CN114487086A - Pentavalent arsenic mass spectrum probe and electrospray mass spectrum detection method for measuring pentavalent arsenic - Google Patents
Pentavalent arsenic mass spectrum probe and electrospray mass spectrum detection method for measuring pentavalent arsenic Download PDFInfo
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- 239000000523 sample Substances 0.000 title claims abstract description 72
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
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Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/68—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using electric discharge to ionise a gas
Abstract
The invention belongs to the technical field of new materials, relates to arsenic detection, and particularly relates to a pentavalent arsenic mass spectrometry probe and an electrospray mass spectrometry detection method for measuring pentavalent arsenic3O4With CeO2The magnetic nanocomposite material is prepared by passing CeO2Adsorbing a signal molecule, wherein the signal molecule is glycerophosphorylcholine. And adding the pentavalent arsenic mass spectrometry probe into a solution to be detected for incubation, and carrying out electrospray ionization mass spectrometry detection by taking the incubated clear solution as a sample. The invention can realize simple, quick, low-cost and ultra-sensitive detection of trace As (V).
Description
Technical Field
The invention belongs to the technical field of new materials, relates to arsenic detection, and particularly relates to a pentavalent arsenic mass spectrometry probe and an electrospray mass spectrometry detection method for measuring pentavalent arsenic.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
According to the research of the inventor, the arsenic is mainly detected by qualitatively/quantitatively analyzing inorganic substances, and utilizing an inductively coupled plasma emission spectrometer, an atomic absorption spectrometer, an atomic fluorescence spectrometer, a mercury detector, a high-efficiency liquid phase and the like. While these methods can accurately measure arsenic reduction in environmental samples to micrograms per liter concentrations (concentrations on the order of micrograms per liter), most of them are limited by matrix interference, high cost, poor stability, time consuming, complex and cumbersome equipment enrichment steps, and some methods also require time consuming procedures and often do not readily distinguish between heavy metal ions of different valence states.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a pentavalent arsenic mass spectrometry probe and an electrospray mass spectrometry detection method for measuring pentavalent arsenic, which can realize simple, quick, low-cost and ultrasensitive detection of trace As (V).
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the pentavalent arsenic mass spectrometry probe comprises a magnetic nano composite material, wherein the magnetic nano composite material is Fe3O4With CeO2The magnetic nanocomposite material is prepared by passing CeO2Adsorbing a signal molecule, wherein the signal molecule is glycerophosphorylcholine.
The invention takes glycerophosphorylcholine as a signal molecule which can be substituted by CeO2And adsorption, when encountering arsenate (V) in the solution, the arsenic (V) and the magnetic nano composite material have stronger binding capacity, so that the signal molecules are replaced, and the electrospray mass spectrometry detection of the arsenic (V) is realized through the detection of the signal molecules. At the same time, magnetic Fe is adopted3O4With CeO2The compounding purpose is not only to cooperate with CeO2The binding capacity of the magnetic nano composite material and arsenic (V) is increased, and online detection can be realized by utilizing magnetic separation in the detection process.
On the other hand, the preparation method of the pentavalent arsenic mass spectrometry probe comprises the steps of incubating the magnetic nano composite material and glycerophosphorylcholine in a solvent, and incubating to obtain the pentavalent arsenic mass spectrometry probe.
In a third aspect, the application of the pentavalent arsenic mass spectrometry probe in mass spectrometry detection of pentavalent arsenic in water is provided.
And fourthly, adding the pentavalent arsenic mass spectrometry probe into a solution to be detected for incubation, and performing electrospray mass spectrometry detection by taking the incubated clear solution as a sample.
The pentavalent arsenic mass spectrometry probe provided by the invention can be subjected to magnetic separation so that the probe is separated from a solution, and the detection of the pentavalent arsenic can be subjected to online detection, so that in the fifth aspect, an electrospray mass spectrometry detection system for online detection of the pentavalent arsenic comprises an injector, a filter membrane, a sample inlet pipe, a two-way pipe and a metal electrospray needle which are sequentially connected, wherein the metal electrospray needle points to an electrospray mass spectrometry device, and one side of the injector is provided with a magnetic device.
