CN102590163A - Method for detecting bisulfite ion - Google Patents
Method for detecting bisulfite ion Download PDFInfo
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- CN102590163A CN102590163A CN2012100119596A CN201210011959A CN102590163A CN 102590163 A CN102590163 A CN 102590163A CN 2012100119596 A CN2012100119596 A CN 2012100119596A CN 201210011959 A CN201210011959 A CN 201210011959A CN 102590163 A CN102590163 A CN 102590163A
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Abstract
The invention provides a method for detecting bisulfite ion HSO<3->, and in particular relates to a method for quantitatively detecting the bisulfite ion based on a coumarin derivatives 7-diethylaminocoumarin-3-aldehyde (DEACA). Particularly, the content of the bisulfite ion is quantitatively detected by DEACA in aid of fluorescence spectrum in a 10mM disodium hydrogen phosphate-citric acid buffer solution with pH of 5.0. The method has the characteristics of high sensitivity and selectivity to the bisulfite ion, convenient, sensitive and quick detection process and accurate detection result.
Description
Technical field
The present invention relates to sulphurous acid cyanogen root check and analysis technology, specifically belong to a kind of method based on coumarin derivative detection by quantitative sulphurous acid cyanogen root.
Background technology
Sulphite is owing to the reaction of growth that in production and storage, can stop oxidation and bacterium and control enzyme becomes many foods, beverage and the most basic antiseptic of medical product.Certain density sulphurous acid cyanogen root can cause some individual asthma and irritated.The index of sulphite in food and medicine controlled by strictness.For example in China, the index of sulphite in grape wine and in the beer can not surpass 0.05mgkg
-1With regard to consumer's safety, the new analytical approach of development sulphite is very important.At present the method for sulphurous acid cyanogen root is a Neil WILLIAMS-DARLING Ton method not in the detection food that adopts of official, and this method is dull, and is consuming time; Also have some conventional methods in addition: phosphorimetry, chromatograph, galvanochemistry, enzyme process etc., however these methods need loaded down with trivial details sample pretreatment or need complicated instrument and equipment.
Summary of the invention
The object of the present invention is to provide that a kind of system is simple, easy to operate, selectivity is high, the method for the detection by quantitative sulphurous acid cyanogen root of highly sensitive, good water solubility.
The reagent of the detection sulphurous acid cyanogen root that the present invention adopts is coumarin derivative 7-diethylaminocoumarin-3-aldehyde (DEACA), reference literature (T.-K.Kim, D.-N.Lee; H.-J.Kim, Tetrahedron Lett., 2008; 49,4879.) synthetic.Synthetic route is:
A kind of method that detects sulphurous acid cyanogen root provided by the invention comprises the steps:
(1), preparation pH=5.0,0.2M Na
2HPO
4-citric acid solution, and with the DEACA ethanolic solution of ethanol preparation 2mM;
(2), 400: 1 by volume with Na
2HPO
4-citric acid solution and DEACA ethanolic solution are added in the clean fluorescence cuvette, on XRF, detect, and along with the adding of treating test sample, tangible fluorescence appears in 483nm to be strengthened, and along with the increase of sulphurous acid cyanogen root concentration, fluorescence intensity also increases;
(3), prepare the HSO of 2mM with distilled water
3 -Solution is the Na of 2mL
2HPO
4The DEACA ethanolic solution of-citric acid solution and 5 μ L is added in the fluorescence cuvette, adds HSO gradually
3 -The volume of solution is 5,10,20,40,60,80,100,120,140,160,180,200uL; The fluorescence intensity F that on XRF, measures the correspondence of 483nm simultaneously is 70,78,94,138,160,190,221,252,284,302,329,355, with HSO
3 -Concentration is horizontal ordinate, with relative intensity of fluorescence F-F
0(F
0=40) draw figure for ordinate, obtain the working curve of sulphurous acid cyanogen root concentration; Equation of linear regression is: F-F
0=24.19+1.51c (c=10
-6Mol/L);
(4), during working sample solution with the fluorescence intensity substitution equation of linear regression that records, can try to achieve the concentration of sulphurous acid cyanogen root.
