CN106187884A - 2 [2 hydroxyl 5 (4 nitroazobenzene) styryl] 8 hydroxyquinoline colorimetric reagents and preparation and application - Google Patents
2 [2 hydroxyl 5 (4 nitroazobenzene) styryl] 8 hydroxyquinoline colorimetric reagents and preparation and application Download PDFInfo
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Abstract
The invention discloses a kind of 2 [2 hydroxyl 5 (4 nitroazobenzene) styryl] 8 hydroxyquinoline colorimetric reagents and its preparation method and application, the present invention utilizes quinoline and nitro-azo benzene derivative to prepare one for primary raw material and can apply to detect in analytical chemistry F‑、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 easy, be quickly applied to F‑、AcO‑、pH、H2The visual detection of O.Preparation 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, particularly a kind of 2-[2-hydroxyl-5-(4-nitro
Diphenyl diimide) styryl]-8-hydroxyquinoline colorimetric reagent and its preparation method and application.
Background technology
Colorimetric reagent highly sensitive, high can select detection specific ion, has that testing cost is low, speed is fast, equipment is simple, just
The features such as method is easy, directly perceived, are widely used analyzing detection field.Colorimetric reagent can not only visual detection, qualitative analysis, moreover it is possible to
The spectral quality absorbed by means of ratio, forms isobestic point when utilizing detection, there is the absworption peak ratio of different wave length simultaneously
Change be measured, have higher detection sensitivity and accuracy.Utilize the ratio i.e. ratio absorption detecting mode of absorbance
It is different from the change-detection of the absorbance of single wavelength, the in actual applications composition of object under inspection, colorimetric reagent concentration, survey
The impact of the factors such as strip part, light source fluctuation and instrument sensitivity is little, is changed by the ratio of absorbance under two different wave lengths,
Reduce the factor affecting Accurate Determining, the responsing linear range of detection, detection limit, accuracy can be made to significantly improve.
Anion plays an important role in life sciences and chemical process.The extensively application of anion makes it detect in change
There are important researching value and application prospect in the fields such as work, environment, medicine, life sciences.Anion uses chromatography of ions mostly
Technology for detection.And the design of anion probe techniques middle probe reagent is had less electric charge/radius ratio by anion, lead
The effect causing to utilize electrostatic interaction identification anion is poor；Anion is sensitive to solution ph, can protonate at low ph values and
Cause its electronegative minimizing, thus higher than the difficulty of cations recognition；Anion has different geometry, steric effect
Affect bigger；Anion is affected bigger by solvation.For cation, setting of anion probe reagent
Meter needs to consider more influence factor.
Compared with other anion, F-Can be formed relatively with the hydrogen bonding moieties of detectable such as amino, hydroxyl, acylamino-etc.
Strong hydrogen bond.Therefore, in organic solvent, F-Introducing detectable will be caused the change of obvious color to occur, and for F-
Detection be usually associated with AcO-Interference, developing selective more preferable Anionic recognition reagent or can realize simultaneously to multiple from
The selective enumeration method reagent of son is relatively difficult.Anionic recognition probe reagent is the most much reported, but uses same reagent energy
Close to selective enumeration method F under near-infrared wavelength-、AcO-, the most also can apply to pH, H2The colorimetric reagent of the visual detection of O is not
Appear in the newspapers.
Anionic recognition probe reagent is the most much reported, but can be close to selectivity under near-infrared wavelength with same reagent
Detection F-、AcO-, the most also can apply to pH, H2The colorimetric reagent of the visual detection of O has no report.
Summary of the invention
It is an object of the invention to, it is provided that a kind of 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyl quinoline
Quinoline colorimetric reagent and its preparation method and application, the present invention utilizes quinoline and nitro-azo benzene derivative to be primary raw material
Prepare one and can apply to analytical chemistry detects F-、AcO-, and pH, H2The colorimetric reagent of O.Colorimetric reagent of the present invention leads to
Cross control different solvents, with ratio absorption process selective enumeration method F-、AcO-.Simultaneously, moreover it is possible to easy, be quickly applied to F-、
AcO-、pH、H2The visual detection of O.Preparation cost is cheap, and detection sensitivity is high, selectivity is good, and operating condition is easily controllable, application
Prospect is good.
Technical scheme: a kind of 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline ratio
Color reagent, the chemical structural formula of described colorimetric reagent is:
Aforesaid 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent, described colorimetric
Reagent is mainly salicylide aqueous solution 5-15 part of 0.5M, 8-by the paranitroanilinum 5-15 part calculated by thing mass parts, concentration
Hydroxy-2-methylquinoline 0.3-0.9 part and sodium nitrite in aqueous solution 1-10 part that concentration is 2.5M of by volume part calculating, matter
Amount mark is that concentrated hydrochloric acid 1-8 part of 36-38%, acetic anhydride 5-15 part and pyridine 10-30 part are prepared from.
Aforesaid 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent, described colorimetric
Reagent mainly by the paranitroanilinum calculated by thing mass parts 10 parts, concentration be the salicylide aqueous solution 10 parts of 0.5M, 8-hydroxyl-
The sodium nitrite in aqueous solution that concentration is 2.5M 5 parts, mass fraction that 2-methylquinoline 0.69 part and by volume part calculate are 36-
The concentrated hydrochloric acid of 38% 4 parts, acetic anhydride 10 parts and pyridine 20 parts are prepared from.
A kind of system of aforesaid 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent
Preparation Method, synthesizes according to following route:
The preparation side of aforesaid 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent
In method, comprise the following steps:
(1) in paranitroanilinum, add concentrated hydrochloric acid and the water that mass fraction is 36-38%, dissolve, obtain A product；
(2), after A product are cooled to 0～5 DEG C under cryosel is bathed, it are slowly dropped into the sodium nitrite in aqueous solution that concentration is 2.5M, obtain B
Product；
(3) after B product react 1-3h under ice bath, adjust pH=7 with sodium hydroxide solution, obtain C product；
(4) in C product, add the salicylide aqueous solution that concentration is 0.5M, react 3-5h, after having reacted, have red precipitate to analyse
Go out, filter, dried in vacuum overnight, oxolane recrystallization, obtain D product；
(5), during D product are placed in microwave reaction pipe, add 8-hydroxy-2-methylquinoline and acetic anhydride, be mixed to form orange red molten
Liquid, obtains E product；
(6) E product in 128-132 DEG C, microwave power be 48-52W under the conditions of react 55-65min, obtain F product；
(7) in F product, add frozen water, stir 1-3h, orange/yellow solid occurs, filter, be dried, obtain G product；
(8) G product add pyridine, at N2Under protection, after 80-85 DEG C of backflow 4-6h, add water continuation backflow 18-22h, cold
But, H product are obtained；
(9) H product add frozen water, overnight, have brown-red solid to separate out, filter, dry, thick product through column chromatography purification,
Eluant is ethyl acetate: normal hexane, and eluant volume ratio is 4:6, obtains Orange red solid powder, obtains I product, to obtain final product；
Answering of a kind of aforesaid 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent
With, including
(1) as UV-Vis Spectrophotometry is used 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/water in water contain
Amount；
(3) the ELISA test strip pH value of solution of duty factor color reagent.
