CN106187884B - 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagents and preparation and application - Google Patents
2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagents and preparation and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- 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
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- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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Abstract
The invention discloses a kind of 2 [2 hydroxyl 5 (4 nitroazobenzene) styryl] 8 oxyquinoline colorimetric reagents and its preparation method and application, the present invention can apply to detect F in analytical chemistry using wanting raw material that one kind is prepared based on quinoline and nitro-azo benzene derivative‑、AcO‑And pH, H2The colorimetric reagent of O.Colorimetric reagent of the present invention is by controlling different solvents, with ratio absorption process selective enumeration method F‑、AcO‑.Simultaneously, moreover it is possible to which simplicity is quickly applied to F‑、AcO‑、pH、H2The visual detection of O.Manufacturing cost is cheap, and detection sensitivity is high, selectivity is good, and operating condition is easily controllable, and application prospect is good.
Description
Technical field
The present invention relates to a kind of colorimetric reagent and preparation method and application, especially a kind of 2- [2- hydroxyls -5- (4- nitros
Azobenzene) styryl] -8-hydroxyquinoline colorimetric reagent and its preparation method and application.
Background technology
Colorimetric reagent energy is highly sensitive, high selection detects specific ion, with testing cost is low, speed is fast, equipment is simple, side
The features such as method is easy, intuitive is widely used in analysis detection field.Colorimetric reagent can not only visual detection, qualitative analysis, moreover it is possible to
By means of the spectral quality that ratio absorbs, isobestic point is formed when using detection, exists simultaneously the absorption peak ratio of different wave length
Variation be measured, have higher detection sensitivity and accuracy.In the way of the ratio of absorbance, that is, ratio absorption detecting
It is different from the variation detection of the absorbance of single wavelength, in practical applications the composition of object under inspection, colorimetric reagent concentration, survey
The influence of the factors such as strip part, light source fluctuation and instrument sensitivity is small, is changed by the ratio of absorbance under two different wave lengths,
Reducing influences the factor of Accurate Determining, can make that the responsing linear range of detection, detection limit, accuracy significantly improves.
Anion plays an important role in life science and chemical process.The extensive use of anion makes its detection change
There are important researching value and application prospect in the fields such as work, environment, medicine, life science.Anion mostly uses greatly ion chromatography
Technology detects.And the design of anion probe techniques middle probe reagent is had smaller charge/radius ratio by anion, is led
Cause the effect using electrostatic interaction identification anion poor；Anion is sensitive to solution ph, can protonate at low ph values and
Lead to its negatively charged reduction of institute, to the difficulty higher than cations recognition；Anion has different geometries, three-dimensional effect
It is affected；Anion is affected by solvation.For cation, anion probe reagent is set
Meter needs to consider more influence factors.
Compared with other anion, F-Can be formed with hydrogen bonding moieties such as amino, hydroxyl, acylamino- of detection reagent etc. compared with
Strong hydrogen bond.Therefore, in organic solvent, F-Introducing will cause detection reagent that apparent color change occurs, and for F-
Detection be usually associated with AcO-Interference, the better Anionic recognition reagent of developing selective or can realize simultaneously to it is a variety of from
The selective enumeration method reagent of son is relatively difficult.Anionic recognition probe reagent has many reports, but with same reagent energy
Close to selective enumeration method F under near-infrared wavelength-、AcO-, while also can apply to pH, H2The colorimetric reagent of the visual detection of O is not
It appears in the newspapers.
Anionic recognition probe reagent has many reports, but can be in the selectivity close under near-infrared wavelength with same reagent
Detect F-、AcO-, while also can apply to pH, H2The colorimetric reagent of the visual detection of O has not been reported.
Invention content
The object of the present invention is to provide a kind of 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8- hydroxyl quinolines
Quinoline colorimetric reagent and its preparation method and application, the present invention want raw material using based on quinoline and nitro-azo benzene derivative
One kind is prepared to can apply to detect F in analytical chemistry-、AcO-And pH, H2The colorimetric reagent of O.Colorimetric reagent of the present invention is logical
Control different solvents are crossed, with ratio absorption process selective enumeration method F-、AcO-.Simultaneously, moreover it is possible to which simplicity is quickly applied to F-、
AcO-、pH、H2The visual detection of O.Manufacturing cost is cheap, and detection sensitivity is high, selectivity is good, and operating condition is easily controllable, application
Foreground is good.
Technical scheme of the present invention：A kind of 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline ratio
The chemical structural formula of color reagent, the colorimetric reagent is：
2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent above-mentioned, the colorimetric
Main 5-15 parts of the paranitroanilinum, 5-15 parts of the salicylide aqueous solution of a concentration of 0.5M, 8- by being calculated by amount of substance part of reagent
0.3-0.9 parts of hydroxy-2-methylquinoline and 1-10 parts of the sodium nitrite in aqueous solution of a concentration of 2.5M calculated by parts by volume, matter
Amount score is that 5-15 parts of 1-8 parts of concentrated hydrochloric acid, the acetic anhydride of 36-38% and 10-30 parts of pyridine are prepared.
2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent above-mentioned, the colorimetric
Reagent is mainly by 10 parts of salicylide aqueous solution, the 8- hydroxyls-of 10 parts of the paranitroanilinum, a concentration of 0.5M that are calculated by amount of substance part
5 parts of sodium nitrite in aqueous solution, the mass fraction 36- of 0.69 part of 2- methylquinolines and a concentration of 2.5M calculated by parts by volume
38% 20 parts of 4 parts of concentrated hydrochloric acid, 10 parts of acetic anhydride and pyridine is prepared.
A kind of system of 2- above-mentioned [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent
Preparation Method is synthesized according to following route：
The preparation side of 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent above-mentioned
In method, include the following steps：
(1) concentrated hydrochloric acid and water that mass fraction is 36-38% are added into paranitroanilinum, dissolving obtains A product；
(2) after A product are cooled to 0~5 DEG C under ice salt bath, it is slowly dropped into the sodium nitrite in aqueous solution of a concentration of 2.5M, obtains B
Product；
(3) after B product react 1-3h under ice bath, with sodium hydroxide solution tune pH=7, C product are obtained；
(4) the salicylide aqueous solution of a concentration of 0.5M is added into C product, reacts 3-5h, there is red precipitate analysis after having reacted
Go out, filter, be dried in vacuum overnight, tetrahydrofuran recrystallization obtains D product；
(5) D product are placed in microwave reaction pipe, and 8- hydroxy-2-methylquinolines and acetic anhydride is added, is mixed to form orange red molten
Liquid obtains E product；
(6) E product react 55-65min under the conditions of being 48-52W in 128-132 DEG C, microwave power, obtain F product；
(7) ice water is added into F product, stirs 1-3h, orange/yellow solid occurs, filters, it is dry, obtain G product；
(8) pyridine is added in G product, in N2Under protection, after 80-85 DEG C of reflux 4-6h, water is added to continue the 18-22h that flows back, it is cold
But, H product are obtained；
(9) ice water is added in H product, overnight, there is brown-red solid precipitation, filter, dry, crude product is purified through column chromatography,
Eluant, eluent is ethyl acetate：N-hexane, eluant, eluent volume ratio are 4:6, obtain Orange red solid powder, obtain I product to get；
A kind of 2- above-mentioned [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent is answered
With, including
(1) it is used as in UV-Vis Spectrophotometry for detecting AcO in solution-、F-And the colorimetric reagent of pH；
(2) F in optical colorimetry detection solution-、AcO-, pH and optical colorimetry detection dimethyl sulfoxide (DMSO)/water in water contain
Amount；
(3) the ELISA test strip pH value of solution of colorimetric reagent is loaded.
