CN101424641A - Strong acid type ph fluorescent probe based on fluoro-boron fluorescent dye - Google Patents
Strong acid type ph fluorescent probe based on fluoro-boron fluorescent dye Download PDFInfo
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- CN101424641A CN101424641A CNA2008100797117A CN200810079711A CN101424641A CN 101424641 A CN101424641 A CN 101424641A CN A2008100797117 A CNA2008100797117 A CN A2008100797117A CN 200810079711 A CN200810079711 A CN 200810079711A CN 101424641 A CN101424641 A CN 101424641A
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Abstract
The invention relates to a strong acid type fluorescence molecule probe for pH (pondus Hydrogenii) examination in the field of fine chemistry industry, in particular to a strong acid type pH fluorescence probe based on fluorescent fluor borate dye, which solves the problem that the prior fluorescence probe for the pH examination has non-ideal effect in strong acid environment. The strong acid type pH fluorescence probe based on fluorescent fluor borate dye has a right-structure fomular. Probe molecules of the invention have an important application value. Particularly, the type of probe molecules has very high sensitivity and extremely good selectivity to the pH examination, and excitation wavelength is in a virtual region so that the type of probe molecules has wide application prospects as a reagent for the pH examination.
Description
Technical field
The present invention relates in the field of fine chemical pH and detect and use the strong-acid type fluorescent molecular probe, be specially a kind of strong acid type ph fluorescence probe based on the glimmering dyestuff of fluorine boron.
Background technology
The accurate measurement of pH (proton concentration) is very important to chemistry, biological study.The mensuration of pH value is generally used glass electrode, but galvanochemistry is disturbed owing to existing, possible defectives such as mechanical damage are unsuitable for live body pH monitoring.As everyone knows, the fluorescence of some organic compounds or extinction property can be used to the change of Acidity of Aikalinity in the indicating target medium with the variation of pH.This pH assay method of setting up based on the optical signalling variation can remedy the existing above-mentioned deficiency of glass electrode, thereby obtain significant progress.Since the pH fluorescent molecular probe than traditional pH indicator (as phenolphthalein, thymol etc.) based on change color higher sensitivity is arranged, selectivity is good, the reaction time is fast, can carry out real-time regional pH detection, and is subjected to general attention.Desirable pH fluorescent molecular probe should have following character: chemistry/light stability height, excitation wavelength visible region (〉=400nm), to pH have selectivity and sensitivity, response fast, have suitable fat-soluble and water-soluble, the pair cell toxic action is little etc.
For most of pH fluorescence probes, very big problem be exactly the scope that detects all be very wide (at most a 7-8 pH unit can be arranged) usually, this will cause the sensitivity of probe very low.A lot of probes also are subjected to the interference of metallic ion easily.Therefore design and synthesize and be not subjected to that metallic ion is that disturb, narrow responding range, the pH fluorescence probe of excitation wavelength in visible region, strong acid environment just becomes one of focus of people's research.At present, constantly there is new pH fluorescent molecular probe to be in the news.But these probes mainly design at living things system, therefore all can only be used for physiological pH and detect (pH=6-8).And a lot of environment is in fact also arranged is highly acid, such as hydrochloric acid in gastric juice, lysosome and ribozyme body etc.Fluorescence probe at these strong acid environments is also actually rare.Representative report is pH fluorescence probe [the Diwu Z. of research such as Haugland RP, Chen C.S., Zhang C.et al.A novel acidotropic pH indicator and its potentialapplication in labeling acidic organelles of live cells.Chem.Biol.1999,6:411-418].This fluorescence probe excitation wavelength is in the ultraviolet region.Gunnlaugsson has reported the basic pH fluorescence probe of Eu (III) [Gunnlaugsson T.A novel Eu (III)-based luminescent chemosensor:deterimining pH in a highly acidic environment.Tetrahedron Lett.2001,42:8901-8905].This fluorescence probe excitation wavelength is at 350nm.Their excitation wavelength is in the ultraviolet region, make biological body produce autofluorescence easily and disturb, and short excitation wavelength also can pair cell or biosome generation injury.
The pH fluorescence probe mainly contains following a few clock at present:
The present invention with improve existing hydrogen ion fluorescence probe structure (see compound a-e), design synthesize be applicable to that pH detects in the strong acid environment, function admirable based on the probe molecule of fluorine boron gleaming photoinitiator dye as goal in research.
