF solvent, measure F -time, taking 470nm as fluorescence exciting wavelength, measure the fluorescence intensity at 524nm place, the reduction of fluorescence intensity and F within the scope of finite concentration -concentration is linear, quantitative measurement F -content.
Above-mentioned a kind of fluorescence quenching method is measured Ag +or F -method: (1) measure Ag +when ion, other coexisting ion comprises: Li +, Na +, K +, Ca 2+, Mg 2+, Sr 2+, Ba 2+, Cd 2+, Zn 2+, Cr 3+, Co 2+, Ni 2+, Pb 2+, Cu 2+, Fe 3+, Al 3+one of, at concentration and Ag +quite time, except Al 3+outward, above-mentioned ion-pairing agent s2detect Ag +fluorescence intensity affect error in 5%; (2) measure F -when ion, other coexisting ion comprises: Cl -, Br -, I -, NO 3 -, HSO 4 -, ClO 4 -, PF 6 -, AcO -, H 2pO 4 -one of, at concentration and F -quite time, to reagent s2detect F -fluorescence intensity affect error in 5%.
Above-mentioned a kind of fluorescence quenching method is measured Ag +or F -method: (1) reagent s2detect Trace Ag +concentration, detect the range of linearity be 1.0 × 10 -7~ 7.0 × 10 -5molL -1, detectability is low to moderate 10 -9molL -1; (2) reagent s2detect micro-F -concentration, detect the range of linearity be 1.0 × 10 -7~ 7.5 × 10 -5molL -1, detectability is low to moderate 10 -9molL -1.
The compound method of various reagent is:
(1) reagent s2solution: the reagent that takes 13.7mg s2, with THF dissolving, being mixed with 100mL solution, concentration is 100 μ molL -1;
(2) Ag +standard solution: take silver perchlorate 41.5mg, with distilled water dissolving, be mixed with 100mL solution, Ag +concentration is 2.00 × 10 -3molL -1; Arrive suitable concentration with distilled water stepwise dilution as required;
(3) F -standard solution: the trihydrate ([CH that takes 63.1mg tetrabutyl ammonium fluoride 3(CH 2) 3] 4nF3H 2o) dissolve with THF, be mixed with 100 mL solution, F -concentration is 2.00 × 10 -3molL -1, arrive suitable concentration with THF stepwise dilution as required;
(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: with concentration be 0.01 molL -1hydroxyethyl piperazine second thiosulfonic acid (HEPES) and appropriate NaOH preparation, regulate pH 7 ~ 8;
In the time of volumetric flask volume change, various solution additions will be done corresponding variation in proportion; It is pure that agents useful for same is analysis, and distilled water is redistilled water.
Above-mentioned a kind of fluorescent quenching is measured 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-coumarone amino) thia cup [4] aromatic hydrocarbons, is abbreviated as reagent s2, be that the inventor is synthetic as fluorescent reagent.