The application of 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent above-mentioned is made
To be used to detect AcO in solution in UV-Vis Spectrophotometry-、F-And pH colorimetric reagent when,
Detection method includes：
(1) UV-Vis Spectrophotometry detects F-：In acetonitrile solution, ratio of the colorimetric reagent in 350nm and 595nm
Rate absorbance value and F-Concentration is in a linear relationship, and F is detected with calibration curve method-, F-The range of linearity of concentration is 1.0-25.0 μM,
Detection is limited to 0.63 μM；
(2) UV-Vis Spectrophotometry detects AcO-：In the acetonitrile/water solution that volume ratio is 19/1, colorimetric reagent
In the ratio absorbance value and AcO of 350nm and 560nm-Concentration is in a linear relationship, and AcO is detected with calibration curve method-, AcO-Concentration
The range of linearity be 1.0-45.0 μM, detection be limited to 0.44 μM；
(3) UV-Vis Spectrophotometry detects pH：Dimethyl sulfoxide (DMSO)/aqueous solution that colorimetric reagent is 9/1 in volume ratio
In, be separately added into the Tirs-HCl buffer solutions of at least 3 kinds different pH value, the pH value is 3-9, take solution in cuvette into
Row ultraviolet-visible spectrum measures；It is the absorption peak variation at 355nm and 600nm with wavelength, can detect the molten of pH ranging from 6-9
Liquid.
The application of 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent above-mentioned,
(1) in acetonitrile solution, UV-Vis Spectrophotometry detects F-When, other counter anions are AcO-,
Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -One of, in concentration and F-When identical, to F-Measurement do not interfere；
(2) in the acetonitrile/water solution that volume ratio is 19/1, UV-Vis Spectrophotometry detects AcO-When,
His counter anion is F-, Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -One of, in concentration and AcO-It is right when identical
AcO-Measurement do not interfere；
In the application of 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent above-mentioned,
Optical colorimetry detects F in solution-、AcO-, pH and optical colorimetry detection dimethyl sulfoxide (DMSO)/water in water content when, detection side
Method includes：
(1) F in optical colorimetry detection solution-When, in a concentration of 20 μM of colorimetric reagent acetonitrile solution, under daylight, F-From
When sub- concentration is respectively 0,10,100,1000 μM, the variation of colorimetric reagent solution colour corresponds to faint yellow, light blue, indigo respectively
Blue, cyan, detection are limited to 10 μM；
(2) AcO in colorimetric reagent optical colorimetry detection solution-When, a concentration of 20 μM of colorimetric reagent is in volume ratio
In 19/1 acetonitrile/water solution, under daylight, in AcO-When ion concentration is respectively 0,10,100,1000 μM, colorimetric reagent solution
Color change corresponds to faint yellow, crocus, lightpink, pink respectively, and detection is limited to 10 μM；
(3) when the pH of colorimetric reagent optical colorimetry detection solution, a concentration of 20 μM of colorimetric reagent pH be respectively 6,
7, in the Tirs-HCl buffer solutions of 8,9 a concentration of 5mM, the body so that dimethyl sulfoxide (DMSO)/water is diluted with dimethyl sulfoxide (DMSO)/water
Product is than being 9/1, and under daylight, in pH is respectively 6,7,8,9 buffer solutions, the variation of colorimetric reagent solution colour corresponds to shallow respectively
Yellow, light green color, light blue, sky blue；
(4) in colorimetric reagent optical colorimetry detection dimethyl sulfoxide (DMSO)/water when water content, a concentration of 20 μM of colorimetric reagent
In dimethyl sulfoxide (DMSO)/water buffer solution of different water contents, water content be respectively 1%, 10%, 20%, 30%, 40%,
50%, 60%, 70%, 80% when, under daylight, the variation of colorimetric reagent solution colour corresponds to turquoise, sky blue, purple respectively
It is color, royal purple, light violet magenta, pink, baby pink, pale pinkish grey, ivory white；Colorimetric reagent by visual observation colorimetric it is legal and
H in half-quantitative detection solution2The percentage composition of O, detection are limited to 1%.
The application of 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent above-mentioned is born
When carrying the ELISA test strip pH value of solution of colorimetric reagent, test strips are submerged initially in the colorimetric reagent acetonitrile solution of a concentration of 1mM respectively
Middle progress reagent load is taken out, then test strips are immersed to the Tirs-HCl bufferings for a concentration of 0.05M that pH is 7,8,9,10 respectively
After solution, under daylight, test strips color change corresponds to yellow, light orange, orange red, aubergine respectively.
2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline ratio that applicant synthesizes the present invention
Color reagent has carried out structure characterization test, obtains hydrogen nuclear magnetic resonance modal data, carbon modal data, mass spectrometric data and infrared signature peak light
Modal data, is specifically shown in Table 1, table 2 and table 3.According to the data obtained, it was confirmed that gained 2- [2- hydroxyls -5- (4- nitroazobenzenes) benzene
Vinyl] -8-hydroxyquinoline chemical constitution.
1 structural characterization testing result of table
2 mass spectrometric data of table
3 infrared signature peak spectroscopic data of table
4 carbon-13 nmr spectra data of table
To verify beneficial effects of the present invention, inventor has carried out a large amount of experimental study, part Experiment process and result
It is as follows：
1, to F-、AcO-There is identification test experience.In reagent-acetonitrile solution of a concentration of 10 μM of colorimetric reagent, respectively plus
Enter 200 μM of anion Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -When solution, the purple of colorimetric reagent is not observed
Outside-visible absorption spectra changes significantly；And the F of 200 μM of addition-、AcO-Absorption peak of the colorimetric reagent at 350nm is set to subtract
It is weak, occur new absorption peak at 420nm, 595nm；There is isobestic point at 418nm, ratio suction is formed at 350nm and 595nm
It receives, shows that colorimetric reagent is to F with this condition-、AcO-There is recognition detection effect.It is specifically shown in Fig. 1.