As trivalent arsenic can generate pentavalent arsenic through oxidation, and trivalent arsenic can be detected by adopting the pentavalent arsenic mass spectrometry probe after being oxidized into pentavalent arsenic, the application of the pentavalent arsenic mass spectrometry probe in mass spectrometry detection of trivalent arsenic in water is provided in the sixth aspect.
In the seventh aspect, an electrospray ionization mass spectrometry detection method for measuring trivalent arsenic is provided, wherein a solution to be detected is divided into two parts, the pentavalent arsenic mass spectrometry probe is added into one part of the solution to be detected for incubation, and the incubated clear solution is used as a sample for electrospray ionization mass spectrometry detection to obtain the content of pentavalent arsenic in the solution to be detected; and oxidizing the other solution to be detected, adding a pentavalent arsenic mass spectrometry probe for incubation, carrying out electrospray ionization mass spectrometry detection on the incubated clear solution serving as a sample to obtain the total content of trivalent arsenic and pentavalent arsenic in the solution to be detected, and calculating according to the total content of trivalent arsenic and pentavalent arsenic and the content of pentavalent arsenic to obtain the content of trivalent arsenic in the solution to be detected.
The invention has the beneficial effects that:
the invention utilizes As (V) and Fe3O4@CeO2The strong binding capacity of the probe replaces the signal molecules on the surface of the probe, and the detection of As (V) by electrospray ionization mass spectrometry is realized by detecting the signal moleculesThe quantitative detection of trace heavy metal pollutants As (V) in the biological sample is simple, rapid, ultra-sensitive and high in selectivity.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows Fe prepared in example 1 of the present invention3O4@CeO2Characterization of the composite material, wherein a is a transmission electron micrograph and b is Fe3O4@CeO2XPS characterization of composite material, c is Fe3O4@CeO2Ultraviolet absorption characterization graph of the composite material.
FIG. 2 is a graph showing the examination of glycerophosphorylcholine and Fe after the first incubation step in example 1 of the present invention3O4@CeO2And (b) the binding degree of the composite material, wherein a is a mass spectrogram for directly detecting the supernatant obtained by centrifugation after the first-step incubation is completed, and b is a mass spectrogram for directly detecting the supernatant obtained by centrifugation after 3 times of washing.
FIG. 3 is a graph showing the intensity ratio of arsenic (V) -substituted signal molecules to internal standard signal molecules at each concentration in example 1 of the present invention.
FIG. 4 is a graph showing data for detecting the specificity of arsenic (V) and other high-concentration salt compounds in example 1 of the present invention.
FIG. 5 is a graph showing the relative intensities of arsenic (V) -substituted signaling molecules in example 3 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the problems of poor sensitivity, poor stability, low specificity and the like of the existing method for detecting pentavalent arsenic, the invention provides a pentavalent arsenic mass spectrometry probe and an electrospray mass spectrometry detection method for detecting pentavalent arsenic.
The invention provides a pentavalent arsenic mass spectrometry probe, which comprises a magnetic nano composite material, wherein the magnetic nano composite material is Fe3O4With CeO2The magnetic nanocomposite material is prepared by passing CeO2Adsorbing a signal molecule, wherein the signal molecule is glycerophosphorylcholine.
The invention takes glycerophosphorylcholine as a signal molecule which can be substituted by CeO2And adsorption, when encountering arsenate (V) in the solution, the arsenic (V) and the magnetic nano composite material have stronger binding capacity, so that the signal molecules are replaced, and the electrospray mass spectrometry detection of the arsenic (V) is realized through the detection of the signal molecules. At the same time, magnetic Fe is adopted3O4With CeO2The compounding purpose is not only to cooperate with CeO2The binding capacity of the magnetic nano composite material and arsenic (V) is increased, and online detection can be realized by utilizing magnetic separation in the detection process.
In some examples of this embodiment, Fe3O4With CeO2The composite material of (A) is of a core-shell structure, Fe3O4As a nucleus, CeO2Is a shell. More glycerophosphorylcholine can be combined, so that more arsenic (V) can be replaced, and the detection sensitivity is increased.
The other embodiment of the invention provides a preparation method of the pentavalent arsenic mass spectrometry probe, which comprises the steps of incubating a magnetic nano composite material and glycerophosphorylcholine in a solvent, and incubating to obtain the pentavalent arsenic mass spectrometry probe.