Reagent s2synthetic 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, obtain intermediate feed 1 through wash-out, 2-O, O'(1,1,3,3-tetra isopropyl, two silica ethers) thia cup [4] aromatic hydrocarbons;
Second step is to control configuration, by the intermediate feed obtaining in the first step 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers) thia cup [4] aromatic hydrocarbons reacts in tetrahydrofuran (THF) solution with bromoacetonitrile, obtain intermediate feed 1,2-O, O'(1,1,3,3-tetra isopropyl, two silica ethers)-3,4-bis-(cyanogen methoxyl) thia cup [4] aromatic hydrocarbons;
The 3rd step, in tetrahydrofuran (THF) solution, with diborane (B 2h 6) reduction 1,2-O, O'(1,1,3,3-tetra isopropyl, two silica ethers)-3, cyano group in 4-bis-(cyanogen methoxyl) 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];
The 4th step, intermediate 1,2-O, O'(1,1,3,3-tetra isopropyl, two silica ethers)-3,4-bis-(ammonia ethoxy) thia cup [4] aromatic hydrocarbons and the chloro-7-nitro of 4-benzo-2, the assorted oxadiazole of 1,3-oxygen is at methenyl choloride (CHCl 3) 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-coumarone amino) thia cup [4] aromatic hydrocarbons, i.e. reagent s2, synthetic route is as follows:
Prepare reagent s2the process conditions of each step are:
The first step, intermediate feed 1,2-O, O'(1,1,3,3-tetra isopropyl, two silica ethers) thia cup [4] aromatic hydrocarbons is synthetic
At N 2in there-necked flask under protection, add thia cup [4] aromatic hydrocarbons, imidazoles, dry DMF(N, dinethylformamide), stir, then room temperature drips and contains 1, 3-bis-chloro-1, 1, 3, the dry DMF solution of 3-tetra isopropyl two silicon ethers, 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, adularescent solid is separated out, after dropwising, continue after 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 precipitations, filter, washing, methylene chloride and recrystallizing methanol obtain white intermediate feed,
Temperature of reaction: room temperature
Reaction 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) thia cup [4] aromatic hydrocarbons is synthetic
At N 2in there-necked flask under protection, 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 by the colourless buff that gradually becomes; Temperature is reduced to 20 DEG C, in bottle, adding bromoacetonitrile, is 1,2-O according to mol ratio, O'(1,1,3,3-tetra isopropyl, two silica ethers) 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, and finally approaches black; Cooling, adds the hydrochloric acid of 2M, with after chloroform extraction, then it is washed with saturated aqueous common salt, and colourless dried over mgso, filters, is spin-dried for, and silica gel column chromatography obtains intermediate feed;
Temperature of reaction: reflux
Reaction time: 13h
Reaction dissolvent: anhydrous THF
Eluant, eluent: n-hexane/ethyl acetate (v/v, 9/1)
The 3rd step, intermediate 1,2-O, O'(1,1,3,3-tetra isopropyl, two silica ethers)-3,4-bis-(amino ethoxy) thia cup [4] is synthetic
At N 2in there-necked flask under protection, add 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers)-3,4-bis-(cyanogen methoxyl) thia cup [4] aromatic hydrocarbons, with the THF solution that adds diborane after dry THF dissolving, according to mol ratio 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers)-3,4-bis-(cyanogen methoxyl) thia cup [4] aromatic hydrocarbons: diborane=1:5.5 ~ 6.5, back flow reaction 72h, adds water to without Bubble formation, be spin-dried for solvent, chloroform extraction, anhydrous sodium sulfate drying, purification by silica gel column chromatography obtains white intermediate;
Temperature of reaction: reflux
Reaction time: 72h
Reaction dissolvent: anhydrous THF
Eluant, eluent: methenyl choloride/triethylamine (v/v, 80/1)
The 4th step, 1,2-O, O'(1,1,3,3-tetra isopropyl, two silica ethers)-3,4-bis-(7-nitro-4-2,1,3-coumarone amino) thia cup [4] aromatic hydrocarbons is synthetic
At N 2in there-necked flask under protection, add intermediate 1,2-O; O'(1,1,3; 3-tetra isopropyl two silica ethers)-3,4-bis-(amino ethoxy) thia cup [4], the chloro-7-nitro of 4-benzo-2; 1; 3-Yang Za oxadiazole, sal tartari, dry methenyl choloride; according to mol ratio 1; 2-O, O'(1,1; 3; 3-tetra isopropyl two silica ethers)-3,4-bis-(amino ethoxy) thia cup [4]: the chloro-7-nitro of 4-benzo-2,1; 3-Yang Za oxadiazole: sal tartari=1:2 ~ 3:2.5 ~ 3.5, backflow 24h.After reaction finishes, filtering-depositing, vacuum rotary steam is except after desolventizing, and purification by silica gel column chromatography obtains red 1,2-O, O'(1,1,3,3-tetra isopropyl two silica ethers)-3,4-bis-(7-nitro-4-2,1,3-coumarone amino) thia cup [4] aromatic hydrocarbons;
Temperature of reaction: reflux
Reaction time: 24h
Reaction dissolvent: methenyl choloride
Eluant, eluent: chloroform; N-hexane/ethyl acetate (v/v, 4/1)
Gordian technique in patent of the present invention is to control THF/H 2o mixed solvent ratio and certain pH value, just can make reagent s2become and can detect Ag +ion can detect again F -multifunction fluorescent probe reagent.Although be to adopt the mode of fluorescent quenching to realize the detection of ion, the range of linearity detecting reaches 1.0 × 10 -7~ 7.0 × 10 -5molL -1, detectability is low to moderate 10 -9molL -1, the interference of coexisting ion is little, and identification has reversibility (seeing accompanying drawing and brief description of the drawings 9), and can under neutral water dissolubility medium member, realize Ag +detect; F -detect and do not comprised AcO -the interference of ion, unique properties, analytical performance is better than the fluorescence enhancement mode probe reagent of much having reported, and operation and control method are easy.