2, a concentration of 10 μM of colorimetric reagent different volumes than acetonitrile/water solution in, be separately added into 200 μM of F-
Or AcO-Afterwards, the absorbance of maximum absorption wave strong point is measured.Reagent-the F in acetonitrile solution-, reagent-AcO-The extinction at 595nm
Degree is maximum, in acetonitrile/water solution, reagent-F-, reagent-AcO-Maximum absorption wavelength violet shift to 560nm, absorbance reduces；
At acetonitrile/water (19/1, v/v), reagent-F-Absorbance is reduced than reagent-AcO at 560nm-The absorbance in the wavelength
It reduces apparent.Show colorimetric reagent in acetonitrile solution while detecting F-、AcO-；Colorimetric reagent is molten in acetonitrile/water (19/1, v/v)
AcO is detected in liquid-.Ordinate is the absorbance of maximum absorption wave strong point, and abscissa is the volume ratio of acetonitrile/water in test fluid.
It is specifically shown in Fig. 2.
3, in reagent-acetonitrile solution of a concentration of 10 μM of colorimetric reagent, 200 μM of F is added-There is maximum in 595nm afterwards
Absorption peak, then in the reagent-F-200 μM of AcO is added in mixed solution-Afterwards in the maximum absorption band of 595nm almost without change
Change；Conversely, in the acetonitrile solution of a concentration of 10 μM of colorimetric reagent, 200 μM of AcO is added-There is absorption maximum in 595nm afterwards
Peak, then in the reagent-AcO-200 μM of F is added in mixed solution-It has almost no change afterwards in the maximum absorption band of 595nm.Table
It is bright with this condition, AcO-Presence comparison color reagent detect F-Absorption spectrum have no significant effect；F-Presence compare color reagent
Detect AcO-Absorption spectrum have no significant effect namely F-And AcO-It does not interfere with each other the detection of reagent mutually.It is specifically shown in Fig. 3.
4. in reagent-acetonitrile solution of a concentration of 10 μM of colorimetric reagent, it is separately added into various concentration F-To reagent solution
In, with F-Addition, measure uv-visible absorption spectra titration curve.Absorption peak strength of the colorimetric reagent at 350nm is gradual
It reduces, and absorption peak strength gradually increases at 420nm, 595nm, there is isobestic point at 418nm, is formed at 350nm and 595nm
Ratio absorbs, with F-Concentration and linear change.It is specifically shown in Fig. 4.
5. being separately added into various concentration F in reagent-acetonitrile solution of a concentration of 10 μM of colorimetric reagent-, measure ratio and inhale
Receipts value.Ordinate is the ratio of 595nm and absorbance at 350nm wavelength, abscissa F-Concentration.F-Concentration is 1.0~25.0
It is linear with the ratio absorbance of reagent within the scope of μM.It is specifically shown in Fig. 5.
6. in reagent-acetonitrile solution of a concentration of 10 μM of colorimetric reagent, 200 μM of F is added-, AcO-, Cl-, Br-, I-,
HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -Afterwards, F-, AcO-Absorbance of the colorimetric reagent at 350nm is set to reduce, and at 595nm
Absorbance enhancing, the addition of other anion is without this phenomenon；Measure the absorbance ratio at 595nm and 350nm.Again respectively to
Reagent-F-The absorbance ratio at 595nm and 350nm is measured in mixed solution after other above-mentioned anion of 200 μM of addition.It is black
Vitta indicates to be separately added into the absorbance ratio after above-mentioned anion at wavelength 595nm and 350nm in colorimetric reagent.White
Item is indicated in reagent-F-The extinction at 595nm and 350nm after other above-mentioned counter anions is separately added into mixed solution again
Spend ratio.Show that colorimetric reagent detects F-Ratio absorbance not by including AcO-The shadow that other above-mentioned anion inside coexist
It rings.Ordinate is the ratio that wavelength is respectively absorbance at 595nm and 350nm.It is specifically shown in Fig. 6.
7. in reagent-acetonitrile-water (volume ratio of acetonitrile/water is 19/1) solution of a concentration of 10 μM of colorimetric reagent, point
It Jia Ru not 200 μM of anion F-, Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -When, remove I-And HSO4 -Addition make ratio
The uv-visible absorption spectra of color reagent has faint change outside the pale of civilization, and the light of colorimetric reagent is not observed in the addition of remaining anion
Spectrum has significant change；And the AcO of 200 μM of addition-When, AcO-So that absorption peak of the colorimetric reagent at 350nm is weakened, 420nm,
Occur new absorption peak at 560nm, has isobestic point at 410nm, form ratio absorption at 350nm and 560nm, show herein
Under the conditions of colorimetric reagent only to AcO-There is recognition detection effect.It is specifically shown in Fig. 7.
8. in reagent-acetonitrile-water (volume ratio of acetonitrile/water is 19/1) solution of a concentration of 10 μM of colorimetric reagent, point
It Jia Ru not various concentration AcO-, with AcO-Addition, measure uv-visible absorption spectra titration curve.Colorimetric reagent is in 350nm
The absorption peak strength at place continuously decreases, and absorption peak strength gradually increases at 420nm, 560nm, there is isobestic point at 410nm,
Ratio absorption is formed at 350nm and 560nm, with AcO-Concentration and linear change.It is specifically shown in Fig. 8.
9. in reagent-acetonitrile-water (volume ratio of acetonitrile/water is 19/1) solution of a concentration of 10 μM of colorimetric reagent respectively
Various concentration AcO is added-, measure ratio absorbance value.Ordinate is the ratio of 560nm and absorbance at 350nm wavelength, horizontal seat
It is designated as AcO-Concentration.AcO-Concentration is linear with the ratio absorbance of reagent within the scope of 1.0~45.0 μM.It is specifically shown in
Fig. 9.
10. in reagent-acetonitrile-water (volume ratio of acetonitrile/water is 19/1) solution of a concentration of 10 μM of colorimetric reagent, point
AcO that Jia Ru be 200 μM-, F-, Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -Afterwards, AcO-Colorimetric reagent is set to exist
Absorbance at 350nm weakens, and the absorbance enhancing at 560nm, and the addition of other anion is without this phenomenon；It measures
Absorbance ratio at 560nm and 350nm.Again respectively to reagent-AcO-Be added in mixed solution 200 μM it is above-mentioned other it is cloudy from
The absorbance ratio at 560nm and 360nm is measured after son.Black bar indicates to be added after different anions in wave in colorimetric reagent
Absorbance ratio at long 560nm and 350nm.White bars are indicated in reagent-AcO-Be separately added into again in mixed solution it is above-mentioned its
Absorbance ratio after his counter anion at 560nm and 350nm changes.Show that colorimetric reagent detects AcO-Ratio extinction
Degree is not by including F-The influence that other above-mentioned anion inside coexist.Ordinate is that wavelength is respectively to be inhaled at 560nm and 350nm
The ratio of luminosity.See Figure 10.
