CN105548174A - Method using light on/off mode probe to measure solution pH - Google Patents
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Abstract
The invention discloses a method using a light on/off mode probe to measure the solution pH, and belongs to the field of analytical chemistry. A compound (E)-2-(2,4-dihydroxylphenyl)vinyl-8-hydroxyl quinoline is taken as the pH fluorescence probe, (probe for short). The method comprises the following steps: quantitatively measuring the pH of a solution in pH ranges of 2-5 and 10-12.4 through a fluorescence method; quantitatively measuring the pH of the solution in pH ranges of 2-5 and 5-10 through an ultraviolet-visible absorption spectroscopy method; qualitatively and semi-quantitatively measuring the pH of the solution in pH ranges of 2-5 and 10-13 through a visual method under the UV rays and sunlight; and using the probe to qualitatively and semi-quantitatively measure the pH of the solution in pH ranges of 2-5 and 10-13 under the UV rays and sunlight; wherein the pH florescence probe has a multi-stage light on/off effect: the fluorescence is on when pH is in a range of 2 to 4; the fluorescence is off when pH is in a range of 5 to 9; the fluorescence is on when pH is in a range of 10 to 12; and the fluorescence is off when pH is greater than 13.
Description
Technical field
The invention belongs to analytical chemistry field, specifically a kind of photoswitch type measures the detecting probe method of pH in solution.
Background technology
The accurate measurement of pH value in solution is significant in the research in the fields such as chemistry, biology, medical science, agricultural and environmental science.The carrying out of chemical reaction, complete and process control, measure intracellular pH value, the proliferation and apoptosis of cell, endocytosis, ion transportation and mobile equilibrium, multidrug resistance in cell biology, the blood research in bioanalytical chemistry and medical health is all closely related with pH.Fluorescent spectrometry is a kind of detection method set up based on optical signalling, has high sensitivity, high selectivity, rapid reaction and can the advantage such as counter movement.The pH value adopting fluorescence probe method to measure solution has highly sensitive, not powered signal disturbing, the easier miniaturization of analytical instrument, is convenient to the features such as special biology sample detection and imaging applications.PH fluorescence probe can be used as acid, neutralization indicator uses, Real-Time Monitoring pH value, also by the pH of the color change qualitative judgement environment of solution.In recent years, comprising Coumarins, rhodamine, fluoresceins, fluorine boron two pyroles and anthocyan pH fluorescent optical sensor is that the change of research pH value provides strong prospecting tools to the impact of physiological activity.
The fluorescence of most protonated fluorescence probe is singlely weaken change with the increase of pH value, show as acid for " On " alkalescence be " Off ", only a few be that single enhancing changes with the increase of pH value, shows as acidity " Off " alkalescence " On ".Some the class fluorescence probe fluorescence intensity reported can be subject to coexisting in the interference of biological relevant ions in system and the biological micromolecule such as amino acid, carbohydrate to some extent with pH change.Therefore, it is necessary for seeking superior performance, be applicable to the detection of wider pH range in living things system, also having the fluorescence probe of photoswitch performance simultaneously and detect application.
Summary of the invention
The object of the invention is to research one there is photoswitch effect, under pH2 ~ 5, pH10 ~ 12.4 extreme condition, quantitatively can detect pH with fluorescence and uv-visible absorption spectra, detect the detecting probe method of pH with visual method quantitative and semi-quantitative.
A kind of photoswitch type of the present invention measures the detecting probe method of pH value of solution, is with compound (E)-2-(2,4-dihydroxy phenyl) vinyl-8-hydroxyquinoline as pH probe reagent, and be called for short probe, its structural formula is:
Detection method becomes probe solution with probe acetonitrile solution with the buffer preparation of different pH value, measure by following method: (1) fluorescence spectrum quantitatively detects pH value of solution: probe is in pH2 ~ 5 scope, take 440nm as excitation wavelength, launch the fluorescence of 550nm, intensity and pH linear correlation; Probe, in pH10 ~ 12.4 scope, take 440nm as excitation wavelength, launches the fluorescence of 580nm wavelength, intensity and pH linear correlation; (2) uv-visible absorption spectra quantitatively detects pH value of solution: in pH2 ~ 5, and probe solution forms ratio at 430nm and 360nm place and absorbs, the absorbance at 430nm wavelength place and pH linear correlation; In pH5 ~ 10, probe solution forms ratio at 430nm and 360nm place and absorbs, the absorbance at 360nm wavelength place and pH linear correlation; (3) qualitative, the half-quantitative detection pH value of solution of visual method, under 365nm uviol lamp: probe is in pH2 ~ 5 scope, and solution colour increases with pH value and gradually becomes oyster to colourless by yellow green; In pH10 ~ 13 scope, probe solution color gradually becomes orange with pH value increase by light orange, then gradually becomes orange red; Under daylight: in pH2 ~ 5 scope, probe solution color gradually becomes oyster to colourless with pH value increase by yellow green; In pH10 ~ 13 scope, probe solution color gradually becomes orange red with pH value increase by light orange, then gradually becomes shallow orange red; (4) probe test filter paper is used for qualitative, half-quantitative detection pH value of solution, under 365nm uviol lamp: probe is in pH2 ~ 5 scope, and test filter paper color gradually becomes oyster to colourless from yellow green; In pH10 ~ 13 scope, test filter paper color gradually becomes orange red from light orange, then gradually becomes light orange; In the sunlight: pH2 ~ 5 scope, test filter paper color and gradually become oyster to colourless from yellow green; In pH10 ~ 13 scope, test filter paper color gradually becomes orange red from light orange, then gradually becomes light orange; (5) as the fluorescence probe detecting pH value of solution, have multi-stage light and open (On) pass (Off) effect: pH2 ~ 4, the fluorescence signal of probe is " On "; PH5 ~ 9, the fluorescence signal of probe is " Off "; PH10 ~ 12, the fluorescence signal of probe is " On "; PH > 13, the fluorescence signal of probe is " Off ".