 
brief description of the drawings:
Fig. 1 reagent s2tHF/H 2the fluorescence spectrum of O solution under different metal ion exists.
Concentration is 1.00 × 10 -5mol .l -1reagent s2tHF/H 2o(4/1, v/v, pH 7 ~ 8) solution, do not add respectively metallic ion or add 2.00 × 10 -3mol .l -1metallic ion Ag +, Li +, Na +, K +, Ca 2+, Mg 2+, Sr 2+, Ba 2+, Cd 2+, Al 3+, Zn 2+, Cr 3+, Co 2+, Ni 2+, Pb 2+, Cu 2+, Fe 3+after fluorescence spectrum.Ag +add and make reagent s2fluorescence at 530nm place significantly reduces, and red shift appears in emission wavelength, and the photo under uviol lamp shows that the green fluorescence of solution disappears.And adding of other above-mentioned experiment metallic ions can change reagent hardly s2fluorescence intensity.Excitation wavelength and the emission wavelength of test are respectively 476nm/530nm.
Fig. 2 coexistent metallic ion is to reagent s2fluorometric assay Ag +impact.
Be 1.00 × 10 in concentration -5mol .l -1reagent s2tHF/H 2o(4/1, v/v, pH 7 ~ 8) in solution, measure and add 2.00 × 10 -3molL -1ag +rear reagent s2fluorescence intensity at wavelength at 530nm place.Again measure respectively to s2-ag +in mixed solution, add one of following other metallic ions of isodose: Li +, Na +, K +, Ca 2+, Mg 2+, Sr 2+, Ba 2+, Cd 2+, Zn 2+, Cr 3+, Co 2+, Ni 2+, Pb 2+, Cu 2+, Fe 3+, Al 3+after the variation of fluorescence intensity level.Black bar is illustrated in s2the middle fluorescence intensity that adds respectively different metal ion.Red bar is illustrated in s2-ag +in mixed solution, add respectively again the fluorescence intensity change after above-mentioned metallic ion.Except Al 3+add and can make s2-ag +fluorescence recover outside, the coexisting to reagent of other common metal ion s2detect Ag +fluorescence intensity affect error in 5%.
The Ag of Fig. 3 variable concentrations +to reagent s2fluorescence titration spectrogram.
Be 1.00 × 10 in concentration -5mol .l -1reagent s2tHF/H 2o(4/1, v/v, pH 7 ~ 8) add respectively variable concentrations Ag in solution +to reagent s2in solution, along with Ag +add, the fluorescent spectrum curve recording respectively.Emission peak at 530nm place reduces gradually, and emission wavelength red shift gradually.The excitation wavelength of test is 476nm.
Fig. 4 reagent s2fluorescent spectrometry detect Ag +calibration curve.