In some examples of this embodiment, the magnetic nanocomposite is obtained by mixing the magnetic nanocomposite with a solvent, sonicating, adding glycerophosphorylcholine to incubate, and centrifuging after incubation.
In some examples of this embodiment, Fe is added3O4Is added to CeO2In the dispersion liquid of the nano material, ultrasonic dispersion is carried out, ammonia water is adopted to adjust the pH value, and heating reaction is carried out to obtain Fe3O4@CeO2And (3) microspheres.
In one or more embodiments, the pH is adjusted to 6.5 to 7.0. The heating reaction temperature is 55-65 ℃. The heating reaction time is 3-5 h.
In one or more embodiments, the Fe3O4The preparation method comprises the following steps: adding ferric chloride, polyethylene glycol and sodium acetate into an organic solvent for solvothermal reaction to obtain the iron-based catalyst. The organic solvent is ethylene glycol. The temperature of the solvothermal reaction is 190-210 ℃, and the reaction time is 7-9 h. The adding ratio of ferric chloride to polyethylene glycol to sodium acetate is 1: 0.15-0.25: 0.70-0.80, and the weight ratio of mmol: g: g.
in one or more embodiments, the CeO2The preparation method of the dispersion liquid of the nano material comprises the following steps: adding cerium nitrate and sodium hydroxide into a solvent, heating and stirring, adding hydrogen peroxide for stirring, adding separated precipitate into water for dispersing, then adding nitric acid to adjust the pH, and heating and reacting to obtain the cerium nitrate-cerium dioxide composite material. The heating and stirring temperature is 46-55 ℃, and the time is 22-26 h. Adjusting the pH value to 0.05-0.15. The heating reaction temperature is 36-45 ℃, and the time is 1-3 h. The solvent is ethanol.
The third embodiment of the invention provides an application of the pentavalent arsenic mass spectrometry probe in mass spectrometry detection of pentavalent arsenic in water.
In a fourth embodiment of the invention, an electrospray ionization mass spectrometry detection method for detecting pentavalent arsenic is provided, wherein the pentavalent arsenic mass spectrometry probe is added into a solution to be detected for incubation, and the incubated clear solution is used as a sample for electrospray ionization mass spectrometry detection.
In some examples of this embodiment, after incubation, centrifugation is performed, and the centrifuged solution is filtered to obtain a clear solution.
In some embodiments of this embodiment, the incubation time is 80-100 min.
The fifth embodiment of the invention provides an electrospray mass spectrometry detection system for online measurement of pentavalent arsenic, which comprises an injector, a filter membrane, a sample inlet tube, a two-way tube and a metal electric spray needle which are sequentially connected, wherein the metal electric spray needle points to an electrospray mass spectrometry device, and a magnetic device is arranged on one side of the injector to prevent magnetic nanoparticles from entering a mass spectrum.
The sixth embodiment of the invention provides an application of the pentavalent arsenic mass spectrometry probe in mass spectrometry detection of trivalent arsenic in water.
The seventh embodiment of the invention provides an electrospray ionization mass spectrometry detection method for measuring trivalent arsenic, which comprises the steps of dividing a solution to be detected into two parts, adding the pentavalent arsenic mass spectrometry probe into one part of the solution to be detected for incubation, and performing electrospray ionization mass spectrometry detection by taking the incubated clear solution as a sample to obtain the content of pentavalent arsenic in the solution to be detected; and oxidizing the other solution to be detected, adding a pentavalent arsenic mass spectrometry probe for incubation, carrying out electrospray ionization mass spectrometry detection on the incubated clear solution serving as a sample to obtain the total content of trivalent arsenic and pentavalent arsenic in the solution to be detected, and calculating according to the total content of trivalent arsenic and pentavalent arsenic and the content of pentavalent arsenic to obtain the content of trivalent arsenic in the solution to be detected.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
1.Fe3O4And (3) synthesis of microspheres:
FeCl is stirred3·6H2O (0.675g, 2.50mmol), polyethylene glycol (PEG)4000.500g) and NaAc (1.80g) were dissolved in 40mL of ethylene glycol for 30 minutes to form a clear solution. The resulting solution was then transferred to a 50mL stainless steel autoclave polytetrafluoroethylene liner. The autoclave was heated at 200 ℃ for 8 h. The precipitate was collected by centrifugation and then washed three times with ethanol.
