CN111610172B - Detection of hydrazine and cyanide in water sample by dual-response optical probe rhodamine B derivative - Google Patents
Detection of hydrazine and cyanide in water sample by dual-response optical probe rhodamine B derivative Download PDFInfo
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- 239000000523 sample Substances 0.000 title claims abstract description 114
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000001514 detection method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 230000003287 optical effect Effects 0.000 title claims abstract description 17
- 230000004044 response Effects 0.000 title claims abstract description 12
- 230000009977 dual effect Effects 0.000 title claims abstract description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical class [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 title description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 61
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 61
- 230000008859 change Effects 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 23
- 238000002189 fluorescence spectrum Methods 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000001506 fluorescence spectroscopy Methods 0.000 claims description 7
- 238000000862 absorption spectrum Methods 0.000 claims description 4
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
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- 125000005597 hydrazone group Chemical group 0.000 abstract 1
- 238000005935 nucleophilic addition reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
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- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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Abstract
The invention relates to a dual-response optical probe for detecting hydrazine and cyanide in a water sample. The optical probe takes dicyano as an identification group, and is designed and synthesized into hydrazine (N) 2 H 4 ) And Cyanide (CN) ‑ ) 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid. When N is present in the sample 2 H 4 When N 2 H 4 The reaction with dicyano can generate corresponding hydrazone structure, so that fluorescence excitation and emission generate blue shift, and hydrazine is detected by utilizing the change of the fluorescence signal, wherein the linear range is 0-10 mu M, and the detection limit is 80nM. Furthermore, when CN is present in the sample ‑ When CN ‑ Can generate nucleophilic addition reaction with dicyano to obviously enhance the fluorescence emission of the probe at 470nm, and the change of the fluorescence signal is utilized to carry out CN ‑ The linear range was 0-30. Mu.M, and the detection limit was 0.33. Mu.M. Thus, the change in the different fluorescent signals can be used for N 2 H 4 And CN ‑ Respectively measuring, overcoming the need of designing and synthesizing two different fluorescent probes to respectively detect N 2 H 4 And CN ‑ Is not enough.
Description
Technical Field
The invention relates to a dual-response optical probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid for detecting hydrazine and cyanide in a water sample.
Background
Hydrazine and cyanide have been widely used in chemical industry and agriculture such as agricultural chemical, synthetic fiber, herbicide, plastic manufacturing, and resin industry as two important roles in industrial production. In sharp contrast to their use, hydrazine and cyanide both exhibit deleterious effects on the body and are readily absorbed by the human body through oral and skin absorption, thereby causing damage to central nervous, cardiac, endocrine and metabolic systems. At the same time, social environmental safety is also facing threats and challenges due to its good water solubility. In order to prevent hydrazine and cyanide from causing harm to the health of people and the surrounding ecological environment, the limit values of hydrazine and cyanide in the environment are strictly regulated in countries around the world. Therefore, the establishment of a method for detecting hydrazine and cyanide with high efficiency, high sensitivity and high selectivity is of great significance.
The currently reported methods for detecting hydrazine and cyanide mainly comprise: chromatographic, titration and electrochemical analysis methods solve the problems of hydrazine and cyanide detection to different degrees, but have different defects in aspects of detection sensitivity, complicated operation conditions, expensive instruments and the like. Fluorescent probes are receiving much attention compared to the above methods because of their high selectivity, high sensitivity, ease of handling, freedom from damage and applicability to biological environments. However, if the fluorescent probes of hydrazine or cyanide are designed and synthesized separately, more financial and material resources are consumed, and the fluorescent probes are not friendly to the environment. Based on the method, the invention establishes a fluorescence analysis method with high efficiency, good selectivity and high sensitivity, monitors hydrazine and cyanide in an environmental water sample, can improve the detection efficiency, reduce the synthesis cost of a probe and achieve the purpose of controlling environmental pollution.