Ordinate is that emission wavelength is the fluorescence intensity level at 530nm place, and horizontal ordinate 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 reagent s2tHF solution different anions exist under fluorescence spectrum.
Concentration is 1.00 × 10 -5mol .l -1reagent s2tHF solution, do not add respectively negative ion or add 2.00 × 10 -3mol .l -1negative ion F -, Cl -, Br -, I -, NO 3 -, HSO 4 -, ClO 4 -, PF 6 -, AcO -, H 2pO 4 -after fluorescence spectrum.Except F -add and make reagent s2fluorescence significantly reduces, AcO -add and also make fluorescence significantly reduce, and adding of other above-mentioned experiment negative ion can change reagent hardly s2fluorescence intensity.Maximum excitation and emission wavelength are respectively 470 nm and 524 nm.
Fig. 6 counter anion is to reagent s2fluorometric assay F -impact.
Be 1.00 × 10 in concentration -5mol .l -1reagent s2tHF solution in, add 2.00 × 10 -3molL -1f -rear fluorescence significantly reduces.Again measure respectively to s2-f -in mixed solution, add one of other following negative ion of isodose: Cl -, Br -, I -, NO 3 -, HSO 4 -, ClO 4 -, PF 6 -, AcO -, H 2pO 4 -after fluorescence intensity change.Black bar is illustrated in reagent s2in solution, add respectively the fluorescence intensity of different anions.Red bar is illustrated in s2-f -in mixed solution, add respectively the fluorescence intensity change after above-mentioned other counter anions.Show reagent s2detect F -fluorescence intensity do not comprised AcO -the impact coexisting at interior above-mentioned other negative ion.Maximum excitation and emission wavelength are respectively 470nm and 524nm.
The F of Fig. 7 variable concentrations -to reagent s2fluorescence method spectra for titration figure.
Be 1.00 × 10 in concentration -5mol .l -1reagent s2tHF solution in add respectively variable concentrations F -to reagent s2in solution, along with F -add, the fluorescent spectrum curve recording respectively.Emission peak at 524nm place reduces gradually.The excitation wavelength of test is 470nm.
Fig. 8 reagent s2spectroscopic methodology detect F -calibration curve.
Ordinate is that emission wavelength is the fluorescence intensity at 524nm place, and horizontal ordinate 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 reagent s2identification Ag +reversibility.
With I -for competition reagent, at reagent s2in add the Ag of 5 times of amounts +rear fluorescent quenching, at reagent s2-Ag +in complex solution, add with respect to 5 times of reagent s2the I of amount -, the fluorescence spectrum of system with do not add Ag +time reagent s2fluorescence spectrum approach, show I -add and captured s2-ag +ag in complex +, formed Ag +-I -complex; And then add again the Ag of 10 times +(with respect to reagent s2) after, fluorescence emission spectrum reduces again at 530 nm places, approaches and adds at first Ag +time intensity.Show excessive Ag +with reagent free in solution s2again formed s2-Ag +complex, also illustrates that recognition reaction is reversible process.
In the synthetic lake water sample of Figure 10, detect Ag +fluorescence spectrum.
In sample liquid, add successively the Ag of different amounts by standard addition method +the fluorescence spectrum figure that standard solution records.
Embodiment
Embodiment mono-:
In the present invention, the compound method of reagent is:
(1) reagent s2the preparation of solution: the reagent that takes 13.7mg s2, with THF dissolving, be mixed with 100mL solution, s2concentration is 1.00 × 10 -4molL -1;
(2) Ag +standard solution: take and analyze pure silver perchlorate 41.5mg, with redistilled water dissolving, and be mixed with 100mL solution, Ag +concentration is 2.00 × 10 -3molL -1; Arrive suitable concentration with redistilled water stepwise dilution as required;
(3) F -standard solution: take 63.1mg 4-butyl ammonium fluoride trihydrate ([CH 3(CH 2) 3] 4nF3H 2o) dissolve with THF, be mixed with 100 mL solution, F -concentration is 2.00 × 10 -3molL -1; Arrive suitable concentration with THF stepwise dilution as required;
(4) preparation of other coexistent metallic ion solution: get perchlorate or the nitrate of analytically pure various metals, dissolve with redistilled water, and to be mixed with concentration be 2.00 × 10 -3molL -1second distillation aqueous solution;
(5) preparation of other counter anion solution: get the 4-butyl ammonium of analytically pure various negative ion, dissolve with THF, and to be mixed with concentration be 2.00 × 10 -3molL -1tHF solution;
(6) HEPES-NaOH buffer preparation: be that 0.01 mol/L hydroxyethyl piperazine second thiosulfonic acid (HEPES) and appropriate NaOH prepare by concentration, regulate pH 7 ~ 8.
