CN111635376A - Trivalent As detection probe, preparation method and application thereof - Google Patents
Trivalent As detection probe, preparation method and application thereof Download PDFInfo
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- CN111635376A CN111635376A CN202010524448.9A CN202010524448A CN111635376A CN 111635376 A CN111635376 A CN 111635376A CN 202010524448 A CN202010524448 A CN 202010524448A CN 111635376 A CN111635376 A CN 111635376A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
- C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- 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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- 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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
Abstract
The invention discloses a trivalent As detection probe, a preparation method and application thereof, wherein the probe has the following structural formula:
the trivalent As detection probe provided by the invention has the advantages of simple preparation method, low cost, high sensitivity, low detection limit and high selectivity, can be specifically used for detecting the content of As, and is particularly suitable for detecting the content of As in products such As naphtha and the like.
Description
Technical Field
The invention relates to the technical field of environmental analysis, in particular to an As detection probe and application thereof.
Background
Arsenic (As) is one of the most toxic species to humans because it can invade the nervous system and circulatory system, interrupt the Krebs cycle, and cause bladder and lung cancer. Arsenic is also a teratogenic toxic element, which, due to its presence in natural water, can cause serious health problems associated with skin toxicity, cardiovascular disease, neurodegenerative disease, and the like. The physical state and chemical structure of the involved compounds show a higher degree of arsenic toxicity, with arsenite (III) in inorganic form being higher than arsenate (V) and the organic form of the element. However, the natural abundance of inorganic species is high. It is well known that arsenite (AsO) is present in an oxidizing environment3-) And arsenous acid (AsH)3) Predominate in reducing atmospheres, while arsenate (AsO)4 3-) Predominate in oxidizing environments. Long term low level consumption is harmful and the risk of cancer is high. The world health organization specifies that 10ppb is the highest tolerance level for arsenic in drinking water. Therefore, determining AS at the ppb level is critical and extremely challenging.
The existing arsenic detection methods mainly comprise AAS, AES, ICP and the like. Given that the above methods require expensive instrumentation and high-tech operations and pre-treatment procedures, colorimetric and fluorescent sensors are potential monitoring methods to advance the ease of use of monitoring devices for in vivo and in vitro species of arsenic. However, there are few reports on the arsenic-based fluorescence sensor compared to other inorganic substances, and the reports on the arsenic-based fluorescence sensor also have little concern about its sensing mechanism and biosensing application. Arsenic species, like naphtha, are often found in mines and petroleum, and the abundance of arsenic species in their surrounding environment has raised global public health concerns.
Therefore, there is a need for a fluorescent sensor for rapid detection of arsenic content in naphtha products and related fields.
Disclosure of Invention
The invention aims to provide a method for rapidly detecting the content of trivalent As, in particular to the content of trivalent As in naphtha products and related fields.
In order to achieve the above object, the present invention provides a trivalent As detection probe having the following structural formula:
the invention also provides a preparation method of the trivalent As detection probe, which takes 2-hydroxy-5-methyl m-phthalaldehyde and o-aminothiophenol As raw materials to prepare according to the following route:
preferably, the dosage ratio of the 2-hydroxy-5-methyl isophthalaldehyde to the o-aminothiophenol is 1 (1-2.5) in terms of molar ratio.
The invention also provides application of the trivalent As detection probe, which is used for detecting the content of trivalent As.
Preferably, the method is used for detecting the content of trivalent As in naphtha.
Preferably, the detection comprises qualitative or quantitative detection.
Preferably, the trivalent As probe is used by the following method: adding the trivalent As detection probe into a sample to be detected of naphtha to ensure that the concentration of the trivalent As detection probe in the sample to be detected is 10-6M above, shaking up at room temperature, and measuring the fluorescence intensity with the excitation wavelength of 410nm by using a fluorescence spectrometer.
The trivalent As detection probe provided by the invention is simple and convenient in preparation method, low in cost, high in sensitivity, low in detection limit and high in selectivity, can be specifically used for detecting the content of trivalent As, and is particularly suitable for detecting the content of trivalent As in products such As naphtha.