11. under daylight, in reagent-acetonitrile solution that a concentration of 20 μM of colorimetric reagent, in F-Ion concentration is respectively 0,10,
100,1000 μM when, colorimetric reagent solution colour variation corresponds to faint yellow, light blue, indigo, cyan respectively.Mesh can be passed through
F is detected depending on colorimetric method quantitative and semi-quantitative-Ion, detection are limited to 10 μM.It is specifically shown in Figure 11.
12. under daylight, reagent-acetonitrile-water (volume ratio of acetonitrile/water is 19/1) that a concentration of 20 μM of colorimetric reagent is molten
Liquid, in AcO-When ion concentration is respectively 0,10,100,1000 μM, the variation of colorimetric reagent solution colour corresponds to yellowish respectively
Color, crocus, lightpink, pink.Thus AcO can be detected by colorimetric method quantitative and semi-quantitative by visual observation-Ion, detection are limited to
10μM.See Figure 12.
13. in reagent-dimethyl sulfoxide (DMSO)-water of a concentration of 10 μM of colorimetric reagent, (volume ratio of dimethyl sulfoxide (DMSO)/water is 9/
1) in solution, the Tirs-HCl buffer solutions of the different pH of a concentration of 5mM are separately added into.When pH is 3~6, colorimetric reagent solution
UV-visible absorption spectrum is without significant change；PH be 7~9 when, colorimetric reagent 355nm absorption peak with pH value increase
Intensity continuously decreases, and occurs new absorption peak at 600nm, and intensity enhances with the increase of pH value, shows colorimetric reagent two
The weak acid of pH ranging from 6~9 be can detect in methyl sulfoxide/water (9/1, v/v) solution to weakly alkaline solution.It is specifically shown in Figure 13.
14. under daylight, reagent-dimethyl sulfoxide (DMSO)-water (volume of dimethyl sulfoxide (DMSO)/water of a concentration of 20 μM of colorimetric reagent
Than for 9/1) solution, be respectively in pH 6,7,8,9 a concentration of 5mM Tirs-HCl buffer solutions in, colorimetric reagent solution face
Color change corresponds to light yellow, light green color, light blue, sky blue respectively.Thus can visual detection pH ranging from 6~9 weak acid
To weakly alkaline solution, it is specifically shown in Figure 14.
15. under daylight, test strips are submerged initially in the dimethyl sulphoxide solution of the colorimetric reagent of a concentration of 1mM, take out, again
After filter paper item to be immersed to the Tirs-HCl buffer solutions for a concentration of 0.05M that pH is 7,8,9,10 respectively, filter paper color change
Yellow, light orange, orange red, aubergine are corresponded to respectively.Showing can visual detection pH ranging from 7~10 with reagent filter paper item
Neutrality is to weakly alkaline solution.
16. under daylight, a concentration of 20 μM of reagent solution, different water contents dimethyl sulfoxide (DMSO)/water (pH 9,
In buffer solution 2mMTirs-HCl), water content be respectively 1%, 10%, 20%, 30%, 40%, 50%, 60%,
70%, 80% when, reagent solution color change corresponds to turquoise, sky blue, purple, royal purple, light violet magenta, powder respectively
It is red, baby pink, pale pinkish grey, ivory white.Thus H in solution can be detected by colorimetric method quantitative and semi-quantitative by visual observation2The percentage of O
Content, detection are limited to 1%.It is specifically shown in Figure 16.
Compared with prior art, the invention has the advantages that：
(1) colorimetric reagent can highly sensitive, high selection detection specific ion, molecule, have that testing cost is low, speed is fast, sets
The features such as standby simple, method is easy, intuitive, is widely used in analysis detection field.Colorimetric reagent can not only visual detection, qualitative
Analysis, moreover it is possible to by means of the spectral quality that ratio absorbs, form isobestic point when using detection, exist simultaneously the suction of different wave length
The variation for receiving peak ratio is measured, and has higher detection sensitivity and accuracy.It is absorbed using ratio, that is, ratio of absorbance
Detection mode is different from the variation detection of the absorbance of single wavelength, in practical applications the composition of object under inspection, colorimetric examination
The influence of the factors such as agent concentration, test condition, light source fluctuation and instrument sensitivity is small, passes through absorbance under two different wave lengths
Ratio changes, and reduces the factor for influencing Accurate Determining, can make that the responsing linear range of detection, detection limit, accuracy significantly improves.
(2) recognition property is superior.The colorimetric reagent of the present invention is inhaled by controlling different solvents or solvent ratio using ratio
Receiving method, selective enumeration method plurality of target ion.Ratio absorption pattern can not only be used to detect, and it is fast to can be used for visual colorimetric determination
Speed detection F-、AcO-、pH、H2O and pH test paper.Realize the multifunctional application of single agents.
Description of the drawings：
Fig. 1 be colorimetric reagent in acetonitrile solution with the UV-visible absorption spectrum of anion；
Fig. 2 be different volumes than acetonitrile/water solution in colorimetric reagent-F-, reagent-AcO-Absorbance change figure；
Fig. 3 is colorimetric reagent and F in acetonitrile solution-、AcO-And F-、AcO-The UV-visible absorption spectrum coexisted；
Fig. 4 is the F of various concentration in acetonitrile solution-Compare the uv-visible absorption spectra titration figure of color reagent；
Fig. 5 is that colorimetric reagent detects F in acetonitrile solution-UV-Vis Spectrophotometry correction graph；
Fig. 6 is counter anion comparison color reagent UV-Vis Spectrophotometry detection F in acetonitrile solution-Influence diagram；
Fig. 7 is the UV-visible absorption spectrum of colorimetric reagent and anion in acetonitrile/water (19/1, v/v) solution；
Fig. 8 is the AcO of various concentration in acetonitrile/water (19/1, v/v) solution-Compare the ultraviolet-ray visible absorbing light of color reagent
Spectrum titration figure；
Fig. 9 is that colorimetric reagent detects AcO in acetonitrile/water (19/1, v/v) solution-UV-Vis Spectrophotometry correction
Curve graph；
Figure 10 is that counter anion compares color reagent UV-Vis Spectrophotometry in acetonitrile/water (19/1, v/v) solution
Detect AcO-Influence diagram；
Figure 11 is colorimetric reagent visual colorimetric determination detection various concentration F under daylight in acetonitrile solution-Solution colour variation shine
Piece；
Figure 12 is colorimetric reagent visual colorimetric determination detection various concentration AcO under daylight in acetonitrile/water (19/1, v/v) solution-
Solution colour change photo；
Figure 13 be dimethyl sulfoxide (DMSO)/water (9/1, v/v), difference pH buffer solution in colorimetric reagent ultraviolet-visible inhale
Receive spectrogram；
Figure 14 is in dimethyl sulfoxide (DMSO)/water (9/1, v/v), and it is molten to detect different pH bufferings for colorimetric reagent visual colorimetric determination under daylight
The color change photo of liquid；
Figure 15 is the test strips color change photo that colorimetric reagent detects different pH buffer solutions；
Figure 16 is colorimetric reagent visual detection difference H2The solution colour photo of O content.