Summary of the invention
The present invention is in order to solve the existing fluorescence probe that detects pH value unfavorable problem of effect and a kind of strong acid type ph fluorescence probe based on the glimmering dyestuff of fluorine boron is provided under strong acid environment.
The present invention uses fluorine boron gleaming photoinitiator dye, connects dye matrix and pH identification body with methylene.
The present invention is realized that by following technical scheme a kind of strong acid type ph fluorescence probe based on the glimmering dyestuff of fluorine boron has following general structure (I):
In the general formula I: R
1, R
2In the phenyl that replaces for F, Cl, Br, I, H, sulfydryl any one.
The composition principle route of the representational compound of the present invention is to allow the benzaldehyde (II) of being with disubstituted amido, and with 2,4-disubstituted pyrroles (III) reaction separates the pure product of probe that obtain through post.In the embodiment of this instructions, understand the synthetic and analyzing detecting method of this probe in more detail.
The glimmering dye fluorescent probe using method of fluorine boron of the present invention does not have special restriction.Usually, probe molecule can be dissolved in the ethanol, add then in the suitable ethanol water and test.Work as R
1, R
2Synthetic route during the phenyl that replaces for Cl or sulfydryl is as follows: meaning as shown in Figure 6,
(1), intermediate 2 is synthetic: 36.5gDMF is added in the there-necked flask, ice bath is cooled to 0-5 ℃, be added dropwise to the phosphorus oxychloride of 38.3g then, molten in 38mLDMF two (2-hydroxyethyl) aniline of the N-of 15.1g, add in the flask then, stir cooling, be heated to 85-90 ℃ then, stir 2.5h, solution is poured in the frozen water of 500mL, slowly add sal tartari then, and stir, be alkalescence up to solution, separate out faint yellow solid, the solid that collection is separated out, recrystallization obtains product twice from ethanol
(2), product 3 is synthetic; the 150mL anhydrous methylene chloride is added in the single port flask, after half an hour, add 0.4mL2 with nitrogen bubble; the 4-dimethyl pyrrole; add 460.6mg intermediate 2 again, under the nitrogen protection, add a trifluoroacetic acid; at room temperature stir 5h; concentration of reaction solution is 50mL then, adds the 490mg tetrachloroquinone, behind the stirring 15min; add the 4mL triethylamine; the 8mL boron trifluoride diethyl etherate, when stirring 3h, reactant liquor washes with water; use anhydrous sodium sulfate drying; the pressure reducing and steaming solvent, the silica gel chromatograph separation obtains product
(3), product 4 is synthetic; 3 addings of 0.15mg product are equipped with in the 50mL single port flask of 10mL dry DMF; add 0.083mg near amino thiophenols, 0.091mg Anhydrous potassium carbonate again; under the nitrogen protection; stir 5h under the room temperature; remove by filter potash solid, the pressure reducing and steaming solvent, the silica gel chromatograph separation obtains brownish red solid target product 4.
The concrete feature of the glimmering dye fluorescent probe of fluorine boron of the present invention is as follows:
Probe molecule excites in 490～510nm scope, itself is transmitted in 520～530nm scope, and is insensitive to solvent polarity, and chemistry-good light stability; Fluorescence quantum yield is lower before the probe molecule identification hydrogen ion, behind the identification hydrogen ion in the pH2.00-0.65 scope fluorescence intensity increase more than 45 times.Probe molecule has good selectivity to hydrogen ion, common metal ion (Na
+, K
+, Mg
2+, Ca
2+, Ba
2+, Mn
2+, Cd
2+, Cr
3+, Co
2+, Ni
2+, Ag
+, Pb
2+, Zn
2+, Fe
3+, Fe
2+, Hg
2+, Cu
2+) and common negative ion (Ac
-, Cl
-, NO
3 -, H
2PO
4 -, PO
4 3-, SO
4 2-) detection of copper ion is not disturbed.Table 1 is the spectral quality of probe I-1 in different solvents
The research probe to pH optionally method be with probe molecule I-1 be added to respectively in the damping fluid of different metal ion of 50 times of equivalents fluorescence intensity and the probe molecule solution (pH=0.65) that does not add metallic ion relatively.
The method of the response of research probe pH is that probe molecule is added ionic strength is that regulating pH value is about 12.0, after the mensuration fluorescence intensity in 0.1 the aqueous solution, add acid solution, slowly reduce pH value, write down corresponding fluorescence intensity and change, with change in fluorescence to pH map (2,3).