Drawings
FIG. 1 shows the concentration of trivalent As in the range of 1.0 × 10-6M to 4.0 × 10-5Fluorescence enhancement of M, M-HBT is plotted as a linear function of arsenic concentration.
FIG. 2 is a bar graph showing the emission intensity ratio of trivalent As of the same concentration detected by M-HBT and all samples after adding other non-ferrous metal ions.
Figure 3 is a graph showing the comparative effect of the M-HBT of the present invention on the ion interference effect of different species in ethanol.
FIG. 4 is a graph showing the linear relationship between the fluorescence intensity and As concentration of M-HBT of the present invention measured in a real sample naphtha.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The reagents and instruments used in the examples of the invention were commercially available analytical grade, all without further purification, all reagents and solvents were used according to standard procedures; the silica gel used in the column chromatography in the synthesis process is 200-300 meshes; the water used in the test was drones deionized water.
The mass spectral data were determined by an LCMS-IT-TOF MS mass spectrometer, where high resolution mass spectral measurements were performed. Nuclear magnetic data (hydrogen, carbon spectra) were determined by Bruker (600MHz) nuclear magnetic resonance apparatus and chemical shifts are reported in ppm (in DMSO-d6 or CDCl)3TMS as internal standard). NMR spectra were recorded at Varian 400 MHz.
Fluorescence measurements were performed on an FS-5 spectrophotometer (Edinburgh, Britain) with slit widths set to 2nm for excitation and emission, respectively. The absorption spectra were measured on a SHIMADZU UV-3600 spectrophotometer. Measurement of solution equilibrium in air at room temperature (10)-6M) is carried out.
The preparation route of the trivalent As detection probe is As follows:
examples
2-hydroxy-5-methyl-isophthalaldehyde (100 mg, 0.6 mmol) was dissolved in 8 ml of a dichloromethane/methanol mixture (dichloromethane: methanol 3: 5 by volume). O-aminothiophenol (152 mg, 1.22 mmol) was then added and stirred at room temperature for 3 hours. The crude product was filtered and purified by column chromatography to give a yellow solid, designated as M-HBT, in 67% yield (150 mg, 0.4 mmol).
1H NMR(400MHz,CDCl3)13.98(s,1H),8.10(d,J＝8.1Hz,4H),7.99(d,J＝7.9Hz,2H),7.61–7.51(m,2H),7.51–7.41(m,2H),2.51(s,3H).13C NMR(100MHz,CDCl3)154.60–153.76(m),152.18–151.26(m),131.90(s),129.57–128.39(m),126.45(s),125.25(s),122.46(s),121.48(s),21.05–19.86(m).MS(m/z):calcd.for C21H15N2OS2:375.0626；found:375.0620[M+H]+。
Properties of trivalent As detection probe M-HBT under test conditions
The stability of the probe in the solvent was tested due to errors in the test instrument and to increase the accuracy of the experimental data. Before each test, the test is carried out after 3min of violent oscillation, and the experimental data of each test are ensured to be changed in equal amount.
1) Fluorescent response of probe M-HBT to pH
The invention researches ESIPT luminescence mechanism of M-HBT in water solution with different pH values (from pH 1 to pH 13), and finds that the maximum emission peak has a large Stokes shift (blue shift) from 610nm to 490 nm. Wherein the fluorescence emission at 610nm corresponds exactly to the maximum emission wavelength at pH 1 of the aqueous solution and the fluorescence emission at 490nm corresponds exactly to the maximum emission wavelength at pH 13 of the aqueous solution. Furthermore, the maximum emission wavelength at pH 7 is around 560nm, which is surprisingly similar to the maximum emission wavelength in ethanol. The Proton Transfer promoted by protonation of phenolic hydroxyl groups in ESIPT (Excited-state Intermolecular Proton Transfer-based) process was demonstrated above, and the emission spectrum gradually blueshifted to 510nm (pH 13) with increasing pH, which means that M-HBT is completely deprotonated in the ground state.
2) Sensitivity of probe M-HBT to arsenic
Based on the above, the sensor M-HBT is particularly sensitive to pH, so it is better to perform experimental tests on the sensor in a neutral environment to avoid pH interference causing deviation of experimental conclusions. However, arsenic compounds are substantially insoluble in water, and therefore the present invention chooses to perform sensitivity testing of arsenic in ethanol solution.