Specific implementation mode
Embodiment 1：
The chemical structural formula of 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline is：
Preparation method is：
A, intermediate：The synthesis of 2- hydroxyls -5- (4- nitroazobenzenes) benzaldehyde：
In 100ml there-necked flasks, paranitroanilinum (1.38g, 10mmol) and 4ml concentrated hydrochloric acids and 5ml water is added, waits for that its is molten
0~5 DEG C is cooled to after solution under ice salt bath, 5ml sodium nitrite in aqueous solution is slowly dropped into wherein, is continued under ice bath after adding
2h is reacted, with sodium hydroxide solution tune pH=7, it is added in the aqueous solution that then will contain salicylide (1.22g, 10mmol) 20ml
In, the reaction was continued 4h has red precipitate precipitation after having reacted, filter, be dried in vacuum overnight, and tetrahydrofuran recrystallization obtains 2- hydroxyls
Base -5- (4- nitroazobenzenes) benzaldehyde.Yield 53.5%.
B, the preparation of 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline
In 25mL microwave reaction pipes, be added 8- hydroxy-2-methylquinolines 0.11g (0.69mmol), above-mentioned preparation 2-
Hydroxyl -5- (4- nitroazobenzenes) benzaldehydes and 10mL acetic anhydrides, are mixed to form orange-red solution, at a temperature of 128-132 DEG C,
Microwave power 50W, microwave reaction 60min；After reaction, round-bottomed flask is moved to, 100mL ice water is added into reaction solution, stirs
2h is mixed, orange-yellow solid occurs, is filtered, it is dry, obtain 0.3g solid intermediates；The intermediate solid is placed in tri- necks of 100mL
In bottle, add 20mL pyridines, in N2Under protection, flow back 5h at 80-85 DEG C, adds 9mL water, continues the 20h that flows back, cooling, adds
The ice water of 100mL has the solid of brownish red to be precipitated, filters overnight, dry, and crude by column chromatography purifying, eluant, eluent is acetic acid
Ethyl ester:N-hexane, eluant, eluent volume ratio are 4:6, obtain Orange red solid powder 2- [2- hydroxyls -5- (4- nitroazobenzenes) benzene second
Alkenyl] -8-hydroxyquinoline.Yield 80.8%.M.p.202~218 DEG C；1H NMR(500MHz,DMSO-d6)δ:11.303(s,
1H ,-OH), 9.639 (s, 1H ,-OH), 8.451 (d, J=11.5Hz, 2H, ArH), 8.323 (s, 1H, ArH), 8.251 (d, 1H,
J=20Hz ,=CH-), 8.302 (d, 1H, J=20.5Hz, ArH), 8.066 (d, 2H, J=11Hz, ArH), 7.902 (d, 1H, J
=10.1Hz, ArH), 7.842 (d, 1H, J=11Hz, ArH), 7.719 (d, 1H, J=20.5Hz ,=CH-), 7.409-7.358
(m, 2H, ArH), 7.177 (d, 1H, J=11Hz, ArH), 7.101 (d, 1H, J=11Hz, ArH)；13C NMR(500MHz,
DMSO-d6)δ:160.65,155.55,153.74,153.03,147.87,145.47,138.25,136.52,130.03,
129.25,127.78,127.08,125.34,125.14,124.31,124.10,123.09,120.85,117.62,116.99,
111.35；IR(cm-1):3340,2924,2853,1593,1561,1455,1341,1301,1258,1086,985,857,828,
755,720,618；MS(ESI)m/z:413.4[M+H]+。
Embodiment 2：
The preparation method of various reagents in analysis method of the present invention：
(1) preparation of colorimetric reagent dimethyl sulfoxide (DMSO) storing solution：20.6mg colorimetric reagents are weighed (to be made by embodiment 1
It is standby), with dmso solution and it is configured to the colorimetric reagent dimethyl sulfoxide (DMSO) storing solution 50mL of a concentration of 1mM；
The preparation of colorimetric reagent acetonitrile storing solution：20.6mg colorimetric reagents (being prepared by embodiment 1) are weighed, acetonitrile is used
Dissolve and be configured to the colorimetric reagent acetonitrile storing solution 50mL of a concentration of 1mM；
(2)F-Storing solution is prepared：Tetrabutyl ammonium fluoride 0.3155g is weighed, dissolved with acetonitrile and is configured to a concentration of 20mM
Tetrabutyl ammonium fluoride acetonitrile storing solution 50mL.
(3)AcO-Storing solution is prepared：Tetrabutylammonium acetate ammonium 0.3015g is weighed, dissolved with acetonitrile and is configured to a concentration of
The tetrabutylammonium acetate acetonitrile storing solution 50mL of 20mM.
Other anion (Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -) storing solution preparation：Take corresponding four
Butylammonium salts acetonitrile dissolves and is diluted to the anion acetonitrile storing solution of 20mM.
(4) Tris-HCl buffer solutions (0.5M)：With a concentration of 0.5M trihydroxy methyls (triamido) ethane (Tris) and
0.5M HCl are prepared, and adjust pH to 2~10；
Tris-HCl buffer solutions (0.2M)：With a concentration of 0.2M trihydroxy methyls (triamido) ethane (Tris) and
0.2MHCl is prepared, and adjusts pH to 9；
Tris-HCl buffer solutions (0.05M)：With a concentration of 0.05M trihydroxy methyls (triamido) ethane (Tris) and
0.05MHCl is prepared, and adjusts pH to 2~10；PH value is measured with compound glass electrode through acidometer.
Agents useful for same is analytical reagents, and test water is ultra-pure water.
Ultraviolet-visible spectrophotometer model UV-1800 (Japanese Shimadzu Corporation) used in the present invention；818 types of Model
Acidometer (Ao Lilong companies of the U.S.)；Microwave Synthesis System model Discover SP, U.S. CE M companies produce.
Embodiment 3：
(1) UV-Vis Spectrophotometry detects F-
Colorimetric reagent acetonitrile storing solution (1mM, 0.1mL) is added in 10mL volumetric flasks to be shaken with dilution in acetonitrile to scale
It is even, colorimetric reagent solution is obtained, colorimetric reagent solution about 3mL is taken to carry out uv-visible absorption spectra survey in the cuvette of 1cm
It is fixed；
After being separately added into colorimetric reagent acetonitrile storing solution (1mM, 0.1mL) in serial 10mL volumetric flasks, then it is separately added into
Anion F-, AcO-, Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -Storing solution (20mM, 0.1mL), uses dilution in acetonitrile
It to scale, shakes up, solution about 3mL is taken to carry out uv-visible absorption spectra measurement in the cuvette of 1cm.
After being separately added into colorimetric reagent acetonitrile storing solution (1mM, 0.1mL) in serial 10mL volumetric flasks, then it is separately added into
Anion F-, AcO-Storing solution (20mM, 0.1mL), is diluted to scale with acetonitrile/water respectively, makes the volume of acetonitrile/water in solution
Than being 100/0,19/1,9/1,17/3,4/1,3/1, shakes up, obtain reagent solution, take reagent solution about 3mL in the cuvette of 1cm
Middle progress uv-visible absorption spectra measurement.