The application of aforesaid 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent, makees
For UV-Vis Spectrophotometry is used for detecting AcO in solution-、F-And during the colorimetric reagent of pH,
Detection method includes:
(1) UV-Vis Spectrophotometry detection F-: in acetonitrile solution, colorimetric reagent is at the ratio of 350nm and 595nm
Rate absorbance and F-Concentration is linear, detects F 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 detection AcO-: in the acetonitrile/water solution that volume ratio is 19/1, colorimetric reagent
Ratio absorbance and AcO at 350nm Yu 560nm-Concentration is linear, detects AcO with calibration curve method-, AcO-Dense
The range of linearity of degree is 1.0-45.0 μM, and detection is limited to 0.44 μM；
(3) UV-Vis Spectrophotometry detection pH: colorimetric reagent is at dimethyl sulfoxide/aqueous solution that volume ratio is 9/1
In, it being separately added into the Tirs-HCl buffer solution of at least 3 kinds of different pH value, described pH value is 3-9, takes solution and enters in cuvette
Row ultraviolet-visible spectrum measures；Absworption peak change with wavelength as 355nm and at 600nm, can detect pH scope is the molten of 6-9
Liquid.
The application of aforesaid 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent,
Described (1), in acetonitrile solution, UV-Vis Spectrophotometry detects F-Time, other counter anions are AcO-,
Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -One of, at concentration and F-Time identical, to F-Mensuration do not disturb；
Described (2), in the acetonitrile/water solution that volume ratio is 19/1, UV-Vis Spectrophotometry detects AcO-Time, its
His counter anion is F-, Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -One of, at concentration and AcO-Time identical, right
AcO-Mensuration do not disturb；
9. 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric as claimed in claim 6
The application of reagent, it is characterised in that: F in optical colorimetry detection solution-、AcO-, pH and optical colorimetry detection dimethyl sub-
In sulfone/water during water content, detection method includes:
(1) F in optical colorimetry detection solution-Time, concentration is in the colorimetric reagent acetonitrile solution of 20 μMs, under daylight, and F-From
When sub-concentration is respectively 0,10,100,1000 μMs, the change of colorimetric reagent solution colour corresponds to faint yellow, light blue, indigo respectively
Blue, cyan, detection is limited to 10 μMs；
(2) AcO in colorimetric reagent optical colorimetry detection solution-Time, concentration is that the colorimetric reagent of 20 μMs is in volume ratio
In the acetonitrile/water solution of 19/1, under daylight, at AcO-When ion concentration is respectively 0,10,100,1000 μMs, colorimetric reagent solution
Color change corresponds to faint yellow, crocus, lightpink, pink respectively, and detection is limited to 10 μMs；
(3) during the pH of colorimetric reagent optical colorimetry detection solution, concentration be the colorimetric reagent of 20 μMs be respectively 6 at pH,
7, during the concentration of 8,9 is the Tirs-HCl buffer solution of 5mM, the body of dimethyl sulfoxide/water is made with dimethyl sulfoxide/water dilution
Long-pending ratio is 9/1, and under daylight, in pH is respectively 6,7,8,9 buffer solution, the change 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/water during water content, concentration is the colorimetric reagent of 20 μMs
In the dimethyl sulfoxide/water buffer solution of different water contents, be respectively 1% at water content, 10%, 20%, 30%, 40%,
50%, 60%, 70%, 80% time, under daylight, colorimetric reagent solution colour change correspond to turquoise, sky blue, purple respectively
Color, royal purple, light violet magenta, pink, baby pink, pale pinkish grey, ivory white；Colorimetric reagent by visual colorimetric determination legal and
H in half-quantitative detection solution2The percentage composition of O, detection is limited to 1%.
The application of aforesaid 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent, negative
When carrying the ELISA test strip pH value of solution of colorimetric reagent, test strips is submerged initially in respectively the colorimetric reagent acetonitrile solution that concentration is 1mM
In carry out reagent load, take out, then test strips immersed respectively the Tirs-HCl that concentration is 0.05M that pH is 7,8,9,10 buffering
After solution, under daylight, the change of test strips color corresponds to yellow, light orange, orange red, aubergine respectively.
2-[2-hydroxyl-5-(4-nitroazobenzene) the styryl]-8-hydroxyquinoline ratio that the present invention is synthesized by applicant
Color reagent has carried out structure characterization test, draws 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 gained 2-[2-hydroxyl-5-(4-nitroazobenzene) benzene
Vinyl] chemical constitution of-8-hydroxyquinoline.
Table 1 structural characterization testing result
Table 2 mass spectrometric data
Table 3 infrared signature peak spectroscopic data
Table 4 carbon-13 nmr spectra data
For checking beneficial effects of the present invention, inventor has carried out substantial amounts of experimentation, part Experiment process and result
As follows:
1, to F-、AcO-There is identification test experience.In reagent-acetonitrile solution that colorimetric reagent concentration is 10 μMs, add respectively
Enter 200 μMs of aniones Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -During solution, do not observe the purple of colorimetric reagent
Outward-visible absorption spectra changes significantly；And add the F of 200 μMs-、AcO-Colorimetric reagent absworption peak at 350nm is made to subtract
Weak, new absworption peak occurs at 420nm, 595nm；At 418nm, there is isobestic point, form ratio at 350nm Yu 595nm and inhale
Receive, show that colorimetric reagent is to F with this understanding-、AcO-There is recognition detection effect.It is specifically shown in Fig. 1.