2.CeO2And (3) synthesis of nano materials:
1.000gCe (NO)3)3·6H2O and 1.000gNaOH was dissolved in 20.0mL of ethanol, respectively. The mixture was stirred vigorously at 50 ℃ for 24 hours. H is to be2O2(30％H2O250.0. mu.L) was added to the mixture solution, and stirred for 2 hours. The precipitate was washed and collected by centrifugation and then dried at 60 ℃ for 4 hours. Then 0.500g of the precipitate was dispersed in 10.0mL of distilled water with continuous stirring. The pH of the solution was then adjusted to 0.1 by the addition of concentrated nitric acid. The reaction was allowed to proceed at 40 ℃ for 2 hours with continuous stirring. Naturally cooling the solution to room temperature to obtain a transparent light yellow solution, namely CeO2A nanomaterial dispersion.
3.Fe3O4@CeO2And (3) synthesis of microspheres:
0.10g of Fe3O4The microspheres were ultrasonically treated for 15min and dispersed in a mixture of 30mL of distilled water and 3mL of CeO2A mixture of nanomaterial dispersions. Subsequently, 0.500 mol. L was added-1NH3·H2O solution to adjust pH to 6.8. The final mixed solution was vigorously stirred by stirring at 60 ℃ for 4 hours. After completion of the reaction, the particles were collected by an external magnet and washed thoroughly with ethanol, and then dried overnight in a 60 ℃ drying oven to obtain Fe3O4@CeO2Microspheres, as shown in figure 1. Wherein, FIG. 1a is Fe3O4@CeO2Transmission electron microscope picture of composite material, light color area is CeO2The dark region is Fe3O4Microspheres, which can be seen to be bonded; FIG. 1b is Fe3O4@CeO2The XPS characteristic diagram of the composite material shows Fe according to the marked characteristic peak3O4@CeO2The composite material contains Fe3O4And CeO2Characteristic element peak of (1); FIG. 1c is Fe3O4@CeO2UV characterization of the composite, from which Fe can be seen3O4@CeO2The composite material has Fe3O4And CeO2Characteristic absorption peak of (1).
4. And (3) synthesis of a pentavalent arsenic mass spectrometry probe:
weighing Fe3O4@CeO2Microspheres 2.75mg into a 1.5mL EP tube, 500. mu. L H was added2And performing ultrasonic treatment. After homogenization, glycerophosphorylcholine (500. mu.L, 100. mu.M) was added and mixed and incubated for 90min at 20 ℃ and 1000rpm using a shaking incubator. Then centrifuged, the supernatant discarded and 1mL of H was added2Washing with O, washing and precipitating for three times, and then leaving precipitate to obtain Fe3O4@CeO2Glycerophosphorylcholine, namely a pentavalent arsenic mass spectrometry probe.
Carrying out electrospray ionization mass spectrometry detection on As (V) by adopting a pentavalent arsenic mass spectrometry probe, wherein the process comprises the following steps:
to the pentavalent arsenic mass spectrometer probe, 200. mu.L of IS (D-glucose-6-disodium phosphate, final concentration 20. mu.M, mass spectrum peak 306) solution and 200. mu.L of different concentrations of H were added2O4As-·Cs+(final concentrations were 1.00nM,10.0nM,20.0nM,50.0nM,60.0nM,80.0nM,100nM, respectively) and a final volume of 400. mu.L. Incubating the sample for 90min, centrifuging for 10min, taking out the centrifuged supernatant, and performing electrospray mass spectrometry by using a designed method, wherein the voltage of electrospray is 3600V, and the sample introduction flow rate is 5 mu L/min. Signals were recorded using the positive ion mode of Q-exact orbitrap, with the ion transfer tube voltage set to +30V, the ion transfer tube temperature set to 320 ℃, and the sheath gas pressure and flow rate set to zero.
Meanwhile, in order to detect the specificity of arsenic (V) detected by a pentavalent arsenic mass spectrometry probe, 11 salts (100 mu M) such as nitroso salt, acetate, phosphate, carbonate, bromide, chloride, iodide and the like are used for comparing and detecting arsenic (V) (1 mu M) and comparing the signal intensity.