200 μM of anion F is separately added into a concentration of 10 μM of colorimetric reagent acetonitrile solution-, AcO-, Cl-, Br-,
I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -After solution, only F-And AcO-Addition make colorimetric reagent solution in the suction of 350nm
It receives peak to weaken, occurs new absorption peak in 420nm, 595nm or so；There is isobestic point at 418nm, shape at 350nm and 595nm
It is absorbed at ratio, shows that reagent is to F with this condition-、AcO-There is recognition detection effect.(such as Fig. 1).
A concentration of 10 μM of colorimetric reagent different volumes than acetonitrile/water solution in, be separately added into 200 μM of AcO-Or
F-Afterwards, the absorbance of maximum absorption wave strong point is measured.Reagent-the F in acetonitrile solution-, reagent-AcO-Absorbance is most at 595nm
Greatly, in acetonitrile/water solution, reagent-F-, reagent-AcO-Maximum absorption wavelength violet shift to 560nm, absorbance reduces, and reduces
Degree is different；At acetonitrile/water (19/1, v/v), reagent-F-Absorbance is reduced than reagent-AcO at 560nm-In the wavelength
Absorbance reduce apparent (Fig. 2).Therefore, the ratio of acetonitrile/water in colorimetric examination solution is surveyed in control, keeps colorimetric reagent molten in acetonitrile
F is detected in liquid-；Colorimetric reagent detects AcO in acetonitrile/water (19/1, v/v) solution-。
In a concentration of 10 μM of colorimetric reagent acetonitrile solution, 200 μM of F is added-There is maximum absorption band in 595nm afterwards,
Again in the reagent-F-200 μM of AcO is added in mixed solution-It has almost no change afterwards in the maximum absorption band of 595nm；Conversely,
In the acetonitrile solution of a concentration of 10 μM of reagent, 200 μM of AcO is added-There is maximum absorption band in 595nm afterwards, then in the examination
Agent-AcO-200 μM of F is added in mixed solution-It has almost no change (Fig. 3) in the maximum absorption band of 595nm afterwards.Show herein
Under the conditions of, AcO-Presence comparison color reagent detect F-Absorption spectrum have no significant effect；F-Presence comparison color reagent detection
AcO-Absorption spectrum have no significant effect namely F-And AcO-It does not interfere with each other the detection of colorimetric reagent mutually.
In the acetonitrile solution of a concentration of 10 μM of colorimetric reagent, it is separately added into the F of various concentration-It measures afterwards and obtains purple
Outside-visible absorption spectra titration curve (such as Fig. 4).Measure F-Extinction of the colorimetric reagent at 350nm and 595nm when concentration changes
The ratio of degree obtains ratio absorption correction curve (such as Fig. 5).By the standard deviation of 10 blank values of slope and measurement of calibration curve
Difference measures and colorimetric reagent ultraviolet-ray visible absorbing method detection F is calculated-The concentration range of linearity and detection limit, be listed in table 5.
Colorimetric reagent detects F-Absorbance ratio at 350nm and 595nm includes AcO in other above-mentioned anion-Point
Not Zuo Wei coexisting ion be present in reagent-F-In mixed solution, as the F of other anion concentrations and test-When suitable, Qi Tayin
Ion pair colorimetric reagent detects F-The relative deviation that influences of ratio absorbance within 5%, not interference measurement (such as Fig. 6).
5 colorimetric reagent UV-Vis Spectrophotometry of table detects F-Analysis parameter
(2) UV-Vis Spectrophotometry detects AcO-
Colorimetric reagent acetonitrile storing solution (1mM, 0.1mL) is added in 10mL volumetric flasks, scale is diluted to acetonitrile/water,
It is 19/1 to make acetonitrile/water volume ratio in solution, shakes up, obtains colorimetric reagent solution, takes colorimetric reagent solution about 3mL in the ratio of 1cm
Uv-visible absorption spectra measurement is carried out in color ware；
After being separately added into colorimetric reagent acetonitrile storing solution (1mM, 0.1mL) in serial 10mL volumetric flasks, then it is separately added into
Anion F-, AcO-, Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6-- storing solution (20mM, 0.1mL) uses acetonitrile/water
It is diluted to scale, it is 19/1 to make acetonitrile/water volume ratio, shakes up, solution about 3mL is taken to carry out ultraviolet-visible in the cuvette of 1cm
Absorption spectromtry.
In a concentration of 10 μM colorimetric reagent acetonitrile/water (19/1, v/v) solution, it is separately added into 200 μM of anion
F-, Cl-, Br-, I-, AcO-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -When, only AcO-Addition so that colorimetric reagent solution is existed
Absorption peak at 350nm weakens, and occurs new absorption peak 420nm, 560nm at, there is isobestic point at 410nm, 350nm and
Ratio absorption is formed at 560nm, shows that colorimetric reagent is to AcO with this condition-There is recognition detection to act on (such as Fig. 7).
In a concentration of 10 μM colorimetric reagent acetonitrile/water (19/1, v/v) solution, the AcO of various concentration is added-After survey
Surely uv-visible absorption spectra titration curve (such as Fig. 8) is obtained.Measure AcO-When concentration changes colorimetric reagent in 350nm and
The ratio of absorbance at 560nm obtains ratio absorption correction curve (such as Fig. 9).By calibration curve slope and measure 10 times
The standard deviation of blank value measures and colorimetric reagent UV-Vis Spectrophotometry detection AcO is calculated-Concentration it is linear
Range and detection limit are listed in table 6.
Colorimetric reagent detects AcO-Absorbance ratio at 350nm and 560nm includes F in other above-mentioned anion-Point
Not Zuo Wei coexisting ion be present in reagent-AcO-In mixed solution, as the AcO of other anion concentrations and test-When suitable,
Its anion compares color reagent and detects AcO-Ratio absorbance influence relative deviation within 5%, not interference measurement (as scheme
10)。
6 colorimetric reagent UV-Vis Spectrophotometry of table detects AcO-Analysis parameter
(3) UV-Vis Spectrophotometry detects pH
In 10mL volumetric flasks be added colorimetric reagent dimethyl sulfoxide (DMSO) stock solution (1mM, 0.1mL), with dimethyl sulfoxide (DMSO)/
Water is diluted to scale, and it is 9/1 to make dimethyl sulfoxide (DMSO)/water volume ratio, shakes up, obtains colorimetric reagent solution, takes colorimetric reagent solution about
3mL carries out uv-visible absorption spectra measurement in the cuvette of 1cm；
After being separately added into colorimetric reagent dimethyl sulfoxide (DMSO) stock solution (1mM, 0.1mL) in serial 10mL volumetric flasks, then
The Tirs-HCl buffer solutions (0.5M, 20 μ L) that pH is 3,4,5,6,7,8,9 are separately added into, are diluted to dimethyl sulfoxide (DMSO)/water
Scale, make dimethyl sulfoxide (DMSO)/water volume ratio be 9/1, after shaking up, take solution about 3mL carried out in the cuvette of 1cm it is ultraviolet-can
See absorption spectromtry.