2, at the colorimetric reagent that concentration is 10 μMs in the acetonitrile/water solution of different volumes ratio, it is separately added into the F of 200 μMs-
Or AcO-After, measure the absorbance of maximum absorption wave strong point.Reagent-F in acetonitrile solution-, reagent-AcO-Extinction at 595nm
Degree maximum, in acetonitrile/water solution, reagent-F-, reagent-AcO-Maximum absorption wavelength violet shift to 560nm, absorbance reduces；
When acetonitrile/water (19/1, v/v), reagent-F-At 560nm, absorbance reduces than reagent-AcO-The absorbance at this wavelength
Reduce substantially.Show that colorimetric reagent detects F in acetonitrile solution simultaneously-、AcO-；Colorimetric reagent is molten in acetonitrile/water (19/1, v/v)
Liquid detects AcO-.Vertical coordinate 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 that colorimetric reagent concentration is 10 μMs, the F of 200 μMs is added-After have maximum at 595nm
Absworption peak, then at this reagent-F-Mixed solution adds the AcO of 200 μMs-After at the maximum absorption band of 595nm almost without change
Change；Otherwise, in the acetonitrile solution of the colorimetric reagent that concentration is 10 μMs, add the AcO of 200 μMs-After have absorption maximum at 595nm
Peak, then at this reagent-AcO-Mixed solution adds the F of 200 μMs-After have almost no change at the maximum absorption band of 595nm.Table
Bright with this understanding, AcO-Existence contrast color reagent detection F-Absorption spectrum have no significant effect；F-Existence contrast color reagent
Detection 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 that colorimetric reagent concentration is 10 μMs, it is separately added into variable concentrations F-To reagent solution
In, with F-Addition, record uv-visible absorption spectra titration curve.Colorimetric reagent absorption peak strength at 350nm is gradually
Reduce, and absorption peak strength gradually strengthens at 420nm, 595nm, has isobestic point at 418nm, formed at 350nm Yu 595nm
Ratio absorbs, with F-Concentration and linear change.It is specifically shown in Fig. 4.
5. in reagent-acetonitrile solution that colorimetric reagent concentration is 10 μMs, it is separately added into variable concentrations F-, measure ratio and inhale
Receipts value.Vertical coordinate is the ratio of absorbance at 595nm Yu 350nm wavelength, and abscissa is F-Concentration.F-Concentration is 1.0～25.0
In the range of μM, the ratio absorbance with reagent is linear.It is specifically shown in Fig. 5.
6., in reagent-acetonitrile solution that colorimetric reagent concentration is 10 μMs, add the F of 200 μMs-, AcO-, Cl-, Br-, I-,
HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -After, F-, AcO-Colorimetric reagent absorbance at 350nm is made to reduce, and at 595nm
Absorbance strengthen, the addition of other aniones is without this phenomenon；Measure the absorbance ratio at 595nm Yu 350nm.The most respectively to
Reagent-F-The absorbance ratio at 595nm and 350nm is measured after mixed solution adds other aniones above-mentioned of 200 μMs.Black
Vitta represents the absorbance ratio being separately added in colorimetric reagent after above-mentioned anion at wavelength 595nm Yu 350nm.White
Bar represents at reagent-F-Mixed solution is separately added into the suction at 595nm Yu 350nm again after other counter anions above-mentioned
Luminosity ratio.Show that colorimetric reagent detects F-Ratio absorbance do not included AcO-Coexist in interior other aniones above-mentioned
Impact.Vertical coordinate is that wavelength is respectively the ratio of absorbance at 595nm Yu 350nm.It is specifically shown in Fig. 6.
7. in reagent-acetonitrile-water (volume ratio of acetonitrile/water the is 19/1) solution that colorimetric reagent concentration is 10 μMs, point
Jia Ru 200 μMs of aniones F-, Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -Time, except I-And HSO4 -Addition make ratio
The uv-visible absorption spectra of color reagent has outside faint change, and the light of colorimetric reagent is not observed in the addition of remaining anion
Spectrum has significant change；And add the AcO of 200 μMs-Time, AcO-Make colorimetric reagent absworption peak at 350nm weaken, 420nm,
New absworption peak occurs at 560nm, at 410nm, has isobestic point, form ratio at 350nm Yu 560nm and absorb, show at this
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 the is 19/1) solution that colorimetric reagent concentration is 10 μMs, point
Jia Ru variable concentrations AcO-, with AcO-Addition, record uv-visible absorption spectra titration curve.Colorimetric reagent is at 350nm
The absorption peak strength at place is gradually lowered, and at 420nm, 560nm, absorption peak strength gradually strengthens, and has isobestic point at 410nm,
Form ratio at 350nm Yu 560nm to absorb, with AcO-Concentration and linear change.It is specifically shown in Fig. 8.
9. in reagent-acetonitrile-water (volume ratio of acetonitrile/water the is 19/1) solution that colorimetric reagent concentration is 10 μMs respectively
Add variable concentrations AcO-, measure ratio absorbance.Vertical coordinate is the ratio of absorbance at 560nm Yu 350nm wavelength, horizontal seat
It is designated as AcO-Concentration.AcO-Concentration ratio absorbance with reagent in the range of 1.0～45.0 μMs is linear.It is specifically shown in
Fig. 9.
10. in reagent-acetonitrile-water (volume ratio of acetonitrile/water the is 19/1) solution that colorimetric reagent concentration is 10 μMs, point
Jia Ru the AcO of 200 μMs-, F-, Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -After, AcO-Colorimetric reagent is made to exist
Absorbance at 350nm weakens, and the absorbance at 560nm strengthens, and the addition of other aniones is without this phenomenon；Measure
Absorbance ratio at 560nm Yu 350nm.The most respectively to reagent-AcO-In mixed solution add 200 μMs other the moon above-mentioned from
The absorbance ratio at 560nm and 360nm is measured after son.Black bar represents and adds after different anions at ripple in colorimetric reagent
Absorbance ratio at long 560nm Yu 350nm.White bars represents at reagent-AcO-Mixed solution is separately added into again above-mentioned its
After his counter anion, the absorbance ratio at 560nm Yu 350nm changes.Show that colorimetric reagent detects AcO-Ratio extinction
Degree is not included F-In the impact that interior other aniones above-mentioned coexist.Vertical coordinate is that wavelength is respectively suction at 560nm Yu 350nm
The ratio of luminosity.See Figure 10.
Under 11. daylight, colorimetric reagent concentration is in the reagent-acetonitrile solution of 20 μMs, at F-Ion concentration is respectively 0,10,
100,1000 μMs time, colorimetric reagent solution colour change correspond to faint yellow, light blue, indigo, cyan respectively.Mesh can be passed through
F is detected depending on colorimetry quantitative and semi-quantitative-Ion, detection is limited to 10 μMs.It is specifically shown in Figure 11.