To evaluate the sensitivity of M-HBT to arsenic, a fluorescence titration experiment was performed with arsenic in ethanol, with a gradient concentration of arsenic compound stock solution added for ethanol configuration, with a blank probe without added arsenic having a fluorescence maximum emission wavelength around 580nm, with a large blue shift in the fluorescence emission spectrum after increasing arsenic concentration, with an arsenic concentration of 1.0 × 10-6In the M state, two fluorescence emission peaks at 520nm and 580nm were found, and as the concentration of arsenic increased, the fluorescence emission peak at 580nm gradually disappeared, and the fluorescence emission intensity at 520nm gradually increased until it increased to 4.0 × 10-5M became the maximum fluorescence intensity, which was 5 times the fluorescence intensity before arsenic addition.
Before arsenic is added, the hydrogen bond of the phenolic hydroxyl group can form intramolecular hydrogen bond to be connected with an N atom on the benzothiazole, and at the moment, the sensor emits orange yellow fluorescence. However, upon addition of trivalent As, the ESIPT mechanism of compound M-HBT was blocked, breaking the H to N, O linkage, resulting in a change in the fluorescence emitted by the sensor from orange-yellow to green and also visible to the naked eye.
The detection limit is an important parameter for evaluating the fluorescence sensor, and means that the sensor detects the lowest concentration of the sampleTherefore, the invention takes the fluorescence intensity ratio of the M-HBT (5 mu M) at 525nm as the ordinate and the arsenic compound concentration as the abscissa to make a point chart (as shown in figure 1), and the concentration is 1.0 × 10-6M to 4.0 × 10-5M. selected to be 1.0 × 10-6M to 5.0 × 10-6There is a good linear relationship between the arsenide concentrations in the M range, with a correlation coefficient k of 0.9470, about 0.95. By the formula of detection limits
Where represents the standard deviation of repeated injections, the limit of detection (LOD) was calculated to be 69.7nM, which is lower than the American environmental protection agency's minimum standard (6.7. mu.M). It can be seen that the M-HBT sensor has a high sensitivity to arsenic.
3) Study of Selectivity
The selectivity of the fluorescent probe is important for evaluating the performance of the probe, so that the invention evaluates the selective performance of the M-HBT of the fluorescent probe, and other interfering ions with the same concentration are added into ethanol at room temperature as a comparison experiment under the same experimental conditions of arsenic sensitivity, and 1 × 10 is added respectively-5MFe3+,Cu2+,Al3+,Co2+,Cd2+,Hg2+,Cr3+,Ag+Then, no obvious fluorescence enhancement or fluorescence reduction occurs in the fluorescence of M-HBT, but in contrast, the fluorescence is enhanced by 5 times after the same concentration of trivalent As is added, and FIG. 2 is a selectivity bar chart, so that the emission intensity ratio (I/I) of all samples after the trivalent As is added and other non-ferrous metal ions are added can be clearly seen0At 525 nm) was 85.7 times, which is a sufficient indication that the probe M-HBT has good selectivity for arsenic.
4) Study of anti-interference effect
After evaluating the selectivity of the M-HBT, the invention also researches the ion interference effect of the M-HBT by considering that only one metal ion is not necessarily contained in the solution in practical application. The study was conducted on metal ions, such asThe organic arsenic compound and arsenate are in the interference range, such as Zn2+，K+，Fe2+，AsO3 -，AsS3 -，AsPh3And in the experiment, metal ions are added into a probe M-HBT and an ethanol solution to obtain the fluorescence intensity of a yellow column, and then As is added into a mixed solution of the metal ions to obtain the fluorescence intensity of a green column. The experimental result shows that all interference factors do not interfere the response of M-HBT to As, As shown in figure 3, when Zn is added2+，Hg2+，Cu2+，Ag+The fluorescence of the latter mixed solution is enhanced but negligible in relation to the fluorescence intensity after addition of As. The experimental result shows that all the interfering species can judge the detection of As As to be non-interfering, so that the M-HBT can be considered As a high-selectivity non-interfering excellent fluorescent probe for detecting As.