The inventive method reagent used is analytical reagent, and water is redistilled water.
The present invention's fluorospectrophotometer model used is Cary Eclipse fluorospectrophotometer, and VARIAN company of the U.S. produces.
Embodiment bis-: to Ag +ion detection
In 10.0 mL volumetric flasks, add reagent s2tHF storing solution (1.00 × 10 -4molL -1, 1mL), metallic ion Ag +(2.00 × 10 -3molL -1, 1 mL), HEPES-NaOH damping fluid (1.00 × 10 -3mol/L, 1.0 mL), use THF/H 2o(4/1, v/v) solvent dilution is to scale, shakes up, pH 7 ~ 8, the quartz colorimetric utensil that moves into 1cm carries out fluorescence spectrometry.
It is 476nm that fluorescence exciting wavelength is set, to reagent s2(1.00 × 10 -5molL -1) THF/H 2o(4/1, v/v, pH 7 ~ 8) solution carries out fluorescence spectrum test, reagent s2there is fluorescent emission at 530 nm wavelength places.Add Ag +(2.00 × 10 -4molL -1) after, reagent s2solution significantly reduces (quencher rate 75%) in the fluorescence intensity at 530nm place, emission wavelength red shift is to 569nm, and the photo under uviol lamp shows that the green fluorescence of solution disappears.Under the same terms, at reagent s2in solution, add respectively Li +, Na +, K +, Ca 2+, Mg 2+, Sr 2+, Ba 2+, Cd 2+, Al 3+, Zn 2+, Cr 3+, Co 2+, Ni 2+, Pb 2+, Cu 2+, Fe 3+after metallic ion, can change hardly reagent s2fluorescence spectrum and intensity.Reagent s2only to Ag +selective fluoroscopic examination response performance, selects the fluorescence intensity at 530nm wavelength place to carry out quantitative measurement (accompanying drawing 1).
Identical with above-mentioned test condition, reagent s2detect Ag +fluorescence intensity at 530nm wavelength place is present in as coexisting ion respectively at above-mentioned metallic ion s2-Ag +in mixed solution, as the Ag of coexistent metallic ion concentration and test +ion Phase at that time, except Al 3+add and can make s2-ag +fluorescence recover outside, other metallic ions coexist to reagent s2detect Ag +fluorescence intensity affect all in 5% (accompanying drawing 2) of error.
Under above-mentioned test-strips, measure respectively Ag +concentration changes and reagent s2fluorescence spectrum at 530nm place changes, and obtains 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 calculate reagent s2detect Ag +the concentration range of linearity and detectability list in table 1.
Table 1 reagent s2detect Ag +the analytical parameters of ion
Calibration curve range of linearity molL -1 Related coefficient Detectability molL -1
1.0×10 -7 ~7.0×10 -5 0.9924(n=10) 7.42×10 -9
Embodiment tri-: to F -ion detection
In 10mL volumetric flask, add reagent s2tHF storing solution (1.00 × 10 -4molL -1, 1mL), negative ion F -(2.00 × 10 -3molL -1, 1mL)., shake up to scale with THF solvent dilution, the quartz colorimetric utensil that moves into 1cm carries out fluorescence spectrometry.