Probe molecule of the present invention has very, and important use is worth.Particularly should the series probe molecule very high to the pH detection sensitivity, selectivity spy be good, and excitation wavelength makes this class probe have broad application prospects as the reagent of measuring pH in the visible range.This class probe has following characteristics:
The first, fluorescent probe molecule of the present invention excite with emission spectrum in the visible range, the fluorescence quantum yield height, insensitive to solvent polarity, and chemistry/good light stability.
The second, the design of fluorescent probe molecule of the present invention is based on photoinduction electron transfer principle, and fluorescence intensity increases more than 45 times before and after the probe molecule identification hydrogen ion.Probe molecule has good selectivity to copper ion, common metal ion (Na
+, K
+, Mg
2+, Ca
2+, Ba
2+, Mn
2+, Cd
2+, Cr
3+, Co
2+, Ni
2+, Ag
+, Pb
2+, Zn
2+, Fe
3+, Fe
2+, Hg
2+, Cu
2+) and common negative ion (Ac
-, Cl
-, NO
3 -, H
2PO
4 -, PO
4 3-, SO
4 2-) detection of pH is not disturbed.
The 3rd, fluorescent probe molecule of the present invention can detect the narrow range (0.65-2.00) of pH.
Description of drawings
Fig. 1 is the graph of a relation of fluorescent probe molecule I-1 fluorescence intensity of the present invention and wavelength under certain metallic ion, anion concentration
Common metal ion (Na
+, K
+, Mg
2+, Ca
2+, Ba
2+, Mn
2+, Cd
2+, Cr
3+, Co
2+, Ni
2+, Ag
+, Pb
2+, Zn
2+, Fe
3+, Fe
2+, Hg
2+, Cu
2+) and common negative ion (Ac
-, Cl
-, NO
3 -, H
2PO
4 -, PO
4 3-, SO
4 2-) concentration be 100 μ M.The concentration of fluorescent probe molecule I-1 is 1 μ M.Horizontal ordinate is wavelength (nm), and ordinate is a fluorescence intensity.
Fig. 2 is the fluorescence intensity of fluorescent probe molecule I-1 of the present invention and the graph of a relation of pH
Horizontal ordinate is wavelength (nm), and ordinate is a fluorescence intensity.The concentration of fluorescent probe molecule I-1 is 1 μ M, and arrow represents that the variation of pH is followed successively by 0.5,0.9,1.3,1.7,2.3,2.5,2.7,3.4,4.3,5.1,6.3,7.5,8.2,9.2,10.5,11.3,12.1 from small to large.
Fig. 3 is the fluorescence intensity of fluorescent probe molecule I-1 of the present invention and the graph of a relation of pH
Horizontal ordinate is wavelength (nm), and ordinate is a fluorescence intensity.The concentration of fluorescent probe molecule I-1 is 1 μ M, and arrow represents that the variation of pH is followed successively by 0.5,0.9,1.3,1.7,2.3,2.5,2.7,3.4,4.3,5.1,6.3,7.5,8.2,9.2,10.5,11.3,12.1 from small to large.
Fig. 3 is fluorescence intensity and the pH variation relation figure of fluorescent probe molecule I-1 of the present invention.Horizontal ordinate is pH, and ordinate is a fluorescence intensity.The concentration of fluorescent probe molecule I-1 is 1 μ M.λem＝516nm
Fig. 4 is the crystal structure synoptic diagram of fluorescent probe molecule I-1
Fig. 5 is the crystal structure synoptic diagram of fluorescent probe molecule I-2
Fig. 6 is the synthetic route synoptic diagram
Embodiment
Wherein:
R
1, R
2Phenyl for Cl or sulfydryl replacement.
As schematically shown in Figure 6, concrete synthetic route is as follows:
(1) intermediate 2 is synthetic: 36.5g (0.50mol) DMF is added in the there-necked flask of 250mL, install mechanical stirrer, ice bath is cooled to 0-5 ℃, slowly is added dropwise to the phosphorus oxychloride of 38.3g (0.25mol) then, and approximately 0.5h adds.Molten in 38mLDMF two (2-hydroxyethyl) aniline of the N-of 15.1g (0.08mol), add then in the flask, stir cooling.Be heated to 85-90 ℃ then, stir 2.5h, solution is poured in the frozen water of 500mL.Slowly add sal tartari then, and vigorous stirring, be alkalescence up to solution, separate out faint yellow solid.The solid that collection is separated out, recrystallization obtains white object compound 15.3g (78.1%) for twice from ethanol.Fusing point is 85-88 ℃.