Through experiment showed, other negative ion comprise halfcystine (Cys) not interference system to the mensuration of sulphurous acid cyanogen root.
Compared with prior art, the present invention has following advantage and effect: 1, detection architecture is with low cost, and reagent is to make in two steps of primary raw material by salicylaldehyde derivatives, and raw material is cheap, and reaction conditions is simple, is easy to produce; 2, detection method of the present invention has shown high sensitivity and selectivity to sulphurous acid cyanogen root; 3, testing process is easy, quick, and testing result is accurate; 4, detection means is simple, only needs to borrow XRF.
Description of drawings:
The single crystal diffraction structural drawing of Fig. 1 embodiment 1DEACA.
The fluorescent emission figure of Fig. 2 embodiment 2DEACA and the effect of sulphurous acid cyanogen root.
The fluorescent emission figure of Fig. 3 embodiment 3DEACA and various negative ion effects.
The fluorescence histogram of Fig. 4 embodiment 4DEACA and various negative ion effects and color map.
Fig. 5 embodiment 5 working curve diagrams.
Sulphurous acid cyanogen radical content is measured figure in Fig. 6 embodiment 6 sugar.
Embodiment:
Embodiment 1
DEACA's is synthetic: with the ethylenediamine salicylide of 0.01mol, the diethyl malonate of 0.02mol, 1mL piperidines are dissolved in the ethanol of 30mL, refluxing and stirring 6 hours; Steam ethanol, stirred concentrated hydrochloric acid and each this system of 20mL adding of glacial acetic acid again 6 hours, add the 100mL frozen water; Using 40% NaOH solution accent pH is 5, stirs 30 minutes again, and potpourri filters; Washing, drying obtains 7-diethylaminocoumarin with the benzene recrystallization.
Dry 2mLDMF, 2mLPOCl
3, 30 ℃ down stir 30 minutes after, merge with the 10mLDMF solution of the 7-diethylaminocoumarin of 0.007mol; Stirred 12 hours down at 60 ℃, add the 100mL frozen water then, transfer pH to occur until a large amount of depositions with NaOH; Filtration of crude product, washing obtains DEACA with ethyl alcohol recrystallization.
Growing the grain in ethanol obtains yellow monocrystalline.
The sign of DEACA:
1H-NMR(CDCl
3)δ10.13(s，1H)，8.26(s，1H)，7.43(d，1H)，6.67(d，1H)，6.50(s，1H)，3.49(m，4H)，1.25(t，6H)；Elemental?analysis(calcd.％)for?C
14H
15NO
3：68.56；H，6.16；N，5.71：Found：C，68.57；H，6.18；N，5.74；EI-MS?m/z?245[M]
+.Crystal?data?for?C
14H
15NO
3：crystal?size：0.20×0.12×0.02，monoclinic，space?group?C2/c(No.15).
β＝153.003(9)°，
Z＝4，T＝173K，θ
max＝25.0°，5129?reflections?measured，2145unique(R
int＝0.0525).Final?residual?for?176?parameters?and?2145?reflections?with?I＞2σ(I)：R
1＝0.0864，wR
2＝0.1681?and?GOF＝1.174。The single crystal diffraction structural drawing is seen Fig. 1.
Preparation pH=5.0,0.2M Na
2HPO
4-citric acid solution, and with the DEACA solution of ethanol preparation 2mM; The Na of 2mL
2HPO
4The DEACA ethanolic solution of-citric acid solution and 5 μ L is added in the clean fluorescence cuvette, gets HSO
3 -Solution, be added in this cuvette with microsyringe gradually, application of sample limit, limit is detected on the fluorescence spectrophotometry appearance, along with HSO
3 -Adding, 483nm place fluorescence intensity strengthens gradually.Fluorescent emission figure sees Fig. 2.