It is 470nm that excitation wavelength is set, in THF solution, and reagent s2(concentration is 1.00 × 10 -5molL -1) transmitting 524 nm wavelength hyperfluorescenceZeng Yongminggaoyingguangs, under 365nm uviol lamp, observe strong green fluorescence.Add F -(concentration is 2.00 × 10 -4molL -1) after, reagent s2the fluorescence intensity of solution significantly reduces (quencher 99%), except F -add and have outside significant fluorescent quenching signal, AcO -add and also make the obvious quencher of fluorescence, other experiment negative ion Cl -, Br -, I -, NO 3 -, HSO 4 -, ClO 4 -, PF 6 -, H 2pO 4 -to reagent s2solution all, without obvious signal response, shows reagent s2only to F -, AcO -selective fluorescent quenching detects response performance (accompanying drawing 5).
Under above-mentioned fluorescence method test condition, reagent s2detect F -fluorescence intensity experiment negative ion be present in as coexisting ion respectively s2-F -in mixed solution, when coexisting ion comprises AcO -at interior concentration and the F of test -ion Phase at that time, to detect F -all in 5% (accompanying drawing 6) of relative deviation of fluorescence intensity impact.
Under above-mentioned test condition, measure respectively F -concentration changes and reagent s2fluorescence spectrum at 530nm place changes, and obtains the fluorescence titration curve of spectrum (accompanying drawing 7) and calibration curve (accompanying drawing 8).By the slope of calibration curve and the standard deviation of 10 blank values of mensuration, measure and calculate detection F -the range of linearity and the detectability of ion concentration are listed in table 2.
Table 2 reagent s2detect F -the analytical parameters of ion
Calibration curve range of linearity molL -1 Related coefficient Detectability molL -1
1.0×10 -7 ~7.5×10 -5 0.9972(n=11) 4.70×10 -9
Embodiment tetra-: reagent s2-Ag +the reversible character of complex
With I -for competition reagent, at reagent s2(1.00 × 10 -5molL -1) in add the Ag of 5 times of amounts +(with respect to reagent s2) after fluorescence significantly reduce (quencher rate 74%), at reagent s2-Ag +in mixture solution, add with respect to 5 times of reagent s2the I of amount -, the fluorescence intensity of system strengthens, and does not add Ag +time reagent s2fluorescence spectrum approach, for 97% of original fluorescence intensity, show I -add and captured s2-Ag +ag in complex +, formed Ag +-I -complex; And then add again the Ag of 10 times +(with respect to reagent s2) after, fluorescence emission spectrum reduces again at 530 nm places, approaches and adds at first Ag +time intensity (Fig. 9).Show excessive Ag +with reagent free in solution s2again formed reagent s2-Ag +complex, illustrates and is identified as reversible process.
Embodiment five: Ag in synthetic lake water sample +content detection
1. lake water sample pre-treatments: get lake water sample 2.0 L, boil 10 minutes, cooling, leave standstill and place 12 hours, filter, detect water sample pH value.Simmer down to 10mL, cooling for subsequent use.
2. detect: pipette the lake water sample of the treated mistake of 1mL in 10mL volumetric flask, add 1 mL reagent s2(1.00 × 10 -5molL -1, THF), 1 mL HEPES-NaOH, adds 0,0.1,0.3,0.5mL Ag successively +(1.00 × 10 -4molL -1), use THF/H 2o(4:1, v/v) mixed solvent constant volume, pH 7 ~ 8.Measure the fluorescence intensity at 530nm wavelength place and carry out quantitative test, replicate determination 3 times.
3. calculate according to the method described above measurement result in table 3.