Under 12. daylight, colorimetric reagent concentration is that the reagent-acetonitrile-water (volume ratio of acetonitrile/water is 19/1) of 20 μMs is molten
Liquid, at AcO-When ion concentration is respectively 0,10,100,1000 μMs, the change of colorimetric reagent solution colour corresponds to yellowish respectively
Color, crocus, lightpink, pink.Thus can detect AcO by optical colorimetry quantitative and semi-quantitative-Ion, detection limit
It it is 10 μMs.See Figure 12.
13. at reagent-dimethyl sulfoxide-water that colorimetric reagent concentration is 10 μMs, (volume ratio of dimethyl sulfoxide/water is 9/
1), in solution, it is separately added into the Tirs-HCl buffer of the different pH that concentration is 5mM.When pH is 3～6, colorimetric reagent solution
Uv-visible absorption spectra figure is without significant change；When pH is 7～9, colorimetric reagent at the absworption peak of 355nm with the increase of pH value
Intensity is gradually lowered, and occurs new absworption peak at 600nm, and intensity strengthens with the increase of pH value, shows that colorimetric reagent is two
Methyl sulfoxide/water (9/1, v/v) solution can detect weak acid that pH scope is 6～9 to weakly alkaline solution.It is specifically shown in Figure 13.
Under 14 daylight, colorimetric reagent concentration is reagent-dimethyl sulfoxide-water (volume ratio of dimethyl sulfoxide/water of 20 μMs
It is 9/1) solution, in the Tirs-HCl buffer solution that concentration is 5mM of pH respectively 6,7,8,9, colorimetric reagent solution colour
Change corresponds to light yellow, light green color, light blue, sky blue respectively.Thus can visual detection pH scope be 6～9 weak acid extremely
Weakly alkaline solution, is specifically shown in Figure 14.
Under 15. daylight, test strips is submerged initially in the dimethyl sulphoxide solution of the colorimetric reagent that concentration is 1mM, takes out, again
After filter paper bar immerses the Tirs-HCl buffer solution that concentration is 0.05M that pH is 7,8,9,10 respectively, filter paper bar color changes
Correspond to yellow, light orange, orange red, aubergine respectively.Show that with reagent filter paper bar can visual detection pH scope be 7～10
Neutral to weakly alkaline solution.
Under 16. daylight, concentration is the reagent solution of 20 μMs, at dimethyl sulfoxide/water (pH 9,2mM of different water contents
Tirs-HCl), in buffer solution, be respectively 1% at water content, 10%, 20%, 30%, 40%, 50%, 60%, 70%,
When 80%, reagent solution color change correspond to respectively turquoise, sky blue, purple, royal purple, light violet magenta, pink,
Baby pink, pale pinkish grey, ivory white.Thus can be by H in optical colorimetry quantitative and semi-quantitative detection solution2The percentage composition of O,
Detection is limited to 1%.It is specifically shown in Figure 16.
Compared with prior art, the method have the advantages that
(1) colorimetric reagent highly sensitive, high can select detection specific ion, molecule, has that testing cost is low, speed fast, sets
Standby simple, method easy, the feature such as directly perceived, be widely used analyzing detection field.Colorimetric reagent can not only visual detection, qualitative
Analyze, moreover it is possible to the spectral quality absorbed by means of ratio, form isobestic point when utilizing detection, there is the suction of different wave length simultaneously
The change receiving peak ratio is measured, and has higher detection sensitivity and accuracy.The i.e. ratio of ratio utilizing absorbance absorbs
Detection mode is different from the change-detection of the absorbance of single wavelength, the in actual applications composition of object under inspection, colorimetric examination
The impact of the factors such as agent concentration, test condition, light source fluctuation and instrument sensitivity is little, by absorbance under two different wave lengths
Ratio changes, and reduces the factor affecting Accurate Determining, and the responsing linear range of detection, detection limit, accuracy can be made to significantly improve.
(2) recognition property is superior.The colorimetric reagent of the present invention, by controlling different solvents or solvent ratio, uses ratio to inhale
Receiving method, selective enumeration method plurality of target ion.Can not only detect with ratio absorption pattern, and can be used for visual colorimetric determination
Quickly detect F-、AcO-、pH、H2O and pH reagent paper.Realize the multifunctional application of single agents.
Accompanying drawing illustrates:
Fig. 1 be colorimetric reagent in acetonitrile solution with the uv-visible absorption spectra figure of anion；
Fig. 2 be different volumes ratio acetonitrile/water solution in colorimetric reagent-F-, reagent-AcO-Absorbance variation diagram；
Fig. 3 is colorimetric reagent and F in acetonitrile solution-、AcO-And F-、AcO-The uv-visible absorption spectra figure coexisted；
Fig. 4 is the F of variable concentrations in acetonitrile solution-The uv-visible absorption spectra titration figure of contrast color reagent；
Fig. 5 is colorimetric reagent detection F in acetonitrile solution-UV-Vis Spectrophotometry correction graph；
Fig. 6 is counter anion contrast color reagent UV-Vis Spectrophotometry detection F in acetonitrile solution-Affect figure；
Fig. 7 is colorimetric reagent and the uv-visible absorption spectra figure of anion in acetonitrile/water (19/1, v/v) solution；
Fig. 8 is the AcO of variable concentrations in acetonitrile/water (19/1, v/v) solution-The ultraviolet-ray visible absorbing light of contrast color reagent
Spectrum titration figure；
Fig. 9 is colorimetric reagent detection AcO in acetonitrile/water (19/1, v/v) solution-UV-Vis Spectrophotometry correction
Curve chart；
Figure 10 is counter anion contrast color reagent UV-Vis Spectrophotometry in acetonitrile/water (19/1, v/v) solution
Detection AcO-Affect figure；
Figure 11 is in acetonitrile solution, colorimetric reagent visual colorimetric determination detection variable concentrations F under daylight-Solution colour change shine
Sheet；
Figure 12 is in acetonitrile/water (19/1, v/v) solution, colorimetric reagent visual colorimetric determination detection variable concentrations AcO under daylight-
Solution colour change photo；
Figure 13 be dimethyl sulfoxide/water (9/1, v/v), different pH buffer solution in the ultraviolet-visible of colorimetric reagent inhale
Receive spectrogram；
Figure 14 is in dimethyl sulfoxide/water (9/1, v/v), and under daylight, colorimetric reagent visual colorimetric determination detection different pH buffering is molten
The color change photo of liquid；
Figure 15 is the test strips color change photo of the different pH buffer solution of colorimetric reagent detection；
Figure 16 is colorimetric reagent visual detection difference H2The solution colour photo of O content.