Existing fluorescent probe technology for detecting N 2 H 4 And CN - Two different fluorescent probes need to be designed and synthesized respectively, so that more time and cost are consumed, and environmental pollution is caused. The invention overcomes the defects of the prior art. The dual-response optical probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid was synthesized by a simple reaction. The probe can be respectively connected with N based on different reaction mechanisms and solvent proportions 2 H 4 And CN - And the reaction is carried out, so that the detection under different fluorescent signals is realized. Probe and N 2 H 4 After the reaction, the (Z) -2- (6- (diethylamino) -4- (benzidine) -2, 3-dihydro-1H-xanthene) benzoic acid is generated, the maximum wavelength of ultraviolet absorption is obviously reduced at 623nm, the maximum wavelength is slightly enhanced at 420nm, and the fluorescence emission ratio I is improved 565 /I 645 With N 2 H 4 The increase in concentration is enhanced. Probe and CN - The fluorescence emitted by the product after the addition reaction at 470nm is obviously enhanced,fluorescence emission value with CN - The increase in concentration is enhanced. The invention is used for N in wastewater samples 2 H 4 And CN - Content is measured separately based on the ratio I of fluorescence emission intensity 565 /I 645 And N 2 H 4 Concentration, fluorescence enhancement at 470nm and CN - The linear relation of the concentration is calculated, the minimum detection limit is 80nM and 0.33 mu M respectively, and the safety of the detected environment can be reasonably evaluated.
The synthesized double-response optical probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid has stable optical property, good selectivity and high sensitivity, and is a rapid and simple method for detecting traps and cyanide.
Disclosure of Invention
The purpose of the invention is that: double-response optical probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid for N in water sample 2 H 4 And CN - Is detected.
The invention aims at realizing the following technical scheme:
synthesis of optical probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid:
0.403g of 2- (6- (diethylamino) -4-formyl-2, 3-dihydro-1H-xanthene) benzoic acid and 0.08g of malononitrile were dissolved in 10mL of acetonitrile, followed by dropwise addition of 5 to 7 drops of piperidine and reflux under nitrogen for 6 hours. After the reaction, the mixture was dried by spin-drying, and the obtained solid was dissolved in methylene chloride. Then washing with water three times, drying with anhydrous sodium sulfate, and finally separating and purifying by column chromatography, wherein the eluent ratio is dichloromethane/methanol=50: 1, a bluish violet solid was obtained in 0.288g with a yield of 64%.
The synthetic structural formula of the optical probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid is shown in figure 1.
The invention has the advantages and the beneficial effects that:
if the existing fluorescent probe technology is used for detecting N 2 H 4 And CN - Then respectively design and synthesis of twoDifferent fluorescent probes are used, so that the environment is polluted, and more time and cost are consumed. The invention overcomes the defects of the prior art. The dual-response optical probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid is synthesized by utilizing a simple organic reaction. The probe can be respectively connected with N based on different reaction mechanisms and solvent proportions 2 H 4 And CN - The reaction takes place, fig. 2, enabling detection under different fluorescent signals. Probe and N 2 H 4 After the reaction, the (Z) -2- (6- (diethylamino) -4- (benzidine) -2, 3-dihydro-1H-xanthene) benzoic acid is generated, the maximum wavelength of ultraviolet absorption is obviously reduced at 623nm, the maximum wavelength is slightly enhanced at 420nm, and the fluorescence emission ratio I is improved 565 /I 645 With N 2 H 4 The increase in concentration is enhanced. Probe and CN - The fluorescence emission of the product after the addition reaction is obviously enhanced at 470nm, and the fluorescence emission value is along with CN - The increase in concentration is enhanced. The invention is used for N in wastewater samples 2 H 4 And CN - Content is measured separately based on the ratio I of fluorescence emission intensity 565 /I 645 And N 2 H 4 Concentration, fluorescence enhancement at 470nm and CN - The linear relation of the concentration is calculated, the minimum detection limit is 80nM and 0.33 mu M respectively, and the safety of the detected environment can be reasonably evaluated. The synthesized double-response optical probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid has stable optical property, good selectivity and high sensitivity, and is a rapid and simple method for detecting traps and cyanide.
Drawings
FIG. 1 is a diagram showing the synthesis of 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid.