The detecting probe method that described a kind of photoswitch type measures pH value of solution is: (1) fluorescent spectrometry detects, in pH2.2 ~ 4.6, pH10.0 ~ 11.4, pH11.4 ~ 12.2 scope, fluorescence intensity and the solution ph of probe are proportional, and related coefficient is respectively 0.9951,0.9995,0.9891; (2) probe uv-visible absorption spectra detects, in pH2.2 ~ 4.6,5.0 ~ 10.0 scopes, absorbance and solution ph proportional, related coefficient is respectively 0.9923,0.9847.
The detecting probe method that described a kind of photoswitch type measures pH value of solution is: (1) dissolves probe reagent with acetonitrile, be made into the acetonitrile solution of concentration and probe concentration 100 μMs, be the HCl solution of trishydroxymethylaminomethane Tris and 50mM of 50mM again by concentration, regulate with pH meter, be made into the buffer solution of the different pH value of pH=2 ~ 9, finally get the probe acetonitrile solution 1mL that concentration is 100 μMs, add Tris-HCl buffer solution 4mL, 10mL is diluted to acetonitrile solution, acetonitrile and Tris-HCl volume ratio is made to be 3:2, be mixed with the probe solution of the different pH value of pH=2 ~ 9, (2) probe reagent is dissolved with acetonitrile, be made into the acetonitrile solution of concentration and probe concentration 100 μMs, be the 4-hydroxyethyl piperazine ethanesulfonic acid HEPES of 50mM and the NaOH solution of 50mM by concentration again, regulate with pH meter, be made into the buffer solution of the different pH value of pH=10 ~ 12.4, finally get the probe acetonitrile solution 1mL that concentration is 100 μMs, add HEPES-NaOH buffer solution 4mL, 10mL is diluted to acetonitrile solution, make acetonitrile and HEPES-NaOH volume ratio be 3:2, be mixed with the probe solution of the different pH value of pH=10 ~ 12.4.
The detecting probe method that described a kind of photoswitch type measures pH value of solution is fluorescence probe or ultravioletvisible spectroscopy when quantitatively detecting pH, when certain density coexisting ion, molecule comprise Na
2+, K
+, Mg
2+, Ca
2+, Ba
2+, Hg
2+, Zn
2+, Al
3+, Ni
2+, Pb
2+, Fe
3+, Ag
+, Cu
2+, lysine, halfcystine, glutamic acid, tryptophane, arginine, tyrosine, bovine serum albumin, fructose, when bovine hemoglobin exists respectively, is less than 5% to the mensuration mushing error of pH.
The detecting probe method that described a kind of photoswitch type measures pH value of solution be the fluorescence of probe or absorption spectrum with the reversible change of pH: from pH=2 to pH=7, iterative cycles changes, spectrum and intensity constant; From pH7 to pH11.4, iterative cycles change, spectrum and intensity constant; From pH=11.4 to pH=12.4, iterative cycles change, spectrum and intensity constant; The stabilization time of probe fluorescence intensity is at various ph values greater than 20min.
The detecting probe method that described a kind of photoswitch type measures pH value of solution is the assay method of sample solution pH: be mixed with sample probe solution with probe acetonitrile solution and sample solution, measure by following method: (1) sample probe solution is in pH=2 ~ 5, take 440nm as excitation wavelength, launch the fluorescence of 550nm; In pH=10 ~ 12.4, take 440nm as excitation wavelength, launch the fluorescence of 580nm wavelength, according to fluorescence intensity, can find sample pH on working curve, if at 550nm or 580nm unstressed configuration, interpret sample pH value is not in 2 ~ 5 or 10 ~ 12.4 scopes; (2) quantitatively detect pH value of solution with uv-visible absorption spectra, sample probe solution, in pH=2 ~ 5, has absorption peak at 430nm and 360nm, measures 430nm place absorbance, can find sample pH value on working curve; Sample probe solution, in pH=5 ~ 10, has absorption peak at 430nm and 360nm, measures 360nm place absorbance, can find sample pH value on working curve; If at 430nm and 360nmw without absorption peak, interpret sample pH is not in this scope; (3) visual method is qualitative, half-quantitative detection sample solution pH: sample probe solution is pH2 ~ 5 scope under 365nm uviol lamp, and solution colour gradually becomes oyster to colourless with pH value increase by yellow green; In pH10 ~ 13 scope, probe solution color gradually becomes orange with pH value increase by light orange, then gradually becomes orange red, can estimate solution ph, equally according to the color of visualization solution, also can estimate the pH value of solution according to solution colour; (4) sample probe solution drops on filter paper, under 365nm uviol lamp, according to the change of filter paper color, and also can the pH value of sample estimates solution.
Feature (1) the fluorescence probe method detection pH that a kind of photoswitch type of the present invention measures the detecting probe method of pH in solution is different from other as the measuring technique such as pH meter, chromatography of ions, preferablyly to use in the particular surroundings such as biological sample, minimum system, also be convenient to fluorescence imaging application (2) pH probe of the present invention can pH be 2 ~ 4 and 10 ~ 12 extreme ph values scope fluorescence and ultraviolet-visible spectrum quantitatively detect, be different from most of pH probe to be difficult to detect under strong acid, strong basicity, or probe does not fluoresce with this understanding.This method extends the range of application of probe; (3) middle probe of the present invention fluorescence and absorbing wavelength and intensity pH is different has significant change, have more visuality and multifunctionality; (4) the present invention not only can be used for Fluorescence and Absorption Spectroscopies and quantitatively detects pH, and also available visual method qualitative and quantitative analysis pH, metering system is various.
Accompanying drawing explanation
Fig. 1 probe (10mM, acetonitrile/Tris-HCl, v/v, 3/2) is at trishydroxymethylaminomethane (the Tris)-HCl(50mM of different pH) fluorescence spectrum (A) in buffer solution and uv-visible absorption spectra (B).
The absorbance at the fluorescence intensity of probe at 550nm place or 430nm place increases linear increasing with pH.Figure A illustration is fluorescence intensity, figure B illustration is that absorbance is with pH change curve.Maximum excitation and emission wavelength are respectively 440nm and 550nm, and maximum absorption wavelength is 430nm.
Fig. 2 probe (10mM, acetonitrile/HEPES-NaOH, v/v, 3/2) at 4-hydroxyethyl piperazine ethanesulfonic acid (the HEPES)-NaOH(50mM of different pH) fluorescence spectrum (A:pH=9.0 ~ 11.5, B:pH=11.4 ~ 12.4) in buffer solution and uv-visible absorption spectra (C).
The absorbance at the fluorescence intensity of probe at 580nm place or 360nm place increases linear increasing with pH.Figure A, B illustration be fluorescence intensity with pH change curve, figure C illustration is that absorbance is with pH change curve.Maximum excitation and emission wavelength are respectively 440nm and 580nm, and maximum absorption wavelength is 360nm.
The solution colour change at various ph values of Fig. 3 probe.
Under 365nm uviol lamp: (figure A) Tris-HCl buffer solution, pH=2.2 ~ 4.8, probe solution color is extremely colourless by becoming oyster from yellow green; (figure B) HEPES-NaOH buffer solution, pH=10.0 ~ 12.4, probe solution color gradually becomes orange by light orange, then gradually becomes orange red.
In the sunlight: (figure C) Tris-HCl buffer solution, pH=2.2 ~ 4.8, it is colourless that probe solution color gradually becomes oyster by yellow green; (figure D) HEPES-NaOH buffer solution, pH=10.0 ~ 12.4, probe solution color gradually becomes orange red by light orange, then gradually becomes shallow orange red.
Fig. 4 probe (10mM, acetonitrile/water, v/v, the 3/2) calibration curve to pH.
(figure A) Tris-HCl(50mM) in buffer solution, between pH2.2 ~ 4.6, the fluorescence intensity of probe at 550nm place and pH value proportional, linear equation is y=1040-226.1 × pH, related coefficient is 0.9951, and maximum excitation and emission wavelength are respectively 440nm and 550nm;
(figure B) Tris-HCl(50mM) in buffer solution, between pH2.2 ~ 4.6, the absorbance of probe at 430nm place and pH value proportional, linear equation is y=0.7020-0.1366 × pH, and related coefficient is 0.9923.
(figure C) HEPES-NaOH(50mM) in buffer solution, between pH10.0 ~ 11.4, probe 580nm place fluorescence intensity and pH value proportional, linear equation is y=-2923.6+295.0 × pH, coefficient R is 0.9995, and maximum excitation and emission wavelength are respectively 440nm and 580nm;
(figure D) HEPES-NaOH(50mM) in buffer solution, between pH11.4 ~ 12.2, the fluorescence intensity of probe at 580nm place and pH value proportional, linear equation is y=4184-329.3 × pH, related coefficient is 0.9891, and maximum excitation and emission wavelength are respectively 440nm and 580nm;
(figure E) HEPES-NaOH(50mM) in buffer solution, between pH5.0 ~ 10.0, the absorbance of probe at 360nm place and pH value proportional, linear equation is y=0.1418+0.02191 × pH, and related coefficient is 0.9847.
Fig. 5 probe (10mM, acetonitrile/water, v/v, 3/2) fluorescence spectrum is with the reversible change of pH.
(figure A) Tris-HCl(50mM in pH2.0 ~ 7.0) in buffer solution, continuously changing pH value of solution is 2.0 or 7.0, the spectrum change of six circulations.Figure A illustration is the photoswitch cyclic process that the fluorescence intensity of probe at 550nm place changes with pH.Maximum excitation and emission wavelength are respectively 440nm and 550nm.
(figure B) HEPES-NaOH(50mM in pH7.0 ~ 11.4) in buffer solution, continuously changing pH value of solution is 7.0 or 11.4, the spectrum change of six circulations.Figure B illustration is the photoswitch cyclic process that the fluorescence intensity of probe at 550nm place changes with pH.The maximum excitation measured when pH is 7.0 and emission wavelength are respectively 440nm and 550nm; The maximum excitation measured when pH is 11.4 and emission wavelength are respectively 440nm and 580nm.
(figure C) HEPES-NaOH(50mM in pH11.4 ~ 12.4) in buffer solution, continuously changing pH value of solution is 11.4 or 12.4, the spectrum change of six circulations.Figure C illustration is the photoswitch cyclic process that the fluorescence intensity of probe at 580nm place changes with pH.Maximum excitation and emission wavelength are respectively 440nm and 580nm.
Fig. 6 probe (10mM, acetonitrile/water, v/v, 3/2) fluorescence intensity at various ph values over time.
PH=3.6, Tris-HCl(50mM) damping fluid, maximum excitation and emission wavelength are respectively 440nm and 550nm; PH=7.0, Tris-HCl damping fluid (50mM), maximum excitation and emission wavelength are respectively 440nm and 550nm; PH=10.6, HEPES-NaOH damping fluid (50mM), maximum excitation and emission wavelength are respectively 440nm and 580nm.Stablize in the fluorescence intensity of 20min internal probe.
The fluorescence intensity of Fig. 7 probe (10mM, acetonitrile/water, v/v, 3/2) in different pH solution is by the impact of ion, molecule mutual interference.
White bars represents the fluorescence intensity of probe when specific pH; Black bar represents the fluorescence intensity change adding different metal ion, molecule in the probe solution when specific pH.The fluorescence intensity the showing probe in detecting pH not impact that coexists of tested person metallic ion, molecule.
1 ~ 13 represents respectively in probe solution or probe solution and adds Na respectively
2+, K
+, Mg
2+, Ca
2+, Ba
2+, Hg
2+, Zn
2+, Al
3+, Ni
2+, Pb
2+, Fe
3+, Ag
+, Cu
2+; 14 ~ 19 represent lysine respectively, halfcystine, glutamic acid, tryptophane, arginine, tyrosine; 20 ~ 23 represent bovine serum albumin respectively, fructose, bovine hemoglobin.
The Tris-HCl(50mM of figure A:pH=3.6) damping fluid, maximum excitation and emission wavelength are respectively 440nm and 550nm.Coexistent metallic ion and molecule: Na
2+, Ca
2+, Zn
2+(10mM), K
+, Mg
2+(2mM), Ni
2+(30mM), Ba
2+, Pb
2 +, Ag
+(0.5mM), Al
3+, Fe
3+, Hg
2+(10mM), Cu
2+(20mM); Lysine (0.1mM), halfcystine, glutamic acid, tryptophane, tyrosine, bovine serum albumin, bovine hemoglobin, fructose (1mM), arginine (0.2mM).
The HEPES-NaOH(50mM of figure B:pH=10.6) damping fluid, maximum excitation and emission wavelength are 440/580nm.Coexistent metallic ion and molecule: Na
2+(10mM), Ca
2+, Ag
+(0.2mM), Zn
2+(20mM), K
+, Mg
2+(2mM), Fe
3+(50mM), Ni
+, Ba
2+, Hg
2+(0.1mM), Al
3+, Pb
2+, Cu
2+(10mM); Lysine (0.2mM), glutamic acid (0.5mM), halfcystine, tryptophane, arginine, TYR, bovine serum albumin, bovine hemoglobin, fructose (1mM).
Fig. 8 makes the change of color with pH value of probe test filter paper by oneself.
Under the purple lamp of 365nm, (figure A) pH=2.2 ~ 4.6 scope, test filter paper color gradually becomes oyster to colourless from yellow green; (figure B) pH=10.2 ~ 12.2 scope, test filter paper color gradually becomes orange red from light orange, then gradually becomes light orange.
In the sunlight, (figure C) pH=2.2 ~ 4.6 scope, test filter paper color gradually becomes oyster to colourless from yellow green; (figure D) pH=10.2 ~ 12.2 scope, test filter paper color gradually becomes orange red from light orange, then gradually becomes light orange.
The pH value of the physiological saline synthetic sample of the different pH of Fig. 9 measures spectrogram.
The sample solution of 4 different pH is prepared respectively with Tris-HCl or HEPES-NaOH buffer solution.Wherein, sample 1 is acid; Sample 2 is neutral; Sample 3,4 is alkalescence.Add probe (10 μMs) solution respectively in the sample of above-mentioned unknown pH value after, respectively ultraviolet and fluorescence spectrometry are carried out to solution.According to surveyed absorbance and fluorescence intensity, respectively with the calibration curve of the different pH scopes provided in Fig. 4, calculate the pH value of testing sample solution.Upper figure is the ultraviolet spectrum of mensuration 1,2 sample, and ordinate is absorbance, and horizontal ordinate is wavelength, and the maximum absorption wavelength of mensuration is respectively 430nm and 360nm.Figure below is the fluorescence spectrum of mensuration 2,3,4 sample, and ordinate is fluorescence intensity, and horizontal ordinate is wavelength, and the excitation wavelength of mensuration is 440nm, and wavelength of fluorescence is respectively 550nm, 580nm and 580nm.
Embodiment
Embodiment one: the compound method of each reagent in the inventive method.
(1) probe solution: the probe (molecular formula: C taking 2.8mg
17h
13nO
3molecular weight: 279.09), dissolve with acetonitrile, be mixed with 100mL solution, concentration is 100 μMs.
(2) Tris-HCl buffer solution: with concentration be 50mM trishydroxymethylaminomethane (Tris) and 50mM HCl preparation, with pH meter regulate pH to needed for;
(3) HEPES-NaOH buffer solution: with concentration be 50mM4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) and 50mM NaOH preparation, with pH meter regulate pH to needed for;
(4) other coexisting ion, molecular solution: nitrate or the perchlorate of getting analytically pure various metal, dissolves with redistilled water, and is mixed with the second distillation aqueous solution that concentration is 20mM; Get analytically pure each seed amino acid, bovine serum albumin, bovine hemoglobin and D-Fructose redistilled water to dissolve, and be mixed with the second distillation aqueous solution that concentration is 50mM.
The present invention's ultraviolet-visible spectrophotometer model used is UV-1800, and company of Japanese Shimadzu Corporation produces; Fluorospectrophotometer model is CaryEclipse fluorospectrophotometer, and VARIAN company of the U.S. produces, and acidometer model is that vertical dragon 818, U.S. Ao Lilong (Orion) company difficult to understand produces.
Embodiment two: the preparation of probe compound.
With 8-hydroxyl quinaldine, 2,4-4-dihydroxy benzaldehyde is raw material, and respectively with acetic anhydride, pyridine/water is solvent, first synthetic intermediate, then is hydrolyzed in the mixed solvent of pyridine/water by intermediate, and synthetic route is as follows:
In there-necked flask; in the solution of acetic anhydride being dissolved with 8-hydroxyl quinaldine, add 2,4-4-dihydroxy benzaldehyde; 8-hydroxyl quinaldine in molar ratio: 2; 4-4-dihydroxy benzaldehyde equals 1:2, under nitrogen protection, and backflow; reaction terminates; concentrated removing solvent acetic acid acid anhydride, through silica gel column chromatography wash-out, obtains intermediate.Temperature of reaction: 139 DEG C (backflow), reaction time: 5h, reaction dissolvent: acetic anhydride, eluant, eluent: volume ratio chloroform: ethyl acetate (3:1).
N
2under protection, add intermediate in there-necked flask, pyridine is solvent, heating reflux reaction, cooling; adding water makes the volume ratio of pyridine and water be 3:1, continues backflow, and reaction terminates, and adds water extraction; drying, filters, and silica gel column chromatography is separated and wash-out, obtains probe compound.Temperature of reaction: 100 DEG C, reaction time: 12h, reaction dissolvent: pyridine: water (3:1), eluant, eluent: volume ratio chloroform: methyl alcohol (9:1).
The spectroscopic assay of embodiment three: pH probe.
Acetonitrile storing solution (the 0.1mM of probe is added in 10.0mL volumetric flask, 1mL), add Tris-HCl or the HEPES-NaOH buffer solution of different pH value respectively, the ratio of solvent of test solution is made to be acetonitrile/buffer solution (v/v, 3/2), be diluted to scale, shake up, the quartz colorimetric utensil moving into 1cm carries out fluorescence spectrum and uv-visible absorption spectra mensuration.The maximum excitation wavelength of fluorescence spectrometry is 440nm, and maximum emission wavelength is respectively 550nm or 580nm.
(1) fluorescent spectrometry is to the detection of pH
In the cuvette of 1cm, add the probe solution that concentration is 10 μMs, add the Tris-HCl buffer solution that pH is 1.6,1.8,2.0,2.2,2.4,2.6,2.8,3.0,3.2,3.4,3.6,3.8,4.0,4.2,4.4,4.6,4.8,5.0,5.2,5.4 more respectively, make the ratio of solvent of test solution for (acetonitrile/Tris-HCl, v/v, 3/2).Solution is carried out spectroscopic assay, and the fluorescence intensity of probe at 550nm place increases linear increase [as Fig. 1 (A)] with pH.Maximum fluorescence intensity is mapped to pH value, as the illustration in Fig. 1 (A).Maximum excitation wavelength is 440nm.
In the cuvette of 1cm, add the probe solution that concentration is 10 μMs, then to add pH be respectively 9.0,10.0,10.2,10.4,10.6,10.8,11.0,11.2,11.4) HEPES-NaOH buffer solution, make the ratio of solvent of test solution for (acetonitrile/HEPES-NaOH, v/v, 3/2).Solution is carried out spectroscopic assay, and the fluorescence intensity of probe at 550nm place increases linear increase [as Fig. 2 (A)] with pH.Fluorescence intensity is mapped to pH value, as the illustration in Fig. 2 (A).Maximum excitation wavelength is 440nm.
In the cuvette of 1cm, add the probe solution that concentration is 10 μMs, then add the HEPES-NaOH buffer solution that pH is 11.4,11.6,11.8,12.0,12.2,12.4 respectively, make the ratio of solvent of test solution for (acetonitrile/HEPES-NaOH, v/v, 3/2).Solution is carried out spectroscopic assay, and probe increases linear reduction [as Fig. 2 (B)] in the fluorescence intensity of 580nm with pH.By fluorescence intensity to pH value mapping as, the illustration in Fig. 2 (B).Maximum excitation wavelength is 440nm.
By above spectroscopic assay, obtain the fluorescence intensity of solution respectively at 550nm and 580nm place and the calibration curve [as Fig. 4 (A), (C), (D)] of pH value that fluorescence probe method detects different pH.
Be in the probe solution of 10 μMs in concentration, controlling probe solution pH with acetonitrile/Tris-HCl buffer solution (v/v, 3/2) is 3.6, measures the fluorescence intensity at 550nm place; Add Na respectively again
2+, Ca
2+, Zn
2+(10mM), K
+, Mg
2+(2mM), Ni
2+(30mM), Ba
2+, Pb
2+, Ag
+(0.5mM), Al
3+, Fe
3+, Hg
2+(10mM), Cu
2+(20mM); Lysine (0.1mM), halfcystine, glutamic acid, tryptophane, tyrosine, bovine serum albumin, bovine hemoglobin, fructose (1mM), arginine (0.2mM) is as coexistent metallic ion, molecule, measure the fluorescence intensity of probe solution at 550nm place again, investigate coexisting ion, molecule to the impact of probe in detecting pH, result is as Fig. 7 (A).Probe solution detects the fluorescence intensity of pH not by the interference that above-mentioned metallic ion, molecule coexist.Maximum excitation wavelength is 440nm.
Be in the probe solution of 10 μMs in concentration, controlling probe solution pH with acetonitrile/HEPES-NaOH (v/v, 3/2) buffer solution is 10.6, measures the fluorescence intensity at 580nm place; Add Na respectively again
2+(10mM), Ca
2+, Ag
+(0.2mM), Zn
2+(20mM), K
+, Mg
2+(2mM), Fe
3+(50mM), Ni
+, Ba
2+, Hg
2+(0.1mM), Al
3+, Pb
2+, Cu
2+(10mM); Lysine (0.2mM), glutamic acid (0.5mM), halfcystine, tryptophane, arginine, TYR, bovine serum albumin, bovine hemoglobin, fructose (1mM), as coexistent metallic ion, molecule, then measures the fluorescence intensity of probe solution at 580nm place, investigate coexisting ion, molecule to the impact of probe in detecting pH, result is as Fig. 7 (B).Probe solution detects the fluorescence intensity of pH not by the interference that above-mentioned metallic ion, molecule coexist.Maximum excitation wavelength is 440nm.
(2) UV-Vis Spectrophotometry is to the detection of pH
In the cuvette of 1cm, add the probe solution that concentration is 10 μMs, add the Tris-HCl buffer solution that pH is 1.6,1.8,2.0,2.2,2.4,2.6,2.8,3.0,3.2,3.4,3.6,3.8,4.0,4.2,4.4,4.6,4.8,5.0 more respectively, make the ratio of solvent of test solution for (acetonitrile/Tris-HCl, v/v, 3/2).Solution is carried out uv-visible absorption spectra mensuration, and the absorbance of probe at 430nm place increases linear increase [as Fig. 1 (B)] with pH.Absorbance is mapped to pH value, as the illustration in Fig. 1 (B).
In the cuvette of 1cm, add the probe solution that concentration is 10 μMs, then add the HEPES-NaOH buffer solution that pH is 5.0,6.0,7.0,8.0,9.0,10.0 respectively, make the ratio of solvent of test solution for (acetonitrile/HEPES-NaOH, v/v, 3/2).Solution is carried out uv-visible absorption spectra mensuration, and the absorbance of probe at 360nm place increases linear increase [as Fig. 2 (C)] with pH.Absorbance is mapped to pH value, as the illustration of Fig. 2 (C).
By above spectroscopic assay, obtain the absorbance of solution respectively at 430nm and 360nm place and the calibration curve [as Fig. 4 (B), (E)] of pH value of the different pH of probe in detecting.
(3) the fluorescence photoswitch process of pH probe
Concentration is the probe solution (acetonitrile/Tris-HCl, v/v, 3/2) of 10mM, with Tris-HCl(50mM) regulate its pH to be 2.0, measure its fluorescence spectrum and intensity; And then regulate the pH of probe to be 7.0 with Tris-HCl, then measure its fluorescence spectrum and intensity; So repeatedly, continuously changing pH value of solution is 2.0 or 7.0, obtains the spectrum change of six circulations [as Fig. 5 (A).The cyclic process that fluorescence intensity and pH change is as Fig. 5 (A) illustration.Exciting with emission wavelength is 440/550nm.
Concentration is the probe solution (acetonitrile/HEPES-NaOH, v/v, 3/2) of 10mM, with HEPES-NaOH(50mM) regulate its pH value to be 7.0, measure its fluorescence spectrum and intensity; And then regulate the pH value of probe to be 11.4 with HEPES-NaOH, then measure its fluorescence spectrum and intensity; So continuously changing pH value of solution is 7.0 or 11.4, obtains the spectrum change [as Fig. 5 (B)] of six circulations.The cyclic process that fluorescence intensity and pH change is as Fig. 5 (B) illustration.Exciting of measuring when pH is 7.0 is respectively 440nm and 550nm with emission wavelength; Exciting of measuring when pH is 11.4 is respectively 440nm and 580nm with emission wavelength.
Concentration is the probe solution (acetonitrile/HEPES-NaOH, v/v, 3/2) of 10mM, with HEPES-NaOH(50mM) regulate its pH to be 11.4, measure its fluorescence spectrum and intensity; And then regulate the pH of probe to be 12.4 with HEPES-NaOH, then measure its fluorescence spectrum and intensity; So continuously changing pH value of solution is 11.40 or 12.4, and obtain the spectrum change [as Fig. 5 (C)] of six circulations, the cyclic process that fluorescence intensity and pH change is as Fig. 5 (C) illustration.Excite and be respectively 440nm and 580nm with emission wavelength.
Under said determination condition, different pH value (3.6,7.0, the 10.6) solution of probe, its fluorescence intensity is stablized constant (as Fig. 6) in 20min.
Embodiment four: the fluorescence of probe and ultraviolet-visible spectrum calibration curve method and pH meter method measure the pH of the physiological saline sample of synthesis.
With the normal saline solution sample of the unknown pH value of Tris-HCl or HEPES-NaOH buffer preparation 2 groups.The calibration curve method of pH is detected compared with the glass electrode detection method test result of pH meter with the fluorescence spectrum in the present invention and uv-visible absorption spectra middle probe.Fluorescence and the ultraviolet-visible method of testing of probe are: add probe at the sample solution of unknown pH, its concentration is made to be 10 μMs, fluorescence and ultraviolet spectroscopy (see accompanying drawing 9) are carried out to solution, measured fluorescence intensity or absorbance are brought into corresponding linear equation (table 1,2), calculate pH value; PH glass electrode test then direct pH meter is tested, and the results are shown in Table 3.Show, two kinds of method testing result deviations are ± 0.10%, and the inventive method has high accuracy.
Claims (6)
1. photoswitch type measures a detecting probe method for pH value of solution, it is characterized in that with compound (E)-2-(2,4-dihydroxy phenyl) vinyl-8-hydroxyquinoline as pH probe reagent, and be called for short probe, its structural formula is:
Detection method becomes probe solution with probe acetonitrile solution with the buffer preparation of different pH value, measure by following method: (1) fluorescence spectrum quantitatively detects pH value of solution: probe is in pH2 ~ 5 scope, take 440nm as excitation wavelength, launch the fluorescence of 550nm, intensity and pH linear correlation; Probe, in pH10 ~ 12.4 scope, take 440nm as excitation wavelength, launches the fluorescence of 580nm wavelength, intensity and pH linear correlation; (2) uv-visible absorption spectra quantitatively detects pH value of solution: in pH2 ~ 5, and probe solution forms ratio at 430nm and 360nm place and absorbs, the absorbance at 430nm wavelength place and pH linear correlation; In pH5 ~ 10, probe solution forms ratio at 430nm and 360nm place and absorbs, the absorbance at 360nm wavelength place and pH linear correlation; (3) qualitative, the half-quantitative detection pH value of solution of visual method, under 365nm uviol lamp: probe is in pH2 ~ 5 scope, and solution colour increases with pH value and gradually becomes oyster to colourless by yellow green; In pH10 ~ 13 scope, probe solution color gradually becomes orange with pH value increase by light orange, then gradually becomes orange red; Under daylight: in pH2 ~ 5 scope, probe solution color gradually becomes oyster to colourless with pH value increase by yellow green; In pH10 ~ 13 scope, probe solution color gradually becomes orange red with pH value increase by light orange, then gradually becomes shallow orange red; (4) probe test filter paper is used for qualitative, half-quantitative detection pH value of solution, under 365nm uviol lamp: probe is in pH2 ~ 5 scope, and test filter paper color gradually becomes oyster to colourless from yellow green; In pH10 ~ 13 scope, test filter paper color gradually becomes orange red from light orange, then gradually becomes light orange; In the sunlight: pH2 ~ 5 scope, test filter paper color and gradually become oyster to colourless from yellow green; In pH10 ~ 13 scope, test filter paper color gradually becomes orange red from light orange, then gradually becomes light orange; (5) as the fluorescence probe detecting pH value of solution, have multi-stage light and open (On) pass (Off) effect: pH2 ~ 4, the fluorescence signal of probe is " On "; PH5 ~ 9, the fluorescence signal of probe is " Off "; PH10 ~ 12, the fluorescence signal of probe is " On "; PH > 13, the fluorescence signal of probe is " Off ".
2. a kind of photoswitch type according to claim 1 measures the detecting probe method of pH value of solution, it is characterized in that: (1) fluorescent spectrometry detects, in pH2.2 ~ 4.6, pH10.0 ~ 11.4, pH11.4 ~ 12.2 scope, fluorescence intensity and the solution ph of probe are proportional, related coefficient is respectively 0.9951,0.9995,0.9891; (2) probe uv-visible absorption spectra detects, in pH2.2 ~ 4.6,5.0 ~ 10.0 scopes, absorbance and solution ph proportional, related coefficient is respectively 0.9923,0.9847.
3. a kind of photoswitch type according to claim 1 measures the detecting probe method of pH value of solution, it is characterized in that by the method for acetonitrile and buffer preparation probe solution be: (1) dissolves probe reagent with acetonitrile, be made into the acetonitrile solution of concentration and probe concentration 100 μMs, be the HCl solution of trishydroxymethylaminomethane Tris and 50mM of 50mM again by concentration, regulate with pH meter, be made into the buffer solution of the different pH value of pH=2 ~ 9, finally get the probe acetonitrile solution 1mL that concentration is 100 μMs, add Tris-HCl buffer solution 4mL, 10mL is diluted to acetonitrile solution, acetonitrile and Tris-HCl volume ratio is made to be 3:2, be mixed with the probe solution of the different pH value of pH=2 ~ 9, (2) probe reagent is dissolved with acetonitrile, be made into the acetonitrile solution of concentration and probe concentration 100 μMs, be the 4-hydroxyethyl piperazine ethanesulfonic acid HEPES of 50mM and the NaOH solution of 50mM by concentration again, regulate with pH meter, be made into the buffer solution of the different pH value of pH=10 ~ 12.4, finally get the probe acetonitrile solution 1mL that concentration is 100 μMs, add HEPES-NaOH buffer solution 4mL, 10mL is diluted to acetonitrile solution, make acetonitrile and HEPES-NaOH volume ratio be 3:2, be mixed with the probe solution of the different pH value of pH=10 ~ 12.4.
4. a kind of photoswitch type according to claim 1 measures the detecting probe method of pH value of solution, when it is characterized in that fluorescence probe or ultravioletvisible spectroscopy quantitatively detect pH, when certain density coexisting ion, molecule comprise Na
2+, K
+, Mg
2+, Ca
2+, Ba
2 +, Hg
2+, Zn
2+, Al
3+, Ni
2+, Pb
2+, Fe
3+, Ag
+, Cu
2+, lysine, halfcystine, glutamic acid, tryptophane, arginine, tyrosine, bovine serum albumin, fructose, when bovine hemoglobin exists respectively, is less than 5% to the mensuration mushing error of pH.
5. a kind of photoswitch type according to claim 1 measures the detecting probe method of pH value of solution, it is characterized in that the fluorescence of probe or absorption spectrum are with the reversible change of pH: from pH=2 to pH=7, iterative cycles changes, spectrum and intensity constant; From pH7 to pH11.4, iterative cycles change, spectrum and intensity constant; From pH=11.4 to pH=12.4, iterative cycles change, spectrum and intensity constant; The stabilization time of probe fluorescence intensity is at various ph values greater than 20min.
6. the detecting probe method of pH value of solution is measured according to a kind of photoswitch type according to claim 1, it is characterized in that the assay method of sample solution pH is: be mixed with sample probe solution with probe acetonitrile solution and sample solution, measure by following method: (1) sample probe solution is in pH=2 ~ 5, take 440nm as excitation wavelength, launch the fluorescence of 550nm; In pH=10 ~ 12.4, take 440nm as excitation wavelength, launch the fluorescence of 580nm wavelength, according to fluorescence intensity, can find sample pH on working curve, if at 550nm or 580nm unstressed configuration, interpret sample pH value is not in 2 ~ 5 or 10 ~ 12.4 scopes; (2) quantitatively detect pH value of solution with uv-visible absorption spectra, sample probe solution, in pH=2 ~ 5, has absorption peak at 430nm and 360nm, measures 430nm place absorbance, can find sample pH value on working curve; Sample probe solution, in pH=5 ~ 10, has absorption peak at 430nm and 360nm, measures 360nm place absorbance, can find sample pH value on working curve; If at 430nm and 360nmw without absorption peak, interpret sample pH is not in this scope; (3) visual method is qualitative, half-quantitative detection sample solution pH: sample probe solution is pH2 ~ 5 scope under 365nm uviol lamp, and solution colour gradually becomes oyster to colourless with pH value increase by yellow green; In pH10 ~ 13 scope, probe solution color gradually becomes orange with pH value increase by light orange, then gradually becomes orange red, can estimate solution ph, equally according to the color of visualization solution, also can estimate the pH value of solution according to solution colour; (4) sample probe solution drops on filter paper, under 365nm uviol lamp, according to the change of filter paper color, and also can the pH value of sample estimates solution.
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