Preparation pH=5.0,0.2M Na
2HPO
4-citric acid solution, and with the DEACA solution of ethanol preparation 2mM; In 13 fluorescence cuvettes, each adds the Na of 2mL
2HPO
4The DEACA ethanolic solution of-citric acid solution and 5 μ L adds the HSO of 40 molar equivalents more respectively
3 -, and other various (F of 400 molar equivalents
-, Cl
-, Br
-, NO
3 -, CN
-, SCN
-, S
2O
3 2-, AcO
-, CO
3 2-, SO
4 2-, ClO
4 -) and halfcystine (Cys), obtain fluorescent emission figure and see Fig. 3.
Embodiment 4
In 13 fluorescence cuvettes, each adds the Na of 2mL
2HPO
4The DEACA ethanolic solution of-citric acid solution and 5 μ L adds the HSO of 40 molar equivalents more respectively
3 -, and other various (F of 400 molar equivalents
-, Cl
-, Br
-, NO
3 -, CN
-, SCN
-, S
2O
3 2-, AcO
-, CO
3 2-, SO
4 2-, ClO
4 -) and halfcystine (Cys), on the fluorescence spectrophotometry appearance, detect, draw the histogram of the corresponding 483nm fluorescence intensity of different anions, see Fig. 4.
Through experiment showed, other negative ion comprise Cys not interference system to the mensuration of sulphurous acid cyanogen root.
Embodiment 5
HSO with distilled water preparation 2mM
3 -Solution is the Na of 2mL
2HPO
4The DEACA ethanolic solution of-citric acid solution and 5 μ L is added in the fluorescence cuvette, adds HSO gradually
3 -The volume of solution is 5,10,20,40,60,80,100,120,140,160,180,200uL; The fluorescence intensity F that on XRF, measures the correspondence of 483nm simultaneously is 70,78,94,138,160,190,221,252,284,302,329,355, with HSO
3 -Concentration is horizontal ordinate, with relative intensity of fluorescence F-F
0(F
0=40) draw figure for ordinate, obtain the working curve of sulphurous acid cyanogen root concentration; Equation of linear regression is: F-F
0=24.19+1.51c (c=10
-6Mol/L).
Embodiment 6
10g white sugar fully is dissolved in the 15mL water, the Na of 2mL
2HPO
4The DEACA ethanolic solution of-citric acid solution and 5 μ L is added in the fluorescence cuvette, adds the good refined sugar solution 674uL of dissolving, fluorescence intensity F=152 on the XRF, and the equation of linear regression of substitution embodiment 5 gets c
1=58 * 10
-6Mol/L, the concentration of sulphurous acid cyanogen root is c in the refined sugar solution so
M=58 * 10
-6* 2674/674=270 * 10
-6Mol/L, the concentration that obtains sulphurous acid cyanogen root in the white sugar thus is 270 * 10
-6* 15 * 10
-3* 81 * 100=32.8mg/Kg, fluorometric assay figure sees Fig. 6.