FIG. 2 shows the synthesized 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid and N 2 H 4 And CN - Is a reaction mechanism diagram of (a).
FIG. 3 shows the synthesized 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid in deuterated chloroform 1 H NMR spectrum.
FIG. 4 shows the synthesized 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid in deuterated dimethyl sulfoxide 13 C NMR spectrum.
FIG. 5 is a high-resolution mass spectrum of synthesized probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid, 452.1968[ M+H ] + ]Is the molecular ion peak of the probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid.
FIG. 6 shows the synthesis of probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid and N, respectively 2 H 4 And CN - And (5) carrying out high-resolution mass spectrogram on the reacted product.
FIG. 7 is a 20. Mu.M probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid with 40. Mu. M N 2 H 4 Ultraviolet absorption spectrum (a) and fluorescence emission spectrum (B) before (dotted line) and after (solid line) the reaction.
FIG. 8 is a 20. Mu.M probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid with 100. Mu.M CN - Ultraviolet absorption spectrum (a) and fluorescence emission spectrum (B) before (dotted line) and after (solid line) the reaction.
FIG. 9 shows the detection of N by 20. Mu.M probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid in the presence of other interferents 2 H 4 (A) And CN - (B) Fluorescence spectrum histogram.
FIG. 10 shows 20. Mu.M probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid with different concentrations of N 2 H 4 Changes in fluorescence spectrum (A) after action and fluorescence intensity I 565 /I 645 And N 2 H 4 Linear relationship of concentration.
FIG. 11 shows 20. Mu.M probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid with different concentrations of CN - Change (A) in fluorescence spectrum after action and fluorescence intensity lambda em =470 nm and CN - Linear relationship of concentration.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings and examples:
example 1
0.403g of 2- (6- (diethylamino) -4-formyl-2, 3-dihydro-1H-xanthene) benzoic acid and 0.08g of malononitrile were dissolved in 10mL of acetonitrile, followed by dropwise addition of 5 to 7 drops of piperidine and reflux under nitrogen for 6 hours. After the reaction, the mixture was dried by spin-drying, and the obtained solid was dissolved in methylene chloride. Then washing with water three times, drying with anhydrous sodium sulfate, and finally separating and purifying by column chromatography, wherein the eluent ratio is dichloromethane/methanol=50: 1, a bluish violet solid 0.288g was obtained in 64% yield, giving probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid.
9 probe solutions of 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid having a concentration of 20. Mu.M were prepared in parallel, and N having different concentrations was added thereto, respectively 2 H 4 Standard solution, after 35 minutes, respectively measuring fluorescence spectrograms of the above solutions, recording fluorescence emission intensity, and according to fluorescence intensity value I 565 /I 645 And N 2 H 4 The relationship of concentration draws a standard curve.
Preparing 20 mu M probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid solution, adding sample solution into the solution, measuring fluorescence spectrum chart after 35 min, recording fluorescence emission intensity change, calculating N in sample according to the standard curve 2 H 4 Is a concentration of (3).
9 probe solutions of 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid having a concentration of 20. Mu.M were prepared in parallel, and CN having different concentrations was added thereto, respectively - Standard solution, after 30 minutes, respectively measuring fluorescence spectrum of the above-mentioned solution, recording fluorescence emission intensity, according to fluorescence intensity value at 470nm and CN - The relationship of concentration draws a standard curve.
A20. Mu.M probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid solution was prepared, and a sample solution was added theretoAfter 30 minutes, the liquid was measured for fluorescence spectrum, the change of fluorescence emission intensity was recorded, and CN in the sample was calculated from the standard curve described above - Is a concentration of (3).