When pH is 3~6, the uv-visible absorption spectra of colorimetric reagent solution is without significant change；When pH is 7~9, colorimetric
Absorption peak of the reagent solution in 355nm is continuously decreased with the increase intensity of pH value, occurs new absorption peak in 600nm, intensity with
The increase of pH value and enhance, show that colorimetric reagent can detect pH's ranging from 6~9 in dimethyl sulfoxide (DMSO) (9/1, v/v) solution
Weak acid is to weakly alkaline solution (such as Figure 13).
Embodiment 4：
(1) F in colorimetric reagent optical colorimetry detection solution-
In serial bottle, it is separately added into colorimetric reagent acetonitrile storing solution (1mM, 40 μ L), then be separately added into different volumes
A concentration of 20mM F-After storing solution, with dilution in acetonitrile to 2mL, reagent-F is obtained-Solution.Under daylight, in F-Ion concentration is distinguished
When being 0,10,100,1000 μM, the variation of colorimetric reagent solution colour corresponds to faint yellow, light blue, indigo, cyan respectively.
Thus F can be detected by colorimetric method quantitative and semi-quantitative by visual observation-Ion, detection are limited to 10 μM (such as Figure 11).
(2) AcO in colorimetric reagent optical colorimetry detection solution-
In serial bottle, it is separately added into colorimetric reagent acetonitrile storing solution (1mM, 40 μ L), then be separately added into different volumes
A concentration of 20mM AcO-After storing solution, it is diluted to 2mL with acetonitrile/water, it is 19/1 to make acetonitrile/water volume ratio, obtains colorimetric examination
Agent-AcO-Solution；Under daylight, in AcO-When ion concentration is respectively 0,10,100,1000 μM, the variation of colorimetric reagent solution colour
Faint yellow, crocus, lightpink, pink are corresponded to respectively.Thus it colorimetric method quantitative and semi-quantitative can detect by visual observation
AcO-Ion, detection are limited to 10 μM (such as Figure 12).
(3) pH of colorimetric reagent optical colorimetry detection solution
In serial bottle, it is separately added into colorimetric reagent dimethyl sulfoxide (DMSO) stock solution (1mM, 40 μ L), then be separately added into
Tirs-HCl (0.5M, 20 μ L) buffer solution of different pH value, 2mL is diluted to dimethyl sulfoxide (DMSO)/water, make dimethyl sulfoxide (DMSO)/
Water volume ratio is 9/1.Under daylight, dimethyl sulfoxide (DMSO) (9/1, v/v) solution of a concentration of 20 μM of colorimetric reagent is respectively in pH
6, in the Tirs-HCl buffer solutions of 7,8,9 a concentration of 5mM, colorimetric reagent solution colour variation correspond to respectively it is light yellow,
Light green color, light blue, sky blue.Show colorimetric reagent can visual detection pH ranging from 6~9 weak acid to weakly alkaline solution (such as
Figure 14).
(4) the ELISA test strip pH value of solution of colorimetric reagent is loaded
Ordinary filter paper is cut to 15mm × 40mm and makees pH test paper slips, filter paper item is immersed to the colorimetric reagent two of 1.0mM
Methyl sulfoxide solution, after colorimetric reagent is carried on test strips, then the test strips are immersed to the different pH of a concentration of 0.05M
In Tirs-HCl buffer solns, with the difference of pH, under daylight, different colours are presented in test strips.PH is respectively 7,8,9,10
Buffer solution, test strips color change correspond to yellow, light orange, orange red, aubergine.Show after colorimetric reagent loads
Test strips can visual detection pH ranging from 7~10 it is neutral to weakly alkaline solution (such as Figure 15).
(5) water content in colorimetric reagent optical colorimetry detection dimethyl sulfoxide (DMSO)/water
In serial bottle, a concentration of 20 μM are configured to the colorimetric reagent dimethyl sulfoxide (DMSO) stock solution of a concentration of 1mM
Colorimetric reagent solution, in the buffer solution of dimethyl sulfoxide (DMSO)/water (pH 9,2mM Tirs-HCl) of different water contents,
When water content is respectively 1%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, under daylight, colorimetric reagent solution
Color change correspond to respectively turquoise, sky blue, purple, royal purple, light violet magenta, pink, baby pink, it is pale pinkish grey,
It is ivory white；Thus H in solution can be detected by colorimetric method quantitative and semi-quantitative by visual observation2The percentage composition of O, detection are limited to 1% (such as
Figure 16).
Claims (8)
1. a kind of 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent, it is characterised in that：
The chemical structural formula of the colorimetric reagent is：
2. a kind of 2- as described in claim 1 [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric
The preparation method of reagent, it is characterised in that：It is synthesized according to following route：
3. 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent as claimed in claim 2
Preparation method, it is characterised in that：Include the following steps：
A, intermediate：The synthesis of 2- hydroxyls -5- (4- nitroazobenzenes) benzaldehyde：
In 100ml there-necked flasks, paranitroanilinum 1.38g and 4ml concentrated hydrochloric acid and 5ml water is added, in ice salt bath after its dissolving
Under be cooled to 0~5 DEG C, 5ml sodium nitrite in aqueous solution is slowly dropped into wherein, after adding under ice bath the reaction was continued 2h, use hydrogen
Then the aqueous solution 20ml of the 1.22g containing salicylide is added thereto by sodium hydroxide solution tune pH=7, the reaction was continued 4h, after having reacted
There is red precipitate precipitation, filter, be dried in vacuum overnight, tetrahydrofuran recrystallization obtains 2- hydroxyls -5- (4- nitroazobenzenes) benzene first
Aldehyde；Yield 53.5%；
B, the preparation of 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline：
In 25mL microwave reaction pipes, be added 8- hydroxy-2-methylquinolines 0.11g, above-mentioned preparation 2- hydroxyls -5- (4- nitros
Azobenzene) benzaldehyde and 10mL acetic anhydrides, it is mixed to form orange-red solution, at a temperature of 128-132 DEG C, microwave power 50W is micro-
Wave reacts 60min；After reaction, round-bottomed flask is moved to, 100mL ice water is added into reaction solution, stirs 2h, is occurred orange-yellow
Solid, filter, it is dry, obtain 0.3g solid intermediates；The intermediate solid is placed in 100mL three-necked bottles, 20mL pyridines are added,
In N2Under protection, flow back 5h at 80-85 DEG C, adds 9mL water, continues the 20h that flows back, cooling, adds the ice water of 100mL, overnight, has
The solid of brownish red is precipitated, and filters, dry, and crude by column chromatography purifying, eluant, eluent is ethyl acetate:N-hexane, eluant, eluent
Volume ratio is 4:6, obtain Orange red solid powder 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline.