。

Claims (6)

1. a fluorescent quenching is measured 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-coumarone amino) thia cup [4] aromatic hydrocarbons, is abbreviated as reagent s2, as detecting Trace Ag +or F -fluorescent quenching reagent, in different solvent mediums, quantitative measurement Trace Ag +or F -ion, reagent s2molecular formula be C 68h 86n 8o 11s 4si 2, chemical structural formula is:
Concrete grammar is (1) reagent s2at tetrahydrofuran (THF)/H 2o(v/v=4:1),, in hydroxyethyl piperazine second thiosulfonic acid (HEPES)-NaOH buffer solution (pH 7 ~ 8), measure Ag +time, taking 476nm as fluorescence exciting wavelength, measure the fluorescence intensity at 530nm place, the reduction of fluorescence intensity and Ag within the scope of finite concentration +concentration is linear, quantitative measurement Ag +content; (2) reagent s2in THF solvent, measure F -time, taking 470nm as fluorescence exciting wavelength, measure the fluorescence intensity at 524nm place, the reduction of fluorescence intensity and F within the scope of finite concentration -concentration is linear, quantitative measurement F -content.
2. a kind of fluorescence quenching method according to claim 1 is measured Ag +or F -method, it is characterized in that (1) measure Ag +when ion, other coexisting ion comprises: Li +, Na +, K +, Ca 2+, Mg 2+, Sr 2+, Ba 2+, Cd 2+, Zn 2+, Cr 3+, Co 2+, Ni 2+, Pb 2+, Cu 2+, Fe 3+, Al 3+one of, at concentration and Ag +quite time, except Al 3+outward, above-mentioned ion-pairing agent s2detect Ag +fluorescence intensity affect error in 5%; (2) measure F -when ion, other coexisting ion comprises: Cl -, Br -, I -, NO 3 -, HSO 4 -, ClO 4 -, PF 6 -, AcO -, H 2pO 4 -one of, at concentration and F -quite time, to reagent s2detect F -fluorescence intensity affect error in 5%.
3. a kind of fluorescence quenching method according to claim 1 is measured Ag +or F -method, it is characterized in that (1) reagent s2detect Trace Ag +concentration, detect the range of linearity be 1.0 × 10 -7~ 7.0 × 10 -5molL -1, detectability is low to moderate 10 -9molL -1; (2) reagent s2detect micro-F -concentration, detect the range of linearity be 1.0 × 10 -7~ 7.5 × 10 -5molL -1, detectability is low to moderate 10 -9molL -1.
4. a kind of fluorescent quenching according to claim 1 is measured Ag +or F -method, it is characterized in that the compound method of various reagent is:
(1) reagent s2solution: the reagent that takes 13.7mg s2, with THF dissolving, being mixed with 100mL solution, concentration is 100 μ molL -1;
(2) Ag +standard solution: take silver perchlorate 41.5mg, with distilled water dissolving, be mixed with 100mL solution, Ag +concentration is 2.00 × 10 -3molL -1; Arrive suitable concentration with distilled water stepwise dilution as required;
(3) F -standard solution: the trihydrate ([CH that takes 63.1mg tetrabutyl ammonium fluoride 3(CH 2) 3] 4nF3H 2o) dissolve with THF, be mixed with 100 mL solution, F -concentration is 2.00 × 10 -3molL -1, arrive suitable concentration with THF stepwise dilution as required;
(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: with concentration be 0.01 molL -1hydroxyethyl piperazine second thiosulfonic acid (HEPES) and appropriate NaOH preparation, regulate pH 7 ~ 8.
5. a kind of fluorescent quenching according to claim 4 is measured Ag +or F -method, it is characterized in that, in the time of volumetric flask volume change, various solution additions will be done corresponding variation in proportion; It is pure that agents useful for same is analysis, and distilled water is redistilled water.
6. a kind of fluorescent quenching according to claim 1 is measured Ag +or F -method, it is characterized in that 1,2-O, O'(1,1,3,3-tetra isopropyl, two silica ethers)-3,4-bis-(7-nitro-4-2,1,3-coumarone amino) thia cup [4] aromatic hydrocarbons, is abbreviated as reagent s2, be that the inventor is synthetic as fluorescent reagent.
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