After the probe is synthesized, a nuclear magnetic resonance spectrometer is used for testing the product to obtain a hydrogen spectrogram 3, and the chemical shift data are as follows: 1 h NMR (400 mhz, chloro-d) δ=8.21 (d, j=7.8 hz, 1H), 8.09 (s, 1H), 7.69 (t, j=7.6 hz, 1H), 7.57 (t, j=7.6 hz, 1H), 7.15 (d, j=7.5 hz, 1H), 6.53 (d, j=2.5 hz, 1H), 6.47 (d, j=9.0 hz, 1H), 6.37 (dd, j=9.0, 2.5hz, 1H), 3.42 (d, j=7.4 hz, 4H), 2.83 (t, j=6.2 hz, 2H), 2.19-2.09 (m, 2H), 1.67 (p, j=6.3 hz, 2H), 1.22 (t, j=7.0 hz, 6H) gave its carbon shift profile with chemical shift data of 4: 13 C NMR(101MHz,DMSO-d 6 )δ＝167.37,160.66,154.88,150.93,148.28,147.96,135.97,133.20,131.10,131.06,130.14,129.56,127.48,119.62,118.90,118.08,111.85,110.74,108.82,
97.07,62.21,44.58,26.54,25.85,24.79,20.63,19.09,12.99 the high resolution mass spectrum 5 shows that its molecular weight is ESI-MS M/z [ M+H ] + ]＝452.1968.
The above characterization demonstrates the success of the synthesis of the probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid.
High resolution Mass Spectrum 6 verifies that probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid was reacted with N respectively 2 H 4 And CN - Mechanism of reaction.
Example 2
1. Spectral experiments
The ultraviolet-visible absorption spectrum and fluorescence emission spectrum of the compound probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid were first measured. As shown in FIG. 7, 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid itself showed a strong absorption band at 623nm, with N 2 H 4 After 35 minutes of reaction, the absorption band at 623nm was significantly reduced, while the absorption peak at 420nm was slightly enhanced, with a concomitant change in the color of the solution from blue-violet to yellow, indicating N 2 H 4 With 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1HXanthene) benzoic acid reaction to give new species having different spectral properties than the probe. In addition, fluorescence spectroscopy of the probe solution showed that significant fluorescence enhancement and signal attenuation were observed at 565nm and 645nm, respectively, when excited at 515nm, as shown in FIG. 7-B. The probe and N 2 H 4 The change in fluorescence spectral properties before and after the reaction can be used to determine the concentration of N in the sample 2 H 4 Content detection of (2). In addition, the probe and CN - After 30 minutes of reaction, a significantly enhanced fluorescence signal was observed at 470nm, and the red fluorescence of the original probe was found to have been converted to blue under the irradiation of a fluorescent lamp, so that the probe was reacted with CN - The change in fluorescence spectral properties before and after the reaction can also be used to determine the concentration of CN in a sample - Content detection of (e.g., FIG. 8).
To verify the pair N of probes 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid, respectively 2 H 4 And CN - Selectivity of the assay, the invention combines 20. Mu.M 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid with other possible interfering components (500. Mu.M, NH) 4 + ,Ca 2+ ,Mg 2+ ,Zn 2+ ,Fe 3+ ,Ac - ,Br - ,Cl - ,ClO 4 - ,F - ,I - ,NO 2 - ,HSO 3 - ,NO 3 - ,CO 3 2- ,S 2- ,SO 3 2- ,SO 4 2- ,PO 4 3- ,H 2 O 2 ) After incubation for 35 min, fluorescence emission spectra of probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid at 515nm excitation wavelength and 375nm excitation wavelength were recorded with a fluorescence spectrophotometer, respectively. As shown in FIG. 9, when the probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid was reacted with N 2 H 4 And CN - After the action, the fluorescence emission ratio I 565 /I 645 And the emission at 470nm is significantly enhanced, while there is no significant change in fluorescence after interaction with other analytes. At the same time, at N 2 H 4 Or CN - In the coexistence of other interferents, 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid is still opposite to N 2 H 4 Or CN - Has good recognition effect, as shown in figure 9. This result demonstrates that 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid can be used as a substrate for N 2 H 4 And CN - Specific recognition is realized.