Detailed description of the invention
Embodiment 1:
The chemical structural formula of 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline is:
Its preparation method is:
A, intermediate: the synthesis of 2-hydroxyl-5-(4-nitroazobenzene) benzaldehyde:
In 100ml there-necked flask, add paranitroanilinum (1.38g, 10mmol) and 4ml concentrated hydrochloric acid and 5ml water, treat that it is molten
Under cryosel is bathed, it is cooled to 0～5 DEG C after solution, 5ml sodium nitrite in aqueous solution is slowly dropped into wherein, continue under ice bath after adding
Reaction 2h, adjusts pH=7 with sodium hydroxide solution, and the aqueous solution that then will contain salicylide (1.22g, 10mmol) 20ml adds it
In, continue reaction 4h, after having reacted, have red precipitate to separate out, filter, dried in vacuum overnight, oxolane recrystallization, obtain 2-hydroxyl
Base-5-(4-nitroazobenzene) benzaldehyde.Productivity 53.5%.
The preparation of b, 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline
In 25mL microwave reaction pipe, add 8-hydroxy-2-methylquinoline 0.11g (0.69mmol), the 2-of above-mentioned preparation
Hydroxyl-5-(4-nitroazobenzene) benzaldehyde and 10mL acetic anhydride, be mixed to form orange-red solution, at a temperature of 128-132 DEG C,
Microwave power 50W, microwave reaction 60min；After reaction terminates, move to round-bottomed flask, in reactant liquor, add 100mL frozen water, stir
Mix 2h, orange-yellow solid occurs, filter, be dried, obtain 0.3g solid intermediate；This intermediate solid is placed in 100mL tri-neck
In Ping, add 20mL pyridine, at N2Under protection, reflux at 80-85 DEG C 5h, adds 9mL water, continues backflow 20h, cooling, adds
The frozen water of 100mL, overnight, has henna solid to separate out, and filters, and is dried, and crude by column chromatography purification, eluant is acetic acid
Ethyl ester: normal hexane, eluant volume ratio is 4:6, obtains Orange red solid powder 2-[2-hydroxyl-5-(4-nitroazobenzene) benzene second
Thiazolinyl]-8-hydroxyquinoline.Productivity 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 compound method of various reagent in analysis method of the present invention:
(1) preparation of colorimetric reagent dimethyl sulfoxide storing solution: weigh 20.6mg colorimetric reagent and (make by embodiment 1
Standby), with dmso solution and be configured to the colorimetric reagent dimethyl sulfoxide storing solution 50mL that concentration is 1mM；
The preparation of colorimetric reagent acetonitrile storing solution: weigh 20.6mg colorimetric reagent (being prepared by embodiment 1), use acetonitrile
Dissolve and be configured to the colorimetric reagent acetonitrile storing solution 50mL that concentration is 1mM；
(2)F-Storing solution is prepared: weighing tetrabutyl ammonium fluoride 0.3155g, dissolving with acetonitrile and being configured to concentration is 20mM
Tetrabutyl ammonium fluoride acetonitrile storing solution 50mL.
(3)AcO-Storing solution is prepared: weigh tetrabutylammonium acetate ammonium 0.3015g, dissolves with acetonitrile and is configured to concentration and is
The tetrabutylammonium acetate acetonitrile storing solution 50mL of 20mM.
Other aniones (Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4-, PF6 -) preparation of storing solution: take corresponding
4-butyl ammonium acetonitrile dissolves and is diluted to the anion acetonitrile storing solution of 20mM.
(4) Tris-HCl buffer solution (0.5M): with concentration be 0.5M trihydroxy methyl (triamido) ethane (Tris) and
0.5M HCl prepares, and regulates pH to 2～10；
Tris-HCl buffer solution (0.2M): be 0.2M trihydroxy methyl (triamido) ethane (Tris) and 0.2M by concentration
HCl prepares, and regulates pH to 9；
Tris-HCl buffer solution (0.05M): with concentration be 0.05M trihydroxy methyl (triamido) ethane (Tris) and
0.05M HCl prepares, and regulates pH to 2～10；PH value compound glass electrode measures through acidometer.
Agents useful for same is analytical reagent, and test water is ultra-pure water.
Ultraviolet-visible spectrophotometer model used by the present invention is UV-1800 (Shimadzu Corporation of Japan)；Model 818 type
Acidometer (Ao Lilong company of the U.S.)；Microwave Synthesis System model is Discover SP, and U.S. CE M company produces.
Embodiment 3:
(1) UV-Vis Spectrophotometry detection F-
In 10mL volumetric flask, add colorimetric reagent acetonitrile storing solution (1mM, 0.1mL), by dilution in acetonitrile to scale, shake
Even, obtain colorimetric reagent solution, take colorimetric reagent solution about 3mL in the cuvette of 1cm, carry out uv-visible absorption spectra survey
Fixed；
After being separately added into colorimetric reagent acetonitrile storing solution (1mM, 0.1mL) in series 10mL volumetric flask, 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
To scale, shake up, take solution about 3mL in the cuvette of 1cm, carry out uv-visible absorption spectra mensuration.
After being separately added into colorimetric reagent acetonitrile storing solution (1mM, 0.1mL) in series 10mL volumetric flask, then it is separately added into
Anion F-, AcO-Storing solution (20mM, 0.1mL), is diluted to scale by acetonitrile/water respectively, makes the volume of acetonitrile/water in solution
Ratio is 100/0,19/1,9/1,17/3,4/1,3/1, shakes up, and obtains reagent solution, takes reagent solution about 3mL in the cuvette of 1cm
In carry out uv-visible absorption spectra mensuration.
Anion F of 200 μMs it is separately added in the colorimetric reagent acetonitrile solution that concentration is 10 μMs-, 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
Receipts peak weakens, and new absworption peak occurs at about 420nm, 595nm；Isobestic point is had, shape at 350nm Yu 595nm at 418nm
Become ratio to absorb, show that reagent is to F with this understanding-、AcO-There is recognition detection effect.(such as Fig. 1).
