CN111569840B - Adsorption material for organic pollutants, paper spray mass spectrum detection device and detection method - Google Patents
Adsorption material for organic pollutants, paper spray mass spectrum detection device and detection method Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
Abstract
The invention discloses an adsorption material of organic pollutants, a paper spray mass spectrum detection device and a detection method. The adsorption material of the organic pollutants comprises a paper substrate and a covalent organic framework material layer attached to the surface of the paper substrate, and is used for extracting, enriching and separating the organic pollutants; one end of the metal clamp is connected with a high-voltage direct-current power supply, and the other end of the metal clamp clamps the adsorption material, so that the tip of the adsorption material is aligned to a sample inlet of the mass spectrometer; the outlet end of the injection device is connected with one end of a pipeline, and the other end of the pipeline extends to the surface of the adsorption material and is used for injecting an eluent onto the adsorption material to desorb a target object adsorbed on the adsorption material; the mass spectrometer is used for detecting organic pollutants. The paper spray mass spectrometry method is combined with a covalent organic framework, so that effective monitoring of trace tetrabromobisphenol A in an environmental sample is realized, and a novel paper-based spray mass spectrometry detection method for detecting organic pollutants is provided.
Description
Technical Field
The invention belongs to the technical field of analysis and detection, and particularly relates to an adsorption material of organic pollutants, a paper spray mass spectrum detection device and a detection method.
Background
The disclosure of this background section is only intended to increase the 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 already known to those of ordinary skill in the art.
Organic pollutants in the environment seriously harm our health, and the enhancement of the monitoring of the organic pollutants has important significance for protecting the health of people. Tetrabromobisphenol a is one of the common flame retardants, which has high persistent contamination and is very easily accumulated in the human body. The major hazards of tetrabromobisphenol a are twofold: first, prolonged exposure to brominated flame retardants can interfere with brain and skeletal development; second, it releases highly carcinogenic substances when incinerated. However, the inventor finds that the analysis result is seriously affected due to the complex matrix of the environmental water body and the low content of the target substances. In the existing mass spectrum detection process of trace target objects, an extractant is generally used for extracting the target objects, then an eluting solvent is used for eluting the target objects from the extractant, then the eluting solution is concentrated, and finally mass spectrum detection is carried out. The process has the advantages of complicated steps, long time consumption and low analysis efficiency.
The paper spray ionization technology is a new type of normal pressure ionization technology, and its principle is that triangular paper substrate is used as sample separating and ionizing carrier, and during analysis, sample or spray solvent is dropped onto the paper substrate, and under the condition of external power source, target analyte is ionized and then enters into detector for detection. The paper spraying technology can overcome the defects of the traditional ionization technology to a certain extent, and has the advantages of simple operation, low price and no need of complex pretreatment process for products. However, due to the presence of hydroxyl groups on the surface of the paper substrate, when the target compound is analyzed using paper spray, some functional groups of the compound may form hydrogen bonds or van der waals interactions with the hydroxyl groups, resulting in difficulty in eluting the compound in a short time, thereby reducing the sensitivity of the paper spray mass spectrum. In addition, micropores with smaller specific surface area exist on the surface of the filter paper, so that the enrichment capacity of the filter paper is reduced, and the sensitivity of the method is further reduced. Covalent organic frameworks are an important crystalline material with a delicate topological framework and ordered nanopores similar to metal-organic framework materials that can be covalently built by reticulation chemistry from precisely designed organic ligands. The covalent organic framework has higher thermal and chemical stability, larger surface area, wider pore size distribution, and richer functional groups than other crystalline materials. Covalent organic frameworks have been used for specific selective adsorption of guest molecules by rational choice of topology and design of functional ligands and are considered to be one of the excellent solid phase microextraction porous materials.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide an adsorption material for organic pollutants, a paper spray mass spectrum detection device and a detection method. Integrates extraction, enrichment, separation, ionization and detection, solves the problems existing in the detection of the trace tetrabromobisphenol A by a solid-phase microextraction method and a mass spectrometry, and finally realizes the high-efficiency, rapid and convenient detection of the trace target.
To achieve the above object, one or more embodiments of the present invention disclose the following technical solutions:
in a first aspect, there is provided an adsorbent material for organic contaminants comprising a paper substrate and a layer of covalent organic framework material attached to a surface of the paper substrate;
the paper substrate is a paper substrate in paper spray ionization, and the shape of the paper substrate is triangular.
In a second aspect, there is provided a paper spray mass spectrometry detection device for organic contaminants, comprising:
the adsorbent material;
a mass spectrometer;
one end of the metal clamp is connected with a high-voltage direct current power supply, and the other end of the metal clamp clamps the adsorption material, so that the tip of the adsorption material is aligned to a sample inlet of the mass spectrometer;
and the outlet end of the injection device is connected with one end of the pipeline, and the other end of the pipeline extends to the surface of the adsorption material and is used for injecting the eluent onto the adsorption material to desorb the target object adsorbed on the adsorption material.
In a third aspect, there is provided a paper spray mass spectrometry detection method of organic contaminants, comprising the steps of:
preparing an adsorption material, and adhering a covalent organic framework material to the surface of a paper substrate by adopting a starch adhesive;
placing an adsorption material into a water sample, and adsorbing a target object in the water sample;
clamping the adsorption material adsorbed with the target object by using a metal clamp, injecting an eluent on the adsorption material, applying high-voltage electricity on the adsorption material, and forming electrospraying of the target object at the tip of the paper substrate while desorbing the target object;
electrospray is received by a mass spectrometer for detection.
Compared with the prior art, the above one or more embodiments of the invention achieve the following beneficial effects:
1. one or more embodiments of the present invention create a new paper spray mass spectrometry detection method that combines the advantages of covalent organic framework materials with the characteristics of paper spray mass spectrometry, and based on matching the pore channel of the covalent organic framework with the molecular size of tetrabromobisphenol a, achieves the purpose of detecting trace tetrabromobisphenol a organic contaminants in complex matrix samples, integrating extraction, enrichment, separation, ionization and detection.
2. The covalent organic framework modified on the surface of the matrix material has excellent extraction and enrichment capability due to stability, porosity, excellent specific surface area and object adsorption capability; the covalent organic framework is attached to the surface of the paper-based material, so that the enrichment capacity of the paper-based material can be enhanced, and the interaction between the hydroxyl on the surface of the paper-based material and the target can be weakened, so that the target can be desorbed more easily under the elution action of the eluent, and the detection of trace analytes can be realized.
3. The provided detection method does not need to carry out complex pretreatment process on the sample, and directly carries out desorption, ionization and detection after adsorption by adopting an adsorption material, so that the method has the advantages of simplicity in operation, low cost, high efficiency and rapidness.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a schematic diagram of the detection process of embodiment 1 of the present invention;
FIG. 2 is a standard curve for detecting organic contaminants according to example 1 of the present invention.
Wherein, 1, the syringe, 2, paper matrix, 3, copper clip, 4, direct current high voltage power supply.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. 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 present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In a first aspect, there is provided an adsorbent material for organic contaminants comprising a paper substrate and a layer of covalent organic framework material attached to a surface of the paper substrate;
the paper substrate is a paper substrate in paper spray ionization, and the shape of the paper substrate is triangular.
In some embodiments, the covalent organic framework material layer is used in an amount of 1 to 20 milligrams.
In some embodiments, the method of making the adsorbent material is:
placing a paper matrix material in a suction filtration funnel;
uniformly dispersing the nