CN105548174B - A kind of photoswitch type measures the detecting probe method of pH value of solution - Google Patents
A kind of photoswitch type measures the detecting probe method of pH value of solution Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/80—Indicating pH value
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
- G01N2021/3155—Measuring in two spectral ranges, e.g. UV and visible
Abstract
A kind of photoswitch type of the present invention measures the detecting probe method of pH value of solution, belongs to analytical chemistry field.With 8 oxyquinoline of compound (E) 2 (2,4 dihydroxy phenyl) vinyl for pH fluorescence probes, abbreviation probe.Fluorescence method quantitatively detects pH value of solution in pH 2 ~ 5,10 ~ 12.4；Ultravioletvisible absorption method quantitatively detects pH value of solution in pH 2 ~ 5,5 ~ 10；Visual method is under ultraviolet and daylight, pH 2 ~ 5,10 ~ 13 is qualitative, half-quantitative detection pH value of solution；Probe test filter paper is under ultraviolet and daylight, pH 2 ~ 5, pH 10 ~ 13 be qualitative, half-quantitative detection pH value of solution；As pH fluorescence probes, opened with multi-stage light（On）It closes（Off）Effect：2 ~ 4 fluorescence of pH is " On "；5 ~ 9 fluorescence of pH is " Off "；10 ~ 12 fluorescence of pH is " On "；13 fluorescence of pH ＞ is " Off ".
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 has in the research in the fields such as chemistry, biology, medicine, agricultural and environmental science
It is significant.Intracellular pH value, cell are measured in progress, completion and the process control of chemical reaction, cell biology
Multiplication and apoptosis, endocytosis, ion transport and dynamic equilibrium, multidrug resistance, bioanalytical chemistry and medical health
In blood research it is closely related with pH.Fluorescent spectrometry is a kind of detection method established based on optical signalling, has height
Sensitivity, highly selective, fast reactivity and the advantages that can inversely carry out.The pH value for measuring solution using fluorescence probe method has
There is high sensitivity, be more easy to minimize, convenient for special biology sample detection and imaging applications etc. from electric signal interference, analytical instrument
Feature.PH fluorescence probes can be used as acid, neutralization indicator to use, and monitor pH value in real time, can also be qualitative by the color change of solution
Judge the pH of environment.In recent years, it is glimmering including Coumarins, rhodamine, fluoresceins, two pyroles of fluorine boron and anthocyan pH
Optical sensor provides strong prospecting tools for influence of the research pH value variation to physiological activity.
The fluorescence of most protonation fluorescence probe changes with the increase of pH value in single weaken, and showing as acidity is
" On " alkalescence is " Off ", and only a few changes with the increase of pH value in single enhancing, shows as acid " Off " alkalescence " On ".It has reported
Some class fluorescence probe fluorescence intensities in road can be subject to coexist in the biological relevant ions in system to some extent with pH variations
And the interference of the biological micromolecules such as amino acid, carbohydrate.Therefore, superior performance, the wider pH range suitable for biosystem are sought
Detection and meanwhile also with photoswitch performance fluorescence probe and its detection application be necessary.
The content of the invention
It is an object of the invention to study it is a kind of there is photoswitch effect, can be under pH2 ~ 5, the extreme condition of pH10 ~ 12.4
PH is quantitatively detected with fluorescence and uv-visible absorption spectra, with the detecting probe method of visual method quantitative and semi-quantitative detection pH.
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 benzenes
Base) vinyl-8-hydroxyquinoline is as pH probe reagents, abbreviation probe, and structural formula is：
Detection method is into probe solution, as follows with the buffer preparation of probe acetonitrile solution and different pH value
It measures：（1）Fluorescence spectrum quantitatively detects pH value of solution：Probe using 440nm as excitation wavelength, emits 550nm's in 2 ~ 5 scopes of pH
Fluorescence, intensity are linearly related with pH；Probe is in 10 ~ 12.4 scopes of pH, using 440nm as excitation wavelength, transmitting 580nm wavelength
Fluorescence, intensity are linearly related with pH；（2）Uv-visible absorption spectra quantitatively detects pH value of solution：In pH 2 ~ 5, probe solution exists
It forms ratio at 430nm and 360nm to absorb, the absorbance at 430nm wavelength is linearly related with pH；In pH 5 ~ 10, probe solution
It forms ratio at 430nm and 360nm to absorb, the absorbance at 360nm wavelength is linearly related with pH；（3）It is visually legal, half
PH value of solution is quantitatively detected, under 365nm ultraviolet lamps：Probe increases gradual by yellow green in 2 ~ 5 scopes of pH, solution colour with pH value
Become chartreuse to colourless；In 10 ~ 13 scopes of pH, probe solution color increases with pH value gradually becomes orange by light orange,
It gradually becomes again orange red；Under daylight：In 2 ~ 5 scopes of pH, probe solution color increases with pH value gradually becomes shallow by yellow green
Yellow green is to colourless；In 10 ~ 13 scopes of pH, probe solution color increases with pH value gradually becomes orange red by light orange, then by
It fades to shallow orange red；（4）Probe test filter paper is used for qualitative, half-quantitative detection pH value of solution, under 365nm ultraviolet lamps：Probe exists
2 ~ 5 scopes of pH, test filter paper color gradually become chartreuse to colourless from yellow green；In 10 ~ 13 scopes of pH, filter paper is tested
Color gradually becomes orange red from light orange, then gradually becomes light orange；In the sunlight：2 ~ 5 scopes of pH test filter paper color
Chartreuse is gradually become to colourless from yellow green；In 10 ~ 13 scopes of pH, test filter paper color gradually becomes orange from light orange
Red, then gradually become light orange；（5）As the fluorescence probe of detection pH value of solution, opened with multi-stage light（On）It closes（Off）Effect
It should：PH 2 ~ 4, the fluorescence signal of probe is " On "；PH 5 ~ 9, the fluorescence signal of probe is " Off "；PH 10 ~ 12, probe it is glimmering
Optical signal is " On "；PH ＞ 13, the fluorescence signal of probe is " Off ".
The detecting probe method that a kind of photoswitch type measures pH value of solution is：（1）Fluorescent spectrometry detect, pH 2.2 ~
4.6th, pH 10.0 ~ 11.4,11.4 ~ 12.2 scopes of pH, the fluorescence intensity and solution ph of probe are proportional, related coefficient difference
For 0.9951,0.9995,0.9891；（2）Probe uv-visible absorption spectra detects, in pH 2.2 ~ 4.6,5.0 ~ 10.0 models
It encloses, absorbance is proportional with solution ph, and related coefficient is respectively 0.9923,0.9847.
The detecting probe method that a kind of photoswitch type measures pH value of solution is with acetonitrile and buffer preparation probe solution
Method be：（1）Probe reagent is dissolved with acetonitrile, is made into the acetonitrile solution of 100 μM of concentration and probe concentration, then with three that concentration is 50mM
The HCl solution of hydroxymethyl aminomethane Tris and 50mM, are adjusted with pH meter, are made into the buffer solution of the different pH value of pH=2 ~ 9,
The probe acetonitrile solution 1mL that concentration is finally taken to be 100 μM, adds Tris-HCl buffer solution 4mL, is diluted to acetonitrile solution
10mL, it is 3 to make acetonitrile and Tris-HCl volume ratios:2, it is configured to the probe solution of the different pH value of pH=2 ~ 9；（2）It is molten with acetonitrile
Probe reagent is solved, is made into the acetonitrile solution of 100 μM of concentration and probe concentration, then the 4- hydroxyethyl piperazineethanesulfonic acids for being 50mM with concentration
The NaOH solution of HEPES and 50mM, is adjusted with pH meter, is made into the buffer solution of the different pH value of pH=10 ~ 12.4, is finally taken dense
The probe acetonitrile solution 1mL for 100 μM is spent, adds HEPES-NaOH buffer solution 4mL, is diluted to 10mL with acetonitrile solution, makes second
Nitrile is 3 with HEPES-NaOH volume ratios:2, it is configured to the probe solution of the different pH value of pH=10 ~ 12.4.
The detecting probe method that a kind of photoswitch type measures pH value of solution is that fluorescence probe or ultravioletvisible spectroscopy quantify
When detecting pH, when certain density coexisting ion, molecule include Na2+, K+, Mg2+, Ca2+, Ba2+, Hg2+, Zn2+, Al3+, Ni2+,
Pb2+, Fe3+, Ag+, Cu2+, lysine, cysteine, glutamic acid, tryptophan, arginine, tyrosine, bovine serum albumin, fructose,
When bovine hemoglobin is respectively present, 5% is less than to the measure mushing error of pH.
The detecting probe method that a kind of photoswitch type measures pH value of solution be probe fluorescence or absorption spectrum it is reversible with pH
Variation：From pH=2 to pH=7, iterative cycles change, and spectrum and intensity are constant；11.4 from pH 7 to pH, iterative cycles variation, light
Spectrum and intensity are constant；From pH=11.4 to pH=12.4, iterative cycles change, and spectrum and intensity are constant；Probe is at various ph values
Fluorescence intensity stabilization time be more than 20 min.
The detecting probe method that a kind of photoswitch type measures pH value of solution is that the assay method of sample solution pH is：Use probe
Acetonitrile solution and sample solution are configured to sample probe solution, measure as follows：（1）Sample probe solution in pH=2 ~ 5,
Using 440nm as excitation wavelength, emit the fluorescence of 550nm；In pH=10 ~ 12.4, using 440nm as excitation wavelength, emit 580nm ripples
Long fluorescence according to fluorescence intensity, can find sample pH on working curve, if in 550nm or 580nm unstressed configurations, say
Bright sample pH is not in 2 ~ 5 or 10 ~ 12.4 scopes；（2）PH value of solution, sample probe are quantitatively detected with uv-visible absorption spectra
Solution has absworption peak in pH=2 ~ 5, in 430nm and 360nm, measures absorbance at 430nm, sample can be found on working curve
Product pH；Sample probe solution has absworption peak in pH=5 ~ 10, in 430nm and 360nm, measures absorbance at 360nm, can be in work
Make to find sample pH value on curve；If illustrate sample pH value not in this scope without absworption peak in 430nm and 360nmw；（3）Visual method
It is qualitative, half-quantitative detection sample solution pH：Sample probe solution 2 ~ 5 scopes of pH under 365nm ultraviolet lamps, solution colour is with pH
Value increase gradually becomes chartreuse to colourless by yellow green；In 10 ~ 13 scopes of pH, probe solution color with pH value increase by
Light orange gradually becomes orange, then gradually becomes orange red, can estimate solution ph according to solution colour, be seen also according to visual
The color of solution is examined, can also estimate the pH value of solution；（4）Sample probe solution is dropped on filter paper, under 365nm ultraviolet lamps, root
According to the variation of filter paper color, the pH value of sample solution can be also estimated.
The characteristics of a kind of photoswitch type of the present invention measures the detecting probe method of pH in solution（1）Fluorescence probe method detection pH is different
It is preferably to be used in the particular surroundings such as biological sample, minimum system in other such as pH meters, ion chromatography measurement technology,
Convenient for fluorescence imaging application（2）The pH probes of the present invention can be in the extreme ph values scope fluorescence and purple that pH is 2 ~ 4 and 10 ~ 12
Outside-visible spectrum quantitatively detects, and it is difficult to be detected under strong acid, strong basicity or probe is in this condition to be different from most of pH probes
Under do not fluoresce.This method extends the application range of probe；（3）The fluorescence and absorbing wavelength and intensity of middle probe of the present invention
Have significant change with pH differences, with more visual and multi-functional；（4）The present invention cannot be only used for Fluorescence and Absorption Spectroscopies and determine
Amount detection pH, also can use visual method qualitative and quantitative analysis pH, measurement method is various.
Description of the drawings
Fig. 1 probes（10 mM, acetonitrile/Tris-HCl, v/v, 3/2）In the trishydroxymethylaminomethane of different pH
（Tris）-HCl（50 mM）Fluorescence spectrum in buffer solution（A）And uv-visible absorption spectra（B）.
Fluorescence intensity of the probe at 550nm or the absorbance at 430nm increase linearly increasing with pH.It is glimmering to scheme A illustrations
Luminous intensity, figure B illustrations are absorbance with pH change curves.Maximum excitation and launch wavelength are respectively 440nm and 550nm, maximum
Absorbing wavelength is 430nm.
Fig. 2 probes（10 mM, acetonitrile/HEPES-NaOH, v/v, 3/2）In the 4- hydroxyethyl piperazineethanesulfonic acids of different pH
（HEPES）-NaOH（50 mM）Fluorescence spectrum in buffer solution（A：PH=9.0 ~ 11.5, B：pH=11.4~12.4）With it is ultraviolet-
Visible absorption spectra（C）.
Fluorescence intensity of the probe at 580nm or the absorbance at 360nm increase linearly increasing with pH.Scheming A, B illustration is
Fluorescence intensity is absorbance with pH change curves with pH change curves, figure C illustrations.Maximum excitation and launch wavelength are respectively
440nm and 580nm, a length of 360nm of maximum absorption wave.
The solution colour variation of Fig. 3 probes at various ph values.
Under 365nm ultraviolet lamps：（Scheme A）Tris-HCl buffer solutions, pH=2.2 ~ 4.8, probe solution color is by yellowish green
Color is by becoming chartreuse to colourless；（Scheme B）HEPES-NaOH buffer solutions, pH=10.0 ~ 12.4, probe solution color is by shallow
It is orange to gradually become orange, then gradually become orange red.
In the sunlight：（Scheme C）Tris-HCl buffer solutions, pH=2.2 ~ 4.8, probe solution color are gradually become by yellow green
It is colourless for chartreuse；（Scheme D）HEPES-NaOH buffer solutions, pH=10.0 ~ 12.4, probe solution color are gradual by light orange
Become orange red, then gradually become shallow orange red.
Fig. 4 probes（10 mM, acetonitrile/water, v/v, 3/2）To the calibration curve of pH.
（Scheme A）Tris-HCl（50 mM）In buffer solution, between pH 2.2 ~ 4.6, fluorescence of the probe at 550 nm
Intensity is proportional with pH value, and linear equation is y=1040-226.1 × pH, related coefficient 0.9951, maximum excitation and transmitted wave
Long is respectively 440nm and 550 nm；
（Scheme B）Tris-HCl（50 mM）In buffer solution, between pH 2.2 ~ 4.6, extinction of the probe at 430 nm
Degree it is proportional with pH value, linear equation be y=0.7020-0.1366 × pH, related coefficient 0.9923.
（Scheme C）HEPES-NaOH（50 mM）In buffer solution, between pH 10.0 ~ 11.4, probe is glimmering at 580 nm
Luminous intensity is proportional with pH value, linear equation be y=- 2923.6+295.0 × pH, coefficient R 0.9995, maximum excitation and
Launch wavelength is respectively 440nm and 580 nm；
（Scheme D）HEPES-NaOH（50 mM）In buffer solution, between pH 11.4 ~ 12.2, probe is glimmering at 580nm
Luminous intensity is proportional with pH value, and linear equation is y=4184-329.3 × pH, related coefficient 0.9891, maximum excitation and transmitting
Wavelength is respectively 440nm and 580 nm；
（Scheme E）HEPES-NaOH（50 mM）In buffer solution, between pH 5.0 ~ 10.0, suction of the probe at 360nm
Luminosity is proportional with pH value, linear equation be y=0.1418+0.02191 × pH, related coefficient 0.9847.
Fig. 5 probes（10 mM, acetonitrile/water, v/v, 3/2）Fluorescence spectrum with pH reversible change.
（Scheme A）In the Tris-HCl of pH 2.0 ~ 7.0（50 mM）In buffer solution, it is continuous change pH value of solution for 2.0 or
7.0, the spectrum change of six Xun Huans.Figure A illustrations are circulated throughout for fluorescence intensity of the probe at 550nm with the pH photoswitches changed
Journey.Maximum excitation and launch wavelength are respectively 440nm and 550nm.
（Scheme B）In the HEPES-NaOH of pH 7.0 ~ 11.4（50 mM）In buffer solution, it is continuous change pH value of solution for 7.0 or
11.4, the spectrum change of six Xun Huans.Figure B illustrations cycle for the photoswitch that fluorescence intensity of the probe at 550nm changes with pH
Process.The maximum excitation and launch wavelength that pH is measured when being 7.0 are respectively 440nm and 550nm；The maximum that pH is measured when being 11.4
Excitation and launch wavelength are respectively 440nm and 580nm.
（Scheme C）In the HEPES-NaOH of pH 11.4 ~ 12.4（50 mM）In buffer solution, the continuous pH value of solution that changes is 11.4
Or 12.4, the spectrum change of six Xun Huans.Figure C illustrations follow for fluorescence intensity of the probe at 580nm with the pH photoswitches changed
Ring process.Maximum excitation and launch wavelength are respectively 440nm and 580nm.
Fig. 6 probes（10 mM, acetonitrile/water, v/v, 3/2）Fluorescence intensity at various ph values changes with time.
PH=3.6, Tris-HCl（50mM）Buffer solution, maximum excitation and launch wavelength are respectively 440nm and 550nm；pH=
7.0, Tris-HCl buffer solutions（50mM）, maximum excitation and launch wavelength are respectively 440nm and 550nm；PH=10.6, HEPES-
NaOH buffer solutions（50mM）, maximum excitation and launch wavelength are respectively 440nm and 580nm.In the fluorescence intensity of 20min internal probes
Stablize.
Fig. 7 probes（10 mM, acetonitrile/water, v/v, 3/2）Fluorescence intensity in different pH solution is common by ion, molecule
Deposit the influence of interference.
White bars represent fluorescence intensity of the probe in specific pH；Black bar represents to add in the probe solution in specific pH
Enter different metal ions, the fluorescence intensity change of molecule.Show the fluorescence intensity of probe in detecting pH not tested person metal ion, point
The influence that son coexists.
1 ~ 13 represents in probe solution or probe solution and is separately added into Na respectively2+, K+, Mg2+, Ca2+, Ba2+, Hg2+, Zn2+,
Al3+, Ni2+, Pb2+, Fe3+, Ag+, Cu2+；14 ~ 19 represent lysine, cysteine, glutamic acid, tryptophan, arginine, junket respectively
Propylhomoserin；20 ~ 23 represent bovine serum albumin, fructose, bovine hemoglobin respectively.
Scheme A：The Tris-HCl of pH=3.6（50mM）Buffer solution, maximum excitation and launch wavelength be respectively 440nm and
550nm.Coexistent metallic ion and molecule：Na2+, Ca2+, Zn2+（10 mM）, K+, Mg2+（2 mM）, Ni2+（30 mM）, Ba2+, Pb2 +, Ag+（0.5 mM）, Al3+, Fe3+, Hg2+（10 m M）, Cu2+（20 mM）；Lysine（0.1 mM）, cysteine, glutamic acid,
Tryptophan, tyrosine, bovine serum albumin, bovine hemoglobin, fructose（1 mM）, arginine（0.2 m M）.
Scheme B：The HEPES-NaOH of pH=10.6（50mM）Buffer solution, maximum excitation and launch wavelength are 440/580nm.Altogether
Deposit metal ion and molecule：Na2+（10 mM）, Ca2+, Ag+（0.2 mM）, Zn2+（20 mM）, K+, Mg2+（2 mM）, Fe3+（50
mM）, Ni+, Ba2+, Hg2+（0.1 mM）, Al3+, Pb2+, Cu2+（10 mM）；Lysine（0.2 mM）, glutamic acid（0.5 mM）, half
Cystine, tryptophan, arginine, tyrosine, bovine serum albumin, bovine hemoglobin, fructose（1 mM）.
Fig. 8 makes the color of probe test filter paper by oneself with the variation of pH value.
Under 365nm purple lamps,（Scheme A）The scope of pH=2.2 ~ 4.6, test filter paper color gradually become light yellow green from yellow green
Color is to colourless；（Scheme B）The scope of pH=10.2 ~ 12.2, test filter paper color gradually becomes orange red from light orange, then gradually becomes
Light orange.
In the sunlight,（Scheme C）The scope of pH=2.2 ~ 4.6, test filter paper color gradually become chartreuse to nothing from yellow green
Color；（Scheme D）The scope of pH=10.2 ~ 12.2, 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 Fig. 9 differences pH measures spectrogram.
Prepare the sample solution of 4 difference pH respectively with Tris-HCl or HEPES-NaOH buffer solutions.Wherein, sample 1
For acidity；Sample 2 is neutrality；Sample 3,4 is alkalescence.Probe is separately added into the sample of above-mentioned unknown pH value（10μM）Solution
Afterwards, ultraviolet and fluorescence spectrometry is carried out to solution respectively.According to surveyed absorbance and fluorescence intensity, provided respectively in Fig. 4
Different pH scopes calibration curve, calculate the pH value of testing sample solution.Upper figure is the ultraviolet spectra for measuring 1,2 samples,
Ordinate is absorbance, and abscissa is wavelength, and the maximum absorption wavelength of measure is respectively 430nm and 360nm.Figure below for measure 2,
3rd, the fluorescence spectrum of 4 samples, ordinate are fluorescence intensity, and abscissa is wavelength, and the excitation wavelength of measure is 440nm, fluorescence
Wavelength is respectively 550nm, 580nm and 580nm.
Specific embodiment
Embodiment one：The preparation method of each reagent in the method for the present invention.
（1）Probe solution：Weigh the probe of 2.8 mg（Molecular formula：C17H13NO3Molecular weight：279.09）, it is molten with acetonitrile
Solution, is configured to 100mL solution, and concentration is 100 μM.
（2）Tris-HCl buffer solutions：It is 50 mM trishydroxymethylaminomethanes with concentration（Tris）Match somebody with somebody with the HCl of 50mM
System adjusts pH to required with pH meter；
（3）HEPES-NaOH buffer solutions：It is 50mM4- hydroxyethyl piperazineethanesulfonic acids with concentration（HEPES）With 50mM's
NaOH is prepared, and pH is adjusted to required with pH meter；
（4）Other coexisting ions, molecular solution：The nitrate or perchlorate of analytically pure various metals are taken, use is secondary
Water dissolution is distilled, and is configured to the second distillation aqueous solution that concentration is 20mM；Take analytically pure various amino acid, cow's serum egg
In vain, bovine hemoglobin and D-Fructose second distillation water dissolution, and it is configured to the second distillation aqueous solution that concentration is 50mM.
Ultraviolet-visible spectrophotometer model UV-1800 used in the present invention, Japanese company of Shimadzu Corporation production；Fluorescence
Spectrophotometer model Cary Eclipse sepectrophotofluorometers, the production of VARIAN companies of the U.S., acidometer model are difficult to understand
Vertical dragon 818, U.S. Ao Lilong（Orion）Company produces.
Embodiment two：The preparation of probe compound.
With 8- hydroxyl quinaldines, 2,4- 4-dihydroxy benzaldehydes are raw material, and respectively with acetic anhydride, pyridine/water is solvent, first
Synthetic intermediate, then hydrolyzed by the mixed solvent of the intermediate in pyridine/water, synthetic route is as follows：
In three-necked flask, in the solution of acetic anhydride dissolved with 8- hydroxyl quinaldines, 2,4- 4-dihydroxy benzaldehydes, massage are added in
You are than 8- hydroxyl quinaldines:2,4- 4-dihydroxy benzaldehydes are equal to 1:2, under nitrogen protection, reflux, reaction terminates, and concentration removes molten
Agent acetic anhydride, elutes through silica gel column chromatography, obtains intermediate.Reaction temperature：139℃（Reflux）, the reaction time：5h, reaction are molten
Agent：Acetic anhydride, eluant, eluent：Volume ratio chloroform:Ethyl acetate（3:1）.
N2Under protection, intermediate is added in three-necked flask, pyridine is solvent, and heating reflux reaction, cooling, adding in water makes pyrrole
The volume ratio of pyridine and water is 3:1, continue to flow back, reaction terminates, and adds in water extraction, dry, filtering, silica gel column chromatography is separated and washed
It is de-, obtain probe compound.Reaction temperature：100 DEG C, the reaction time：12h, reaction dissolvent：Pyridine:Water（3:1）, eluant, eluent：Volume
Compare chloroform:Methanol（9:1）.
Embodiment three：The spectroscopic assay of pH probes.
The acetonitrile storing solution of probe is added in 10.0 mL volumetric flasks（0.1mM, 1mL）, it is separately added into different pH value
Tris-HCl or HEPES-NaOH buffer solutions, the solvent ratio for making test solution are acetonitrile/buffer solution（V/v, 3/2）, dilution
It to scale, shakes up, the quartz colorimetric utensil for moving into 1cm carries out fluorescence spectrum and uv-visible absorption spectra measure.Fluorescence spectrum is surveyed
Fixed maximum excitation wavelength is 440nm, and maximum emission wavelength is respectively 550nm or 580nm.
（1）Detection of the fluorescent spectrometry to pH
In the cuvette of 1cm, it is 10 μM of probe solution to add in concentration, then be separately added into pH for 1.6,1.8,2.0,
2.2nd, 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 Tris-HCl
Buffer solution, the solvent ratio for making test solution are（Acetonitrile/Tris-HCl, v/v, 3/2）.Solution is subjected to spectroscopic assay, probe
Fluorescence intensity at 550nm increases linearly increasing [such as Fig. 1 with pH（A）].Maximum fluorescence intensity maps to pH value, such as Fig. 1
（A）In illustration.Maximum excitation wavelength is 440 nm.
In the cuvette of 1cm, it is 10 μM of probe solution to add in concentration, then be separately added into pH for 9.0,10.0,10.2,
10.4、10.6、10.8、11.0、11.2、11.4）HEPES-NaOH buffer solutions, the solvent ratio for making test solution is（Acetonitrile/
HEPES-NaOH, v/v, 3/2）.Solution is subjected to spectroscopic assay, fluorescence intensity of the probe at 550nm increases linear increase with pH
Add [such as Fig. 2（A）].Fluorescence intensity maps to pH value, such as Fig. 2（A）In illustration.Maximum excitation wavelength is 440 nm.
In the cuvette of 1cm, it is 10 μM of probe solution to add in concentration, then be separately added into pH for 11.4,11.6,
11.8th, 12.0,12.2,12.4 HEPES-NaOH buffer solutions, the solvent ratio for making test solution are（Acetonitrile/HEPES-NaOH,
V/v, 3/2）.Solution is subjected to spectroscopic assay, fluorescence intensity of the probe in 580nm increases linear reduction [such as Fig. 2 with pH（B）].
Fluorescence intensity maps such as to pH value, Fig. 2（B）In illustration.Maximum excitation wavelength is 440 nm.
By more than spectroscopic assay, obtain fluorescence probe method and detect the solution of different pH respectively at 550nm and 580nm
Calibration curve [such as Fig. 4 of fluorescence intensity and pH value（A）、（C)、（D）].
In the probe solution for being 10 μM in concentration, with acetonitrile/Tris-HCl buffer solutions（V/v, 3/2）The probe solution pH is controlled to be
3.6, measure the fluorescence intensity at 550 nm；Na is separately added into again2+, Ca2+, Zn2+（10 mM）, K+, Mg2+（2 mM）, Ni2+（30
mM）, Ba2+, Pb2+, Ag+（0.5 mM）, Al3+, Fe3+, Hg2+（10 m M）, Cu2+（20 mM）；Lysine（0.1 mM）, half Guang
Propylhomoserin, glutamic acid, tryptophan, tyrosine, bovine serum albumin, bovine hemoglobin, fructose（1 mM）, arginine（0.2 m M）Make
For coexistent metallic ion, molecule, then fluorescence intensity of the probe solution at 550nm is measured, investigate coexisting ion, molecule to probe
The influence of pH is detected, as a result such as Fig. 7（A）.The fluorescence intensity of probe solution detection pH coexists from above-mentioned metal ion, molecule
Interference.Maximum excitation wavelength is 440 nm.
In concentration is 10 μM of probe solution, with acetonitrile/HEPES-NaOH (v/v, 3/2) buffer solution control probe
PH value of solution is 10.6, measures the fluorescence intensity at 580 nm；Na is separately added into again2+（10 mM）, Ca2+, Ag+（0.2 mM）, Zn2+
（20 mM）, K+, Mg2+（2 mM）, Fe3+（50 mM）, Ni+, Ba2+, Hg2+（0.1 mM）, Al3+, Pb2+, Cu2+（10 mM）；Rely ammonia
Acid（0.2 mM）, glutamic acid（0.5 mM）, cysteine, tryptophan, arginine, tyrosine, bovine serum albumin, bovine hemoglobin
In vain, fructose（1 mM）, as coexistent metallic ion, molecule, then fluorescence intensity of the probe solution at 580 nm is measured, investigated altogether
The influence of ion, molecule to probe in detecting pH is deposited, as a result such as Fig. 7（B）.The fluorescence intensity of probe solution detection pH is from above-mentioned gold
Belong to ion, the interference that molecule coexists.Maximum excitation wavelength is 440 nm.
（2）Detection of the UV-Vis Spectrophotometry to pH
In the cuvette of 1cm, it is 10 μM of probe solution to add in concentration, then be separately added into pH for 1.6,1.8,2.0,
2.2nd, 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 Tris-HCl bufferings are molten
Liquid, the solvent ratio for making test solution are（Acetonitrile/Tris-HCl, v/v, 3/2）.Solution is subjected to uv-visible absorption spectra survey
Fixed, absorbance of the probe at 430nm increases linearly increasing [such as Fig. 1 with pH（B）].Absorbance maps to pH value, such as Fig. 1
（B）In illustration.
In the cuvette of 1cm, it is 10 μM of probe solution to add in concentration, then be separately added into pH for 5.0,6.0,7.0,
8.0th, 9.0,10.0 HEPES-NaOH buffer solutions, the solvent ratio for making test solution are（Acetonitrile/HEPES-NaOH, v/v, 3/
2）.Solution is subjected to uv-visible absorption spectra measure, absorbance of the probe at 360nm is linearly increasing [as schemed with pH increases
2（C）].Absorbance maps to pH value, such as Fig. 2（C）Illustration.
By more than spectroscopic assay, the solution of the probe in detecting difference pH absorbance at 430nm and 360nm respectively is obtained
With calibration curve [such as Fig. 4 of pH value（B）、（E）].
（3）The fluorescence photoswitch process of pH probes
Concentration is the probe solution of 10 mM（Acetonitrile/Tris-HCl, v/v, 3/2）, use Tris-HCl（50 mM）Adjust it
PH is 2.0, measures its fluorescence spectrum and intensity；Then the pH of probe is adjusted as 7.0 with Tris-HCl again, then measure its fluorescence light
Spectrum and intensity；So repeatedly, the continuous pH value of solution that changes is 2.0 or 7.0, obtains spectrum change [such as Fig. 5 of six Xun Huans（A）.
Fluorescence intensity and cyclic process such as Fig. 5 of pH variations（A）Illustration.Excitation and launch wavelength are 440/550nm.
Concentration is the probe solution of 10 mM（Acetonitrile/HEPES-NaOH, v/v, 3/2）, use HEPES-NaOH（50mM）It adjusts
Its pH value is 7.0, measures its fluorescence spectrum and intensity；Then the pH value of probe is adjusted as 11.4 with HEPES-NaOH again, then survey
Its fixed fluorescence spectrum and intensity；The so continuous pH value of solution that changes is 7.0 or 11.4, obtains the spectrum change of six Xun Huans [as schemed
5（B）].Fluorescence intensity and cyclic process such as Fig. 5 of pH variations（B）Illustration.The excitation and launch wavelength point that pH is measured when being 7.0
It Wei not 440nm and 550nm；The excitation and launch wavelength that pH is measured when being 11.4 are respectively 440nm and 580nm.
Concentration is the probe solution of 10 mM（Acetonitrile/HEPES-NaOH, v/v, 3/2）, use HEPES-NaOH（50mM）It adjusts
Its pH is 11.4, measures its fluorescence spectrum and intensity；Then the pH of probe is adjusted as 12.4 with HEPES-NaOH again, then measure it
Fluorescence spectrum and intensity；The so continuous pH value of solution that changes is 11.40 or 12.4, obtains spectrum change [such as Fig. 5 of six Xun Huans
（C）], fluorescence intensity and cyclic process such as Fig. 5 of pH variations（C）Illustration.Excitation and launch wavelength are respectively 440nm and 580nm.
Under the conditions of said determination, the different pH value of probe（3.6、7.0、10.6）Solution, fluorescence intensity is in 20min
Stablize constant（Such as Fig. 6）.
Example IV：The fluorescence and ultraviolet-visible spectrum calibration curve method of probe and pH meter method are to the physiology salt of synthesis
The pH of water sample is measured.
With the normal saline solution sample of 2 groups of unknown pH value of Tris-HCl or HEPES-NaOH buffer preparations.With this
Fluorescence spectrum and the calibration curve method of uv-visible absorption spectra middle probe detection pH and the glass electrode of pH meter in invention are examined
Survey method test result compares.The fluorescence and ultraviolet-visible test method of probe is：It adds in and visits in the sample solution of unknown pH
Pin, makes its concentration for 10 μM, and fluorescence and ultraviolet spectroscopy are carried out to solution（See attached drawing 9）, by measured fluorescence intensity or suction
Luminosity brings corresponding linear equation into（Table 1,2）, calculate to obtain pH value；The test of pH glass electrodes is then directly tested with pH meter,
It the results are shown in Table 3.It is ± 0.10% to show two methods testing result deviation, and the method for the present invention has high accuracy.
Claims (6)
1. a kind of photoswitch type measures the detecting probe method of pH value of solution, it is characterized in that with compound (E) -2- (2,4- dihydroxy phenyl)
Vinyl-8-hydroxyquinoline is as pH probe reagents, abbreviation probe, structural formula：
Detection method is surveyed as follows into probe solution with the buffer preparation of probe acetonitrile solution and different pH value
It is fixed：(1) fluorescence spectrum quantitatively detects pH value of solution：Probe using 440nm as excitation wavelength, emits 550nm's in 2~5 scopes of pH
Fluorescence, intensity are linearly related with pH；Probe is in 10~12.4 scopes of pH, using 440nm as excitation wavelength, transmitting 580nm wavelength
Fluorescence, intensity are linearly related with pH；(2) uv-visible absorption spectra quantitatively detects pH value of solution：In pH2~5, probe solution exists
It forms ratio at 430nm and 360nm to absorb, the absorbance at 430nm wavelength is linearly related with pH；In pH 5~10, probe is molten
Liquid forms ratio at 430nm and 360nm and absorbs, and the absorbance at 360nm wavelength is linearly related with pH；(3) visually it is legal,
Half-quantitative detection pH value of solution, under 365nm ultraviolet lamps：Probe in 2~5 scopes of pH, solution colour with pH value increase by yellow green by
Chartreuse is faded to colourless；In 10~13 scopes of pH, probe solution color increases with pH value gradually becomes orange by light orange
Color, then gradually become orange red；Under daylight：In 2~5 scopes of pH, probe solution color increases with pH value and is gradually become by yellow green
It is chartreuse to colourless；In 10~13 scopes of pH, probe solution color increases with pH value gradually becomes orange red by light orange
Color, then gradually become shallow orange red；(4) probe test filter paper is used for qualitative, half-quantitative detection pH value of solution, under 365nm ultraviolet lamps：
For probe in 2~5 scopes of pH, test filter paper color gradually becomes chartreuse to colourless from yellow green；In 10~13 scopes of pH,
Test filter paper color gradually becomes orange red from light orange, then gradually becomes light orange；In the sunlight：2~5 scopes of pH, test
Filter paper color gradually becomes chartreuse to colourless from yellow green；In 10~13 scopes of pH, test filter paper color from light orange by
It fades to orange red, then gradually becomes light orange；(5) fluorescence probe as detection pH value of solution has multi-stage light switching effect：
PH 2~4, the fluorescence signal of probe is "ON"；PH 5~9, the fluorescence signal of probe is "Off"；PH 10~12, probe it is glimmering
Optical signal 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) fluorescence light
Spectrometry detects, in pH 2.2~4.6, pH 10.0~11.4,11.4~12.2 scopes of pH, the fluorescence intensity and pH value of solution of probe
It is worth proportional, related coefficient is respectively 0.9951,0.9995,0.9891；(2) probe uv-visible absorption spectra detects, in pH
2.2~4.6,5.0~10.0 scopes, absorbance is proportional with solution ph, and 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 being eased up with acetonitrile
Rush solution prepare probe solution method be：(1) probe reagent is dissolved with acetonitrile, is made into the acetonitrile solution of 100 μM of concentration and probe concentration,
Again with concentration be 50mM trishydroxymethylaminomethane and 50mM HCl solution, adjusted with pH meter, be made into the difference of pH=2~9
The buffer solution of pH value, the probe acetonitrile solution 1mL that concentration is finally taken to be 100 μM add trishydroxymethylaminomethane HCl bufferings molten
Liquid 4mL is diluted to 10mL with acetonitrile solution, and it is 3 to make acetonitrile and trishydroxymethylaminomethane HCl volume ratios:2, it is configured to pH=2
The probe solution of~9 different pH value；(2) probe reagent is dissolved with acetonitrile, is made into the acetonitrile solution of 100 μM of concentration and probe concentration, then
With concentration be 50mM 4- hydroxyethyl piperazineethanesulfonic acids and 50mM NaOH solution, adjusted with pH meter, be made into pH=10~12.4
Different pH value buffer solution, it is 100 μM of probe acetonitrile solution 1mL finally to take concentration, adds 4- hydroxyethyl piperazineethanesulfonic acids
NaOH buffer solution 4mL, 10mL is diluted to acetonitrile solution, and it is 3 to make acetonitrile and 4- hydroxyethyl piperazineethanesulfonic acid NaOH volume ratios:
2, it is configured to 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, it is characterized in that fluorescence probe or
When ultravioletvisible spectroscopy quantitatively detects pH, when certain density coexisting ion, molecule include Na2+, K+, Mg2+, Ca2+, Ba2+,
Hg2+, Zn2+, Al3+, Ni2+, Pb2+, Fe3+, Ag+, Cu2+, lysine, cysteine, glutamic acid, tryptophan, arginine, junket ammonia
Acid, bovine serum albumin, fructose when bovine hemoglobin is respectively present, are less than 5% to the measure 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 is with pH reversible changes：From pH=2 to pH=7, iterative cycles variation, spectrum and intensity are constant；From pH 7 to pH
11.4, iterative cycles variation, spectrum and intensity are constant；From pH=11.4 to pH=12.4, iterative cycles change, spectrum and intensity
It is constant；The stabilization time of the fluorescence intensity of probe at various ph values is more than 20min.
6. a kind of photoswitch type described in accordance with the claim 1 measures the detecting probe method of pH value of solution, it is characterized in that sample solution pH
Assay method be：Sample probe solution is configured to probe acetonitrile solution and sample solution, is measured as follows：(1) sample
Product probe solution using 440nm as excitation wavelength, emits the fluorescence of 550nm in pH=2~5；In pH=10~12.4, with 440nm
For excitation wavelength, emit the fluorescence of 580nm wavelength, according to fluorescence intensity, sample pH can be found on working curve, if
550nm or 580nm unstressed configurations illustrate sample pH not in 2~5 or 10~12.4 scopes；(2) uv-visible absorption spectra is used
Quantitatively detect pH value of solution, sample probe solution has absworption peak in 430nm and 360nm, measures extinction at 430nm in pH=2~5
Angle value can find sample pH value on working curve；Sample probe solution has absworption peak in pH=5~10, in 430nm and 360nm,
Absorbance at 360nm is measured, sample pH value can be found on working curve；If in 430nm and 360nmw without absworption peak, explanation
Sample pH value is not in this scope；(3) visual legal, half-quantitative detection sample solution pH：Sample probe solution is in 365nm ultraviolet lamps
Lower 2~5 scopes of pH, solution colour increases with pH value gradually becomes chartreuse to colourless by yellow green；In 10~13 models of pH
It encloses, probe solution color increases with pH value gradually becomes orange by light orange, then gradually becomes orange red, can be according to solution colour
Estimate solution ph；(4) sample probe solution is dropped on filter paper, under 365nm ultraviolet lamps, according to the variation of filter paper color,
It can estimate the pH value of sample solution.
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