Concentration be the colorimetric reagent of 10 μMs in the acetonitrile/water solution of different volumes ratio, be separately added into the AcO of 200 μMs-Or
F-After, measure the absorbance of maximum absorption wave strong point.Reagent-F in acetonitrile solution-, reagent-AcO-At 595nm, absorbance is
Greatly, in acetonitrile/water solution, reagent-F-, reagent-AcO-Maximum absorption wavelength violet shift to 560nm, absorbance reduces, and reduces
Degree is different；When acetonitrile/water (19/1, v/v), reagent-F-At 560nm, absorbance reduces than reagent-AcO-At this wavelength
Absorbance reduce substantially (Fig. 2).Therefore, control to survey the ratio of acetonitrile/water in colorimetric examination solution, make colorimetric reagent molten at acetonitrile
Liquid detects F-；Colorimetric reagent detects AcO in acetonitrile/water (19/1, v/v) solution-。
In the colorimetric reagent acetonitrile solution that concentration is 10 μMs, add the F of 200 μMs-After have maximum absorption band at 595nm,
Again at this reagent-F-Mixed solution adds the AcO of 200 μMs-After have almost no change at the maximum absorption band of 595nm；Otherwise,
In the acetonitrile solution of the reagent that concentration is 10 μMs, add the AcO of 200 μMs-After have maximum absorption band at 595nm, then in this examination
Agent-AcO-Mixed solution adds the F of 200 μMs-After have almost no change (Fig. 3) at the maximum absorption band of 595nm.Show at this
Under the conditions of, AcO-Existence contrast color reagent detection F-Absorption spectrum have no significant effect；F-Existence contrast color reagent detection
AcO-Absorption spectrum have no significant effect, namely F-And AcO-The most not detection of interference ratio color reagent.
In the acetonitrile solution of the colorimetric reagent that concentration is 10 μMs, it is separately added into the F of variable concentrations-Rear mensuration obtains purple
Outward-visible absorption spectra titration curve (such as Fig. 4).Measure F-Colorimetric reagent extinction at 350nm and 595nm during concentration change
The ratio of degree, it is thus achieved that ratio absorption correction curve (such as Fig. 5).By the slope of calibration trace and the standard deviation of 10 blank values of mensuration
Difference, measures and is calculated colorimetric reagent ultraviolet-ray visible absorbing method detection F-The concentration range of linearity and detection limit, be listed in table 4.
Colorimetric reagent detection F-Absorbance ratio at 350nm and 595nm, includes AcO in other aniones above-mentioned-Point
It is not present in reagent-F as coexisting ion-In mixed solution, as the F of other anion concentrations Yu test-Time quite, other is cloudy
Ion pair colorimetric reagent detection F-Ratio absorbance impact relative deviation within 5%, not interference measurement (such as Fig. 6).
Table 4 colorimetric reagent UV-Vis Spectrophotometry detection F-Analytical parameters
(2) UV-Vis Spectrophotometry detection AcO-
In 10mL volumetric flask, add colorimetric reagent acetonitrile storing solution (1mM, 0.1mL), be diluted to scale by acetonitrile/water,
Making acetonitrile/water volume ratio in solution is 19/1, shakes up, obtains colorimetric reagent solution, takes colorimetric reagent solution about 3mL in the ratio of 1cm
Color ware carries out uv-visible absorption spectra mensuration；
After being separately added into colorimetric reagent acetonitrile storing solution (1mM, 0.1mL) in series 10mL volumetric flask, 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
Being diluted to scale, making acetonitrile/water volume ratio is 19/1, shakes up, and takes solution about 3mL and carries out ultraviolet-visible in the cuvette of 1cm
Absorption spectromtry.
In colorimetric reagent acetonitrile/water (19/1, the v/v) solution that concentration is 10 μMs, it is separately added into the anion of 200 μMs
F-, Cl-, Br-, I-, AcO-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -Time, only AcO-Addition make colorimetric reagent solution exist
Absworption peak at 350nm weakens, and occurs new absworption peak at 420nm, 560nm, has isobestic point at 410nm, 350nm with
Form ratio at 560nm to absorb, show that colorimetric reagent is to AcO with this understanding-There is recognition detection effect (such as Fig. 7).
In colorimetric reagent acetonitrile/water (19/1, the v/v) solution that concentration is 10 μMs, add the AcO of variable concentrations-Rear survey
Surely uv-visible absorption spectra titration curve (such as Fig. 8) is obtained.Measure AcO-During concentration change colorimetric reagent at 350nm and
The ratio of the absorbance at 560nm, it is thus achieved that ratio absorption correction curve (such as Fig. 9).By the slope of calibration trace and measure 10 times
The standard deviation of blank value, measures and is calculated colorimetric reagent UV-Vis Spectrophotometry detection AcO-Concentration linear
Scope and detection limit, be listed in table 5.
Colorimetric reagent detection AcO-Absorbance ratio at 350nm and 560nm, includes F in other aniones above-mentioned-Point
It is not present in reagent-AcO as coexisting ion-In mixed solution, as the AcO of other anion concentrations Yu test-Time quite, its
Its anion contrast color reagent detection AcO-Ratio absorbance impact relative deviation within 5%, not interference measurement (as figure
10)。
Table 5 colorimetric reagent UV-Vis Spectrophotometry detection AcO-Analytical parameters
(3) UV-Vis Spectrophotometry detection pH
In 10mL volumetric flask add colorimetric reagent dimethyl sulfoxide stock solution (1mM, 0.1mL), with dimethyl sulfoxide/
Water is diluted to scale, and making dimethyl sulfoxide/water volume ratio is 9/1, shakes up, and obtains colorimetric reagent solution, takes colorimetric reagent solution about
3mL carries out uv-visible absorption spectra mensuration in the cuvette of 1cm；
After being separately added into colorimetric reagent dimethyl sulfoxide stock solution (1mM, 0.1mL) in series 10mL volumetric flask, then
It is separately added into the Tirs-HCl buffer solution (0.5M, 20 μ L) that pH is 3,4,5,6,7,8,9, is diluted to dimethyl sulfoxide/water
Scale, making dimethyl sulfoxide/water volume ratio is 9/1, after shaking up, takes solution about 3mL and carries out ultraviolet-can in the cuvette of 1cm
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
Reagent solution is gradually lowered with the increase intensity of pH value at the absworption peak of 355nm, new absworption peak occurs at 600nm, intensity with
The increase of pH value and strengthen, showing that colorimetric reagent can detect pH scope in dimethyl sulfoxide (9/1, v/v) solution is 6～9
Weak acid is to weakly alkaline solution (such as Figure 13).