2. Concentration titration experiments based on the probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid can pair N 2 H 4 Or CN - Characteristic features of specific recognition, the present invention studied the probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid for N 2 H 4 Or CN - Is used for the quantitative detection of the strain. The quantitative performance of the invention is examined by using fluorescence emission spectrum. mu.L 1mmol/L probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid was mixed with 480. Mu.L dimethyl sulfoxide and 1mM N was added in various volumes 2 H 4 Solution, fixed volume to 1mL with 12mM phosphate buffer solution, incubating for 35 min, and recording probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid and its and N with a fluorescence spectrophotometer 2 H 4 Fluorescence emission spectrum of the product after the reaction. As can be seen from FIG. 9-A, the fluorescence emission spectrum thereof follows N 2 H 4 The increase in concentration, the fluorescence emission of 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid molecule at 565nm was gradually increased, accompanied by a decrease in fluorescence emission at 645nm, and its emission intensity was 0-10. Mu.MN 2 H 4 The concentrations showed a good linear relationship and the detection limit LOD could reach 80nM, FIG. 9-B. Description probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid can be used for N by fluorescence spectrometer 2 H 4 Quantitative analysis was performed.
mu.L of 1mmol/L probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid was mixed with 880. Mu.L DMSO and 1mM of a different volume of a solution of unsymmetrical dimethylhydrazine was added to the mixture, 1After incubation for 30 minutes with a 2mM phosphate buffer solution to a volume of 1mL, the fluorescence emission spectra of the probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid and its product after reaction with cyanide were recorded with a fluorescence spectrophotometer. As can be seen from FIG. 11-A, the fluorescence emission spectrum thereof follows CN - Increasing concentration, the fluorescence emission of 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid molecule at 470nm is gradually enhanced, and the emission intensity is 0-30 mu M CN - The concentrations showed good linear relationship, the detection limit LOD could reach 0.22. Mu.M, and FIG. 11-B shows that the probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid could be used for the CN with a fluorescence spectrometer - Quantitative analysis was performed.
3. Determination of hydrazine and cyanide content in water sample
To verify that the probe was specific for N in the actual sample 2 H 4 And CN - Suitability for detection the invention measures N in a water sample from the university of Lanzhou Yuxiu lake 2 H 4 And CN - And a labeled recovery experiment was performed. Experiment shows that N in Yuxiu lake water sample 2 H 4 The standard recovery rate of (2) is shown in Table 1, in which the probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid is said to be applicable to N in an actual water sample 2 H 4 And CN - Is detected.
The specific method comprises the following steps:
a. sample processing
Yuxiu lake water sample was obtained from Yuxiu lake, university of Lanzhou, and the obtained water sample was filtered with a microporous membrane of 0.22. Mu.m.
b. Determination of hydrazine and cyanide content in actual sample by fluorescence spectrometry
mu.L of the above-treated actual sample was taken, 20. Mu.L of a 1mmol/L probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid solution and 480. Mu.L of dimethyl sulfoxide were added, and the mixture was shaken and incubated at room temperature for 35 minutes, and fluorescence emission spectra at an excitation wavelength of 515nm were recorded by a fluorescence spectrophotometer. Furthermore, a certain amount of N is added into the actual sample 2 H 4 Standard solutionAnd (3) detecting according to the operation after the volume is fixed, and calculating to obtain the corresponding standard recovery rate. Table 1 shows N in a water sample from Yuxiu lake 2 H 4 And (5) adding standard recovery rate experimental data.
Table 1 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid N in actual samples 2 H 4 And (3) the recovery rate of the addition mark.
mu.L of the above-treated actual sample was taken, 20. Mu.L of a 1mmol/L probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid solution and 880. Mu.L of dimethyl sulfoxide were added, and the mixture was shaken and incubated at room temperature for 30 minutes, and fluorescence emission spectra at an excitation wavelength of 375nm were recorded by a fluorescence spectrophotometer. Furthermore, a certain amount of CN is added into the actual sample - And (3) detecting the standard solution according to the operation after the volume is fixed, and calculating to obtain the corresponding standard adding recovery rate. Table 2 shows CN in Yuxiu lake water sample - And (5) adding standard recovery rate experimental data.