1H-NMR(400MHz，CDCl
3)：δ
H9.79(s，1H，CHO)，7.79(d，2H，J＝8.8Hz)，6.76(d，2H，J＝8.8Hz)，3.85(t，2H，J＝6.8Hz，CH
2N)，3.68(t，2H，J＝6.8Hz，ClCH
2)；
13C-NMR(100MHz，CDCl
3)：δ
C151.48，131.75，125.66，111.51，51.68，40.83，40.13，39.92，39.78.ESI-MS?Positive：m/z[M+H]
+＝246.3。
(2) intermediate 3 is synthetic
The 150mL anhydrous methylene chloride is added in the single port flask, after half an hour, add 0.4mL (4mmol) 2 with nitrogen bubble; the 4-dimethyl pyrrole adds 460.6mg (1.88mmol) intermediate 2, under the nitrogen protection again; add a trifluoroacetic acid, at room temperature stir 5h.Concentration of reaction solution is 50mL then, add 490mg (2mmol) tetrachloroquinone, behind the stirring 15min, add the 4mL triethylamine, the 8mL boron trifluoride diethyl etherate, when stirring 3h, reactant liquor washes with water, uses anhydrous sodium sulfate drying, the pressure reducing and steaming solvent, the silica gel chromatograph separation obtains brownish red solid target product 0.219g, and productive rate 25.2%, developping agent are oil mystery (b.p.60-90 ℃): ethyl acetate (v:v)=6:1.Fusing point is 157-159 ℃.
1H-NMR (400MHz, CDCl
3): δ
H7.12 (d, 2H, J=8.4Hz), 6.79 (d, 2H, J=8.4Hz), 5.98 (s, 2H), 3.79 (t, 4H, J=7.2Hz), 3.68 (t, 4H, J=7.2Hz), 2.55 (s, 6H), 1.46 (s, 6H);
13C-NMR (100MHz, CDCl
3): δ
C155.26,146.79,143.24,142.37,132.20,129.64,121.21,112.38,124.01,53.62,40.42,14.86,14.76.Q-TOFMS:[M+Na]
+Calculated value: 486.1463, measured value: 486.1483.
(3) product (4) is synthetic
Intermediate 30.15mg (0.33mmol) adding is equipped with in the 50mL single port flask of 10mL dry DMF, adds 0.083mg (0.66mmol) near amino thiophenols, 0.091mg (0.66mmol) Anhydrous potassium carbonate again, under the nitrogen protection, stir 5h under the room temperature.Remove by filter potash solid, the pressure reducing and steaming solvent, the silica gel chromatograph separation obtains brownish red solid target product 0.137g, and productive rate 64.9%, developping agent are oil mystery (b.p.60-90 ℃): ethyl acetate (v:v)=5:1.Fusing point is 183-186 ℃.
1H-NMR (400MHz, CDCl
3): δ
H7.39 (d, 2H, J=7.6Hz, C
6H
5N), 7.15 (t, 2H, J=8.4Hz, C
6H
5SN), 6.87 (d, 2H, J=8.4Hz, C
6H
5SN), 6.74 (d, 2H, J=8.0Hz, C
6H
5SN), 6.69 (t, 2H, J=7.6Hz, C
6H
5SN), 6.32 (d, 2H, J=8.8Hz, C
6H
5N), 5.95 (s, 2H, CH), 4.33 (s, 4H, NH
2), 3.44 (t, 4H, J=7.2Hz, CH
2), 2.85 (t, 4H, J=7.2Hz, CH
2), 2.54 (s, 6H, CH
3), 1.42 (s, 6H, CH
3);
13C-NMR (100MHz, CDCl
3): δ
C154.95,148.68,147.13,14.73,143.27,143.06,136.39,132.26,130.41,129.20,122.59,121.04,118.77,116.63,115.23,111.94,51.09,31.26,14.86.Q-TOFMS:[M+H]
+Calculated value: 642.2708, measured value: 642.2714.
The probe I that present embodiment is made-1 pair pH selectivity:
Use above-mentioned synthetic Compound I-1 to estimate selectivity to pH.The Compound I-1 of 1 μ M is added in the ethanol water of 50 times of each excessive metal ion species (ethanol/water=5/5, v/v), the probe excitation wavelength is 500nm, and emission wavelength is 516nm, and test result is shown among Fig. 1.As we can see from the figure, probe I-1 couple pH has very high selectivity,
The identification of probe I-1 couple pH:
Use above-mentioned synthetic Compound I-1 to estimate response to pH, regulating pH value for Compound I-1 in ionic strength is 0.1 aqueous solution is about 12.0, after the mensuration fluorescence intensity, add acid solution, the pH value is slowly reduced, write down corresponding fluorescence intensity and change, test result is shown among Fig. 2.As can be seen from the figure the responding range of probe I-1 couple pH is very narrow, and in the scope of pH2.00-0.65, the fluorescence intensity of probe I-1 increases very big, so probe I-1 can be used for the detection of strong acid system pH.
Claims (3)
1, a kind of strong acid type ph fluorescence probe based on the glimmering dyestuff of fluorine boron is characterized in that having following general structure:
Wherein: R
1, R
2In the phenyl that replaces for F, Cl, Br, I, H, sulfydryl any one.
2, the strong acid type ph fluorescence probe based on the glimmering dyestuff of fluorine boron according to claim 1 is characterized in that: R
1, R
2Be Cl or near amino thiophenols.
3, the strong acid type ph fluorescence probe based on the glimmering dyestuff of fluorine boron according to claim 2 is characterized in that: R
1, R
2During for Cl or near amino thiophenols, its preparation method is:
(1), intermediate 2 is synthetic: 36.5gDMF is added in the there-necked flask, ice bath is cooled to 0-5 ℃, be added dropwise to the phosphorus oxychloride of 38.3g then, molten in 38mLDMF two (2-hydroxyethyl) aniline of the N-of 15.1g, add in the flask then, stir cooling, be heated to 85-90 ℃ then, stir 2.5h, solution is poured in the frozen water of 500mL, slowly add sal tartari then, and stir, be alkalescence up to solution, separate out faint yellow solid, the solid that collection is separated out, recrystallization obtains product twice from ethanol
(2), product 3 is synthetic; the 150mL anhydrous methylene chloride is added in the single port flask, after half an hour, add 0.4mL2 with nitrogen bubble; the 4-dimethyl pyrrole; add 460.6mg intermediate 2 again, under the nitrogen protection, add a trifluoroacetic acid; at room temperature stir 5h; concentration of reaction solution is 50mL then, adds the 490mg tetrachloroquinone, behind the stirring 15min; add the 4mL triethylamine; the 8mL boron trifluoride diethyl etherate, when stirring 3h, reactant liquor washes with water; use anhydrous sodium sulfate drying; the pressure reducing and steaming solvent, the silica gel chromatograph separation obtains product
(3), product 4 is synthetic; 3 addings of 0.15mg product are equipped with in the 50mL single port flask of 10mL dry DMF; add 0.083mg near amino thiophenols, 0.091mg Anhydrous potassium carbonate again; under the nitrogen protection; stir 5h under the room temperature; remove by filter potash solid, the pressure reducing and steaming solvent, the silica gel chromatograph separation obtains brownish red solid target product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492306A (en) * | 2011-12-19 | 2012-06-13 | 大连理工大学 | Boron-dipyrromethene dye containing sulfur and halogen, and preparation method thereof |
| CN105925004A (en) * | 2016-05-04 | 2016-09-07 | 三峡大学 | Fluorine-boron pyrrolizinone fluorochrome and synthesizing method thereof |
| CN107478632A (en) * | 2017-09-22 | 2017-12-15 | 南昌航空大学 | A kind of method of fluoroscopic examination pH value by pH test paper |
-
2008
- 2008-11-01 CN CN2008100797117A patent/CN101424641B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492306A (en) * | 2011-12-19 | 2012-06-13 | 大连理工大学 | Boron-dipyrromethene dye containing sulfur and halogen, and preparation method thereof |
| CN105925004A (en) * | 2016-05-04 | 2016-09-07 | 三峡大学 | Fluorine-boron pyrrolizinone fluorochrome and synthesizing method thereof |
| CN105925004B (en) * | 2016-05-04 | 2017-06-06 | 三峡大学 | A kind of fluorine boron pyrrolizine fluorescent dye and its synthetic method |
| CN107478632A (en) * | 2017-09-22 | 2017-12-15 | 南昌航空大学 | A kind of method of fluoroscopic examination pH value by pH test paper |
| CN107478632B (en) * | 2017-09-22 | 2019-12-24 | 南昌航空大学 | Method for detecting pH value through fluorescence of pH test paper |
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| Publication number | Publication date |
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