Therefore, the invention tries to make a sensitive sensitivity experiment of the M-HBT in the naphtha of an actual sample (As shown in figure 4). before the experiment begins, a solvent system of naphtha: ethanol (4: 1) is determined, and solutions of trivalent As with different concentrations are added, and the result shows that the fluorescent probe M-HBT has fluorescence emission at 490nm and 1.0 × 10 is added before the trivalent As is not added-6The As post-fluorescence of M begins to increase and gradually increases with the increase of the concentration of trivalent As, and As shown in FIG. 4, the fluorescence intensity is linearly and positively correlated with the concentration of trivalent As. Samples were analyzed for different concentrations of trivalent As in naphtha. The experimental results show that the recovery rate of trivalent As by adding standard is between 90% and 108%, therefore, M-HBT can be considered to be effective for quantitative detection of trivalent As in naphtha (naptha) samples.
The use method of the trivalent As detection probe comprises the following steps: the volume of the naphtha sample to be detected in the cuvette is 2mL, and the added 2 microliter concentration is 10-3M-HBT probe, the concentration of the probe in the cuvette reaches 10 after the M-HBT probe is added-6M, shaking up at room temperature, and measuring the fluorescence intensity with the excitation wavelength of 410nm by using a fluorescence spectrometer.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (7)
1. A trivalent As detection probe, characterized in that the probe has the following structural formula:
2. a method for preparing a trivalent As detection probe according to claim 1, wherein the method is prepared by using 2-hydroxy-5-methyl m-phthalaldehyde and o-aminothiophenol As raw materials according to the following route:
3. the method for preparing a trivalent As detection probe according to claim 2, wherein the usage ratio of the 2-hydroxy-5-methyl isophthalaldehyde to the o-aminothiophenol is 1 (1-2.5) in terms of molar ratio.
4. Use of a trivalent As detection probe according to claim 1 for detecting the content of trivalent As.
5. Use according to claim 4, wherein the detection comprises qualitative or quantitative detection.
6. Use according to claim 4 for the detection of the content of trivalent As in naphtha.
7. The use according to claim 4, wherein the trivalent As detection probe is used by a method comprising: adding the trivalent As detection probe into a sample to be detected of naphtha to ensure that the concentration of the trivalent As detection probe in the sample to be detected is 10-6M above, shaking up at room temperature, and measuring the fluorescence intensity with the excitation wavelength of 410nm by using a fluorescence spectrometer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521383A (en) * | 2020-12-11 | 2021-03-19 | 三峡大学 | Benzothiazole derivatives and their use as fluorescent dyes |
| CN115368315A (en) * | 2021-05-19 | 2022-11-22 | 北京工商大学 | Dibenzothiazole tyrosinase fluorescent probe |
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| CN107337654A (en) * | 2017-07-11 | 2017-11-10 | 济南大学 | A kind of fluorescence probe for analyzing mercury ion, preparation method and application |
| CN110372632A (en) * | 2019-07-26 | 2019-10-25 | 广东轻工职业技术学院 | A kind of fluorescent probe molecule and its preparation method and application of quick identification hypochlorite ion |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107337654A (en) * | 2017-07-11 | 2017-11-10 | 济南大学 | A kind of fluorescence probe for analyzing mercury ion, preparation method and application |
| CN110372632A (en) * | 2019-07-26 | 2019-10-25 | 广东轻工职业技术学院 | A kind of fluorescent probe molecule and its preparation method and application of quick identification hypochlorite ion |
Non-Patent Citations (1)
| Title |
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| XUAN ZHANG ET AL.: "Near-infrared fluorescence of p-conjugation extended benzothiazole and its application for biothiol imaging in living cells", 《J. MATER. CHEM. B》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521383A (en) * | 2020-12-11 | 2021-03-19 | 三峡大学 | Benzothiazole derivatives and their use as fluorescent dyes |
| CN115368315A (en) * | 2021-05-19 | 2022-11-22 | 北京工商大学 | Dibenzothiazole tyrosinase fluorescent probe |
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