Table 2 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid on actual sample CN - Is measured and marked to recover
By reacting probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid with N 2 H 4 Or CN - The research of optical properties before and after the reaction proves that the molecular probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid synthesized by the invention can realize the N-fluorescence emission spectrum 2 H 4 Or CN - Compared with the traditional detection method, the invention has stable optical property, good specificity, high sensitivity and high detection efficiency, and is a rapid and simple detection method for detecting N 2 H 4 Or CN - Is a simple method.
Claims (1)
1. A dual-response optical probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid is used for detecting the content of hydrazine and cyanide in a water sample, and comprises the following steps:
a. probe spectroscopic properties probe: accurately weighing 2.25mg of probe, dissolving the probe by using dimethyl sulfoxide and fixing the volume to 5.0mL to obtain 1mmol/L of probe stock solution, taking 20 mu L of 1mmol/L of probe stock solution, adding 480 mu L of dimethyl sulfoxide, and diluting the probe stock solution to 1.0mL by using 12mM phosphate buffer salt solution to obtain 20 mu M of probe solution A; measuring ultraviolet absorption and fluorescence emission spectrums of the probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid by using an ultraviolet absorption spectrometer and a fluorescence spectrometer respectively, wherein the maximum wavelength of ultraviolet absorption is 623nm, and the probe has stronger fluorescence emission at 645 nm;
b. probe pair N 2 H 4 Response to (2): add 40. Mu.L of 1mmol/L N to probe solution A 2 H 4 After 35 minutes in aqueous solution, (Z) -2- (6- (diethylamino) -4- (benzidine) -2, 3-dihydro-1H-xanthene) benzoic acid is generated, the maximum wavelength of ultraviolet absorption is obviously reduced at 623nm, the maximum wavelength of ultraviolet absorption is slightly enhanced at 420nm, the fluorescence emission of the original probe at 645nm is obviously reduced, meanwhile, new fluorescence emission appears at 565nm, and meanwhile, with the change of the color of the solution from deep blue to light yellow, the probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid can perform the fluorescence emission mode on N 2 H 4 Performing qualitative ratio detection analysis; adding N with concentration of 0-40 μm into the probe solution A 2 H 4 After 35 minutes, the aqueous solution was observed for color change, fluorescence emission spectrum was examined, and fluorescence emission intensities at 565nm and 645nm were recorded, according to 0-10. Mu. M N 2 H 4 Ratio I of concentration to fluorescence emission spectrum intensity 565 /I 645 Establishing a standard linear equation: y=0.154+0.738 [ n ] 2 H 4 ]The detection limit LOD can reach 80nM; adding probe solution A to a solution containing N 2 H 4 After 35 minutes, the color change was observed while detecting the presence of N by fluorescence emission spectroscopy 2 H 4 And calculating N in the sample according to a standard curve equation 2 H 4 The content is as follows;
c. probe pair CN - Response to (2): mu.L of 1mmol/L probe stock solution was additionally taken, 880. Mu.L of dimethyl sulfoxide was added, and diluted to 1.0mL with 12mM phosphate buffer solution to give 20. Mu.M probe solution B; to which 100. Mu.M CN was added - After 30 minutes, the maximum wavelength of ultraviolet absorption of the aqueous solution is reduced at 623nm, the fluorescence emission of the generated product at 470nm is obviously enhanced, the color of the solution is changed from deep blue to light blue, the fluorescence color is changed from red to blue, and the probe 2- (4- (2, 2-dicyano) -6- (diethylamino) -2, 3-dihydro-1H-xanthene) benzoic acid can also perform fluorescence emission on CN - Quantitative detection and analysis are carried out; adding CN with concentration of 0-100 μm into probe solution B - After 30 minutes, the aqueous solution was detected by fluorescence emission spectroscopy, the fluorescence emission intensity at 470nm was recorded, according to 0-30. Mu.M CN - Establishing a standard linear equation for the concentration and fluorescence emission spectrum intensity: y=85.85+4.353 [ cn - ]The detection limit LOD can reach 0.22 mu M; adding probe solution B containing CN - After 30 minutes, the wastewater sample containing CN was detected by fluorescence emission spectroscopy - And calculating CN in the sample according to a standard curve equation - The content is as follows.
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