4. a kind of 2- as claimed in any one of claims 1-3 [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8- hydroxyls
The application of base quinoline colorimetric reagent, it is characterised in that：Including
(1) it is used as in UV-Vis Spectrophotometry for detecting AcO in solution-、F-And the colorimetric reagent of pH；
(2) F in optical colorimetry detection solution-、AcO-, pH and optical colorimetry detection dimethyl sulfoxide (DMSO)/water in water content；
(3) the ELISA test strip pH value of solution of colorimetric reagent is loaded.
5. 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent as claimed in claim 4
Application, it is characterised in that：As in UV-Vis Spectrophotometry for detecting AcO in solution-、F-And the colorimetric examination of pH
When agent, detection method includes：
(1) UV-Vis Spectrophotometry detects F-：In acetonitrile solution, ratio extinction of the colorimetric reagent in 350nm and 595nm
Angle value and F-Concentration is in a linear relationship, and F is detected with calibration curve method-, F-The range of linearity of concentration is 1.0-25.0 μM, detection limit
It is 0.63 μM；
(2) UV-Vis Spectrophotometry detects AcO-：In the acetonitrile/water solution that volume ratio is 19/1, colorimetric reagent exists
The ratio absorbance value and AcO of 350nm and 560nm-Concentration is in a linear relationship, and AcO is detected with calibration curve method-, AcO-Concentration
The range of linearity is 1.0-45.0 μM, and detection is limited to 0.44 μM；
(3) UV-Vis Spectrophotometry detects pH：Colorimetric reagent volume ratio be 9/1 dimethyl sulfoxide (DMSO)/aqueous solution in,
The Tirs-HCl buffer solutions of at least 3 kinds different pH value are separately added into, the pH value is 3-9, and solution is taken to be carried out in cuvette
Ultraviolet-visible spectrum measures；It is the absorption peak variation at 355nm and 600nm with wavelength, can detect the pH ranging from solution of 6-9.
6. 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent as claimed in claim 5
Application, it is characterised in that：
(1) in acetonitrile solution, UV-Vis Spectrophotometry detects F-When, other counter anions are AcO-, Cl-,
Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -One of, in concentration and F-When identical, to F-Measurement do not interfere；
(2) in the acetonitrile/water solution that volume ratio is 19/1, UV-Vis Spectrophotometry detects AcO-When, other are total
It is F to deposit anion-, Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -One of, in concentration and AcO-When identical, to AcO-
Measurement do not interfere；
7. 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent as claimed in claim 4
Application, it is characterised in that：Optical colorimetry detects F in solution-、AcO-, pH and optical colorimetry detection dimethyl sulfoxide (DMSO)/
In water when water content, detection method includes：
(1) F in optical colorimetry detection solution-When, in a concentration of 20 μM of colorimetric reagent acetonitrile solution, under daylight, F-Ion is dense
Degree be respectively 0,10,100,1000 μM when, colorimetric reagent solution colour variation correspond to respectively faint yellow, light blue, indigo,
Cyan, detection are limited to 10 μM；
(2) AcO in colorimetric reagent optical colorimetry detection solution-When, a concentration of 20 μM of colorimetric reagent is 19/1 in volume ratio
In acetonitrile/water solution, under daylight, in AcO-When ion concentration is respectively 0,10,100,1000 μM, colorimetric reagent solution colour becomes
Change corresponds to faint yellow, crocus, lightpink, pink respectively, and detection is limited to 10 μM；
(3) when the pH of colorimetric reagent optical colorimetry detection solution, a concentration of 20 μM of colorimetric reagent is respectively 6,7,8,9 in pH
A concentration of 5mM Tirs-HCl buffer solutions in, dilute the volume ratio so that dimethyl sulfoxide (DMSO)/water with dimethyl sulfoxide (DMSO)/water
It is 9/1, under daylight, in pH is respectively 6,7,8,9 buffer solutions, the variation of colorimetric reagent solution colour corresponds to pale yellow respectively
Color, light green color, light blue, sky blue；
(4) in colorimetric reagent optical colorimetry detection dimethyl sulfoxide (DMSO)/water when water content, a concentration of 20 μM of colorimetric reagent is not
With in dimethyl sulfoxide (DMSO)/water buffer solution of water content, water content be respectively 1%, 10%, 20%, 30%, 40%, 50%,
60%, 70%, 80% when, under daylight, the variation of colorimetric reagent solution colour corresponds to turquoise, sky blue, purple, dark purple respectively
It is red, light violet magenta, pink, baby pink, pale pinkish grey, ivory white；Colorimetric reagent colorimetric method quantitative and semi-quantitative by visual observation
Detect H in solution2The percentage composition of O, detection are limited to 1%.
8. 2- [2- hydroxyls -5- (4- nitroazobenzenes) styryl] -8-hydroxyquinoline colorimetric reagent as claimed in claim 4
Application, it is characterised in that：When loading the ELISA test strip pH value of solution of colorimetric reagent, test strips are submerged initially in respectively a concentration of
Reagent load is carried out in the colorimetric reagent acetonitrile solution of 1mM, is taken out, then test strips are immersed to the concentration that pH is 7,8,9,10 respectively
After the Tirs-HCl buffer solutions of 0.05M, under daylight, test strips color change corresponds to yellow, light orange, orange red respectively
Color, aubergine.
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| WO2005115061A1 (en) * | 2004-05-20 | 2005-12-01 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting element and light emitting device |
| CN103342699A (en) * | 2013-07-16 | 2013-10-09 | 贵州大学 | Coumarin-thiacalix [4] arene fluorescent reagent as well as preparation method and application thereof |
| CN103641779A (en) * | 2013-12-24 | 2014-03-19 | 贵州大学 | Quinaldine derivative b fluorescent and colorimetric reagent as well as preparation method and application thereof |
| CN103992787A (en) * | 2014-04-29 | 2014-08-20 | 贵州大学 | Tris [4-(4-morpholine)-1, 8-naphthalimide ethyl] amine fluorescent reagent and preparation and application thereof |
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| WO2005115061A1 (en) * | 2004-05-20 | 2005-12-01 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting element and light emitting device |
| CN103342699A (en) * | 2013-07-16 | 2013-10-09 | 贵州大学 | Coumarin-thiacalix [4] arene fluorescent reagent as well as preparation method and application thereof |
| CN103641779A (en) * | 2013-12-24 | 2014-03-19 | 贵州大学 | Quinaldine derivative b fluorescent and colorimetric reagent as well as preparation method and application thereof |
| CN103992787A (en) * | 2014-04-29 | 2014-08-20 | 贵州大学 | Tris [4-(4-morpholine)-1, 8-naphthalimide ethyl] amine fluorescent reagent and preparation and application thereof |
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