Embodiment 4:
(1) F in colorimetric reagent optical colorimetry detection solution-
In series bottle, it is separately added into colorimetric reagent acetonitrile storing solution (1mM, 40 μ L), then is separately added into different volumes
The F that concentration is 20mM-After storing solution, by dilution in acetonitrile to 2mL, obtain reagent-F-Solution.Under daylight, at F-Ion concentration is respectively
When being 0,10,100,1000 μMs, the change of colorimetric reagent solution colour corresponds to faint yellow, light blue, indigo, cyan respectively.
Thus can detect F by optical colorimetry quantitative and semi-quantitative-Ion, detection is limited to 10 μMs (such as Figure 11).
(2) AcO in colorimetric reagent optical colorimetry detection solution-
In series bottle, it is separately added into colorimetric reagent acetonitrile storing solution (1mM, 40 μ L), then is separately added into different volumes
The AcO that concentration is 20mM-After storing solution, being diluted to 2mL by acetonitrile/water, making acetonitrile/water volume ratio is 19/1, obtains colorimetric examination
Agent-AcO-Solution；Under daylight, at AcO-When ion concentration is respectively 0,10,100,1000 μMs, colorimetric reagent solution colour changes
Correspond to faint yellow, crocus, lightpink, pink respectively.Thus can be detected by optical colorimetry quantitative and semi-quantitative
AcO-Ion, detection is limited to 10 μMs (such as Figure 12).
(3) pH of colorimetric reagent optical colorimetry detection solution
In series bottle, it is separately added into colorimetric reagent dimethyl sulfoxide stock solution (1mM, 40 μ L), then is separately added into
Tirs-HCl (0.5M, the 20 μ L) buffer solution of different pH value, is diluted to 2mL with dimethyl sulfoxide/water, make dimethyl sulfoxide/
Water volume ratio is 9/1.Under daylight, concentration is dimethyl sulfoxide (9/1, the v/v) solution of the colorimetric reagent of 20 μMs, is respectively at pH
6, during the concentration of 7,8,9 is the Tirs-HCl buffer solution of 5mM, colorimetric reagent solution colour change correspond to respectively light yellow,
Light green color, light blue, sky blue.Show colorimetric reagent can visual detection pH scope be 6～9 weak acid to weakly alkaline solution (as
Figure 14).
(4) the ELISA test strip pH value of solution of duty factor color reagent
Ordinary filter paper is cut to 15mm × 40mm and makees pH test paper slip, filter paper bar is immersed the colorimetric reagent two of 1.0mM
Methyl sulfoxide solution, after colorimetric reagent is carried on test strips, then immerses the different pH that concentration is 0.05M by this test strips
In Tirs-HCl buffer soln, with the difference of pH, under daylight, test strips presents different colours.PH is respectively 7,8,9,10
Buffer solution, the change of test strips color corresponds to yellow, light orange, orange red, aubergine.Show after colorimetric reagent loads
Test strips can visual detection pH scope be that the neutrality of 7～10 is to weakly alkaline solution (such as Figure 15).
(5) water content in colorimetric reagent optical colorimetry detection dimethyl sulfoxide/water
In series bottle, being configured to concentration with the colorimetric reagent dimethyl sulfoxide stock solution that concentration is 1mM is 20 μMs
Colorimetric reagent solution, in the buffer solution of the dimethyl sulfoxide/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, pale pinkish grey,
Ivory white；Thus can be by H in optical colorimetry quantitative and semi-quantitative detection solution2The percentage composition of O, detection be limited to 1% (as
Figure 16).
Claims (10)
1. 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent, it is characterised in that:
The chemical structural formula of described colorimetric reagent is:
2. 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric examination as claimed in claim 1
Agent, it is characterised in that: described colorimetric reagent is mainly 0.5M's by the paranitroanilinum 5-15 part calculated by thing mass parts, concentration
Salicylide aqueous solution 5-15 part, 8-hydroxy-2-methylquinoline 0.3-0.9 part and the Asia that concentration is 2.5M that by volume part calculates
Sodium nitrate aqueous solution 1-10 part, mass fraction are concentrated hydrochloric acid 1-8 part of 36-38%, acetic anhydride 5-15 part and pyridine 10-30 part system
For forming.
3. 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric examination as claimed in claim 2
Agent, it is characterised in that: described colorimetric reagent is mainly the water of 0.5M by the paranitroanilinum calculated by thing mass parts 10 parts, concentration
Poplar aldehyde aqueous solution 10 parts, 8-hydroxy-2-methylquinoline 0.69 part and the sodium nitrite that concentration is 2.5M that by volume part calculates
Aqueous solution 5 parts, mass fraction are that the concentrated hydrochloric acid 4 parts of 36-38%, acetic anhydride 10 parts and pyridine 20 parts are prepared from.
4. 2-[2-hydroxyl-5-(4-nitroazobenzene) the styryl]-8-hydroxyl as according to any one of claim 1-3
The preparation method of base quinoline colorimetric reagent, it is characterised in that: synthesize according to following route:
5. 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent as claimed in claim 4
Preparation method, it is characterised in that: comprise the following steps:
(1) in paranitroanilinum, add concentrated hydrochloric acid and the water that mass fraction is 36-38%, dissolve, obtain A product；
(2), after A product are cooled to 0～5 DEG C under cryosel is bathed, it are slowly dropped into the sodium nitrite in aqueous solution that concentration is 2.5M, obtain B product；
(3) after B product react 1-3h under ice bath, adjust pH=7 with sodium hydroxide solution, obtain C product；
(4) in C product, add the salicylide aqueous solution that concentration is 0.5M, react 3-5h, have red precipitate to separate out after having reacted, mistake
Filter, dried in vacuum overnight, oxolane recrystallization, obtain D product；
(5), during D product are placed in microwave reaction pipe, add 8-hydroxy-2-methylquinoline and acetic anhydride, be mixed to form orange-red solution,
Obtain E product；
(6) E product in 128-132 DEG C, microwave power be 48-52W under the conditions of react 55-65min, obtain F product；
(7) in F product, add frozen water, stir 1-3h, orange/yellow solid occurs, filter, be dried, obtain G product；
(8) G product add pyridine, at N2Under protection, after 80-85 DEG C of backflow 4-6h, add water continuation backflow 18-22h, and cooling obtains H
Product；
(9) adding frozen water in H product, overnight, have brown-red solid to separate out, filter, be dried, thick product is through column chromatography purification, eluting
Agent is ethyl acetate: normal hexane, and eluant volume ratio is 4:6, obtains Orange red solid powder, obtains I product, to obtain final product.