Claims (1)
1. a method that detects sulphurous acid cyanogen root is characterized in that, comprises the steps:
(1), preparation pH=5.0,0.2M Na
2HPO
4-citric acid solution, and the DEACA ethanolic solution of preparation 2mM;
(2), 400: 1 by volume with Na
2HPO
4-citric acid solution and DEACA ethanolic solution are added in the clean fluorescence cuvette, on XRF, detect, and along with the adding of treating test sample, tangible fluorescence appears in 483nm to be strengthened, and along with the increase of sulphurous acid cyanogen root concentration, fluorescence intensity also increases;
(3), prepare the HSO of 2mM with distilled water
3 -Solution is the Na of 2mL
2HPO
4The DEACA ethanolic solution of-citric acid solution and 5 μ L is added in the fluorescence cuvette, adds HSO gradually
3 -The volume of solution is 5,10,20,40,60,80,100,120,140,160,180,200uL; The fluorescence intensity F that on XRF, measures the correspondence of 483nm simultaneously is 70,78,94,138,160,190,221,252,284,302,329,355, with HS θ
3 -Concentration is horizontal ordinate, with relative intensity of fluorescence F-F
0(F
0=40) draw figure for ordinate, obtain the working curve of sulphurous acid cyanogen root concentration; Equation of linear regression is: F-F
0=24.19+1.51c (c=10
-6Mol/L);
(4), during working sample solution with the fluorescence intensity substitution equation of linear regression that records, can try to achieve the concentration of sulphurous acid cyanogen root.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103149184A (en) * | 2013-02-04 | 2013-06-12 | 山西大学 | Fluorescence detection method for hypochlorite |
| CN105203512A (en) * | 2015-09-16 | 2015-12-30 | 山西大学 | Carbazole fluorescent probe and preparation method and application thereof |
| CN105334202A (en) * | 2015-11-18 | 2016-02-17 | 华南理工大学 | Method for detecting cyanide ions through triphenylamine dye |
| CN105733566A (en) * | 2016-04-27 | 2016-07-06 | 天津理工大学 | Fluorescent probe used for sulfite or bisulphate and preparation method and application thereof |
| CN106092993A (en) * | 2016-07-14 | 2016-11-09 | 长沙理工大学 | Rapid detection method of cyanide ions |
| CN107474044A (en) * | 2017-08-10 | 2017-12-15 | 河北大学 | A kind of coumarin derivatives, its preparation method and application and a kind of bisulfite detection kit |
| CN112147113A (en) * | 2019-06-26 | 2020-12-29 | 西南交通大学 | Application of coumarin derivative in quantitative detection of sulfur dioxide |
| CN113402468A (en) * | 2021-06-03 | 2021-09-17 | 山西大学 | Biphenylnitrile derivative with AIE and ESIPT characteristics and synthetic method and application thereof |
-
2012
- 2012-01-15 CN CN2012100119596A patent/CN102590163A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 彭梦姣 等: "香豆素类亚硫酸氢根离子探针的合成及荧光性质研究", 《精细化工》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103149184A (en) * | 2013-02-04 | 2013-06-12 | 山西大学 | Fluorescence detection method for hypochlorite |
| CN105203512A (en) * | 2015-09-16 | 2015-12-30 | 山西大学 | Carbazole fluorescent probe and preparation method and application thereof |
| CN105203512B (en) * | 2015-09-16 | 2018-02-06 | 山西大学 | A kind of carbazoles fluorescence probe and its preparation method and application |
| CN105334202A (en) * | 2015-11-18 | 2016-02-17 | 华南理工大学 | Method for detecting cyanide ions through triphenylamine dye |
| CN105733566A (en) * | 2016-04-27 | 2016-07-06 | 天津理工大学 | Fluorescent probe used for sulfite or bisulphate and preparation method and application thereof |
| CN106092993A (en) * | 2016-07-14 | 2016-11-09 | 长沙理工大学 | Rapid detection method of cyanide ions |
| CN106092993B (en) * | 2016-07-14 | 2019-01-18 | 长沙理工大学 | Rapid detection method of cyanide ions |
| CN107474044A (en) * | 2017-08-10 | 2017-12-15 | 河北大学 | A kind of coumarin derivatives, its preparation method and application and a kind of bisulfite detection kit |
| CN107474044B (en) * | 2017-08-10 | 2019-12-06 | 河北大学 | Coumarin derivative, preparation method and application thereof, and bisulfite detection kit |
| CN112147113A (en) * | 2019-06-26 | 2020-12-29 | 西南交通大学 | Application of coumarin derivative in quantitative detection of sulfur dioxide |
| CN113402468A (en) * | 2021-06-03 | 2021-09-17 | 山西大学 | Biphenylnitrile derivative with AIE and ESIPT characteristics and synthetic method and application thereof |
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Application publication date: 20120718 |