The detection results are shown in fig. 2-4, wherein fig. 2a is a mass spectrum of the supernatant obtained by direct centrifugation after the first incubation, and fig. 2b is a mass spectrum of the supernatant obtained by centrifugation after three times of washing. It can be seen that after three washes, a slight excess of glycerophosphorylcholine has been washed to completion, demonstrating that the added glycerophosphorylcholine has been maximally associated with Fe3O4@CeO2And (4) combining the composite materials.
FIG. 3 is a graph of data for the detection of arsenic (V) and other species of salts under the same conditions, wherein the selective specificity of a pentavalent arsenic mass spectrometry probe in detecting arsenic (V) can be demonstrated.
FIG. 4 IS a graph of signal-to-IS mass spectrum signal ratios for signal molecules in the range of 1.00nM to 100nM, with a calculated detection limit of 0.0943 nM.
Example 2
And (3) detecting the content of pentavalent arsenic in water:
the actual samples were derived from tap water from the infranatal region of the city of dennan, black tiger spring, daming lake and yellow river.
To the pentavalent arsenic mass spectrometry probe prepared in example 1, 200. mu.L of IS (final concentration 20. mu.M) solution and 200. mu.L of tap water, black tiger spring, daming lake and yellow river water were added, respectively, to make the final volume of the solution 400. mu.L. And (4) incubating for 90min, then centrifuging for 10min, and carrying out electrospray mass spectrometry detection on the centrifuged supernatant by using a designed method. The results are shown in Table 1.
TABLE 1 test results of pentavalent arsenic content in water
| Sample (I) | Containing arsenic (V) |
| Tap water | 10.89nM |
| Black tiger spring | 9.17nM |
| Ming lake | 8.89nM |
| Yellow River | 13.28nM |
Example 3
And (3) detecting pentavalent arsenic in escherichia coli:
(1) as (V) -containing E.coli culture: after OD measurement, the Escherichia coli grown in the stock culture was divided into 5 portions and added to media containing arsenate at different concentrations, the final concentrations of arsenate being 0mg/L, 0.500mg/L, 1.00mg/L, 2.00mg/L, and 5.00mg/L, respectively.
(2) To the pentavalent arsenic mass spectrometry probes prepared in example 1, 200. mu.L of a solution containing IS (final concentration 20. mu.M) was added, and 10mL of a lysate containing five flasks of bacteria was taken out and lysed after washing twice with 1 XPBS. And (4) incubating for 90min, then centrifuging for 10min, taking out the centrifuged supernatant, and carrying out electrospray mass spectrometry detection by a designed method.
As shown in FIG. 5, it can be seen that, when the final concentration of arsenate (V) is 0mg/L, glycerophosphorylcholine 296[ M + K ] is not observed]+The remaining concentration of 296[ M + K ] can be seen]+The peak of (2). The detection method disclosed by the invention is shown to be capable of detecting pentavalent arsenic in the strain.
Example 4
An electrospray mass spectrometry detection system for online determination of pentavalent arsenic comprises an injector, a filter membrane, a sample inlet pipe, a two-way pipe, a metal electrospray needle and an electrospray mass spectrometry device, wherein a sample inlet of the two-way pipe is connected with an outlet of the sample inlet pipe, an inlet of the sample inlet pipe is connected with an outlet of the injector, a sample outlet of the two-way pipe is connected with the metal electrospray needle, the metal electrospray needle points to the electrospray mass spectrometry device, and a magnet is arranged on one side of the injector.
Example 5
An electrospray ionization mass spectrometry detection method for measuring trivalent arsenic comprises the steps of dividing a solution to be detected into two parts, adding a pentavalent arsenic mass spectrometry probe into one part of solution to be detected for incubation, and carrying out electrospray ionization mass spectrometry detection on an incubated clear solution serving as a sample to obtain the content of the pentavalent arsenic in the solution to be detected; and oxidizing the other solution to be detected, adding a pentavalent arsenic mass spectrometry probe for incubation, carrying out electrospray ionization mass spectrometry detection on the incubated clear solution serving as a sample to obtain the total content of trivalent arsenic and pentavalent arsenic in the solution to be detected, and calculating according to the total content of the trivalent arsenic and the pentavalent arsenic and the content of the pentavalent arsenic to obtain the content of the trivalent arsenic in the solution to be detected.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A pentavalent arsenic mass spectrum probe comprises a magnetic nano composite material, wherein the magnetic nano composite material is Fe3O4With CeO2The magnetic nanocomposite material is prepared by passing CeO2Adsorbing a signal molecule, wherein the signal molecule is glycerophosphorylcholine.
2. The pentavalent arsenic mass spectrometry probe of claim 1, wherein Fe3O4With CeO2The composite material of (A) is of a core-shell structure, Fe3O4As a nucleus, CeO2Is a shell.
3. A method for preparing the pentavalent arsenic mass spectrometry probe of claim 1 or 2, which is characterized in that the magnetic nano composite material and glycerophosphorylcholine are incubated in a solvent and then the probe is obtained after incubation.
4. The method for preparing the pentavalent arsenic mass spectrometry probe as claimed in claim 3, wherein the magnetic nano composite material is mixed with a solvent, subjected to ultrasonic treatment, added with glycerophosphorylcholine for incubation, and subjected to centrifugal separation after incubation;
or, mixing Fe3O4Is added to CeO2In the dispersion liquid of the nano material, ultrasonic dispersion is carried out, ammonia water is adopted to adjust the pH value, and heating reaction is carried out to obtain Fe3O4@CeO2Microspheres;
preferably, the pH is adjusted to 6.5-7.0;
preferably, the Fe3O4The preparation method comprises the following steps: mixing ferric chloride and polyAdding ethylene glycol and sodium acetate into an organic solvent to carry out solvothermal reaction to obtain the compound;
preferably, the CeO2The preparation method of the dispersion liquid of the nano material comprises the following steps: adding cerium nitrate and sodium hydroxide into a solvent, heating and stirring, adding hydrogen peroxide for stirring, adding separated precipitate into water for dispersing, then adding nitric acid to adjust the pH, and heating and reacting to obtain the cerium nitrate-cerium dioxide composite material.
5. Use of a pentavalent arsenic mass spectrometry probe of claim 1 or 2 in mass spectrometry for detecting pentavalent arsenic in water.
6. An electrospray ionization mass spectrometry detection method for detecting pentavalent arsenic, which is characterized in that the pentavalent arsenic mass spectrometry probe of claim 1 or 2 is added into a solution to be detected for incubation, and the incubated clear solution is used as a sample for electrospray ionization mass spectrometry detection.
7. The electrospray mass spectrometry detection method for pentavalent arsenic according to claim 6, characterized in that after incubation, centrifugal separation is performed, and the solution after centrifugal separation is filtered to obtain a clear solution;
or, the incubation time is 80-100 min.
8. An electrospray mass spectrometry detection system for on-line measurement of pentavalent arsenic is characterized by being used for matching with the pentavalent arsenic mass spectrometry probe of claim 1 or 2 for detection, and comprising an injector, a filter membrane, a sample inlet pipe, a two-way pipe and a metal electric spray needle which are sequentially connected, wherein the metal electric spray needle points to an electrospray mass spectrometry device, and one side of the injector is provided with a magnetic device.
9. Use of a pentavalent arsenic mass spectrometry probe of claim 1 or 2 in mass spectrometry for detecting trivalent arsenic in water.
10. An electrospray ionization mass spectrometry detection method for measuring trivalent arsenic is characterized in that a solution to be detected is divided into two parts, a pentavalent arsenic mass spectrometry probe as described in claim 1 or 2 is added into one part of the solution to be detected for incubation, and the incubated clear solution is used as a sample for electrospray ionization mass spectrometry detection to obtain the content of pentavalent arsenic in the solution to be detected; and oxidizing the other solution to be detected, adding a pentavalent arsenic mass spectrometry probe for incubation, carrying out electrospray ionization mass spectrometry detection on the incubated clear solution serving as a sample to obtain the total content of trivalent arsenic and pentavalent arsenic in the solution to be detected, and calculating according to the total content of trivalent arsenic and pentavalent arsenic and the content of pentavalent arsenic to obtain the content of trivalent arsenic in the solution to be detected.
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| CN103403177A (en) * | 2010-10-22 | 2013-11-20 | 弗里堡大学 | Sensor |
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