6. 2-[2-hydroxyl-5-(4-nitroazobenzene) the styryl]-8-hydroxyl as according to any one of claim 1-3
The application of base quinoline colorimetric reagent, it is characterised in that: include
(1) as UV-Vis Spectrophotometry is used 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/water in water content；
(3) the ELISA test strip pH value of solution of duty factor color reagent.
7. 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent as claimed in claim 6
Application, it is characterised in that: as UV-Vis Spectrophotometry is used for detecting AcO in solution-、F-And the colorimetric examination of pH
During agent, detection method includes:
(1) UV-Vis Spectrophotometry detection F-: in acetonitrile solution, colorimetric reagent is at the ratio extinction of 350nm Yu 595nm
Angle value and F-Concentration is linear, detects F with calibration curve method-, F-The range of linearity of concentration is 1.0-25.0 μM, detection limit
It it is 0.63 μM；
(2) UV-Vis Spectrophotometry detection AcO-: in the acetonitrile/water solution that volume ratio is 19/1, colorimetric reagent exists
The ratio absorbance of 350nm Yu 560nm and AcO-Concentration is linear, detects AcO 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 detection pH: colorimetric reagent is in dimethyl sulfoxide/aqueous solution that volume ratio is 9/1,
Being separately added into the Tirs-HCl buffer solution of at least 3 kinds of different pH value, described pH value is 3-9, takes solution and carries out in cuvette
Ultraviolet-visible spectrum measures；Absworption peak change with wavelength as 355nm and at 600nm, can detect pH scope is the molten of 6-9
Liquid.
8. 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent as claimed in claim 7
Application, it is characterised in that:
Described (1), in acetonitrile solution, UV-Vis Spectrophotometry detects F-Time, other counter anions are AcO-, Cl-,
Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -One of, when concentration is identical with F-, to F-Mensuration do not disturb；
Described (2), in the acetonitrile/water solution that volume ratio is 19/1, UV-Vis Spectrophotometry detects AcO-Time, other are altogether
Depositing anion is F-, Cl-, Br-, I-, HSO4 -, NO3 -, ClO4 -, H2PO4 -, PF6 -One of, at concentration and AcO-Time identical, to AcO-
Mensuration do not disturb.
9. 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric reagent as claimed in claim 6
Application, it is characterised in that: optical colorimetry detection solution in F-、AcO-, pH and optical colorimetry detection dimethyl sulfoxide/
In water during water content, detection method includes:
(1) F in optical colorimetry detection solution-Time, concentration is in the colorimetric reagent acetonitrile solution of 20 μMs, under daylight, and F-Ion is dense
When degree is respectively 0,10,100,1000 μMs, the change of colorimetric reagent solution colour correspond to respectively faint yellow, light blue, indigo,
Cyan, detection is limited to 10 μMs；
(2) AcO in colorimetric reagent optical colorimetry detection solution-Time, concentration be the colorimetric reagent of 20 μMs be 19/1 in volume ratio
In acetonitrile/water solution, under daylight, at AcO-When ion concentration is respectively 0,10,100,1000 μMs, colorimetric reagent solution colour becomes
Changing and correspond to faint yellow, crocus, lightpink, pink respectively, detection is limited to 10 μMs；
(3) colorimetric reagent optical colorimetry detection solution pH time, concentration is that the colorimetric reagent of 20 μMs is respectively 6,7,8,9 at pH
The Tirs-HCl buffer solution that concentration is 5mM in, make the volume ratio of dimethyl sulfoxide/water with the dilution of dimethyl sulfoxide/water
Being 9/1, under daylight, in pH is respectively 6,7,8,9 buffer solution, the change 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/water during water content, concentration is that the colorimetric reagent of 20 μMs is not
With in the dimethyl sulfoxide/water buffer solution of water content, be respectively 1% at water content, 10%, 20%, 30%, 40%, 50%,
60%, 70%, 80% time, under daylight, the change of colorimetric reagent solution colour corresponds to turquoise, sky blue, purple, dark purple respectively
Redness, light violet magenta, pink, baby pink, pale pinkish grey, ivory white；Colorimetric reagent passes through optical colorimetry quantitative and semi-quantitative
H in detection solution2The percentage composition of O, detection is limited to 1%.
10. 2-[2-hydroxyl-5-(4-nitroazobenzene) styryl]-8-hydroxyquinoline colorimetric examination as claimed in claim 6
The application of agent, it is characterised in that: during the ELISA test strip pH value of solution of duty factor color reagent, test strips is submerged initially in concentration respectively is
The colorimetric reagent acetonitrile solution of 1mM carries out reagent load, takes out, then test strips is immersed respectively the concentration that pH is 7,8,9,10
After the Tirs-HCl buffer solution of 0.05M, under daylight, the change of test strips color corresponds to yellow, light orange, orange red respectively
Color, aubergine.
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Cited By (4)
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| CN107389572A (en) * | 2017-07-27 | 2017-11-24 | 青岛市食品药品检验研究院 | A kind of detection method of olive oil Determination of Chlorophyll copper |
| CN108548788A (en) * | 2018-04-26 | 2018-09-18 | 贵州大学 | One kind detecting AcO in aqueous solution-Or F-Reagent and its detection method |
| CN111233801A (en) * | 2020-03-06 | 2020-06-05 | 北京师范大学 | Colorimetric probe for rapidly detecting solvent components and preparation method and application thereof |
| CN114989081A (en) * | 2022-05-10 | 2022-09-02 | 南华大学 | Colorimetric probe and preparation method and application thereof |
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| 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107389572A (en) * | 2017-07-27 | 2017-11-24 | 青岛市食品药品检验研究院 | A kind of detection method of olive oil Determination of Chlorophyll copper |
| CN107389572B (en) * | 2017-07-27 | 2020-04-14 | 青岛市食品药品检验研究院 | Method for detecting copper chlorophyll in olive oil |
| CN108548788A (en) * | 2018-04-26 | 2018-09-18 | 贵州大学 | One kind detecting AcO in aqueous solution-Or F-Reagent and its detection method |
| CN111233801A (en) * | 2020-03-06 | 2020-06-05 | 北京师范大学 | Colorimetric probe for rapidly detecting solvent components and preparation method and application thereof |
| CN111233801B (en) * | 2020-03-06 | 2021-09-07 | 北京师范大学 | Colorimetric probe for rapidly detecting solvent components and preparation method and application thereof |
| CN114989081A (en) * | 2022-05-10 | 2022-09-02 | 南华大学 | Colorimetric probe and preparation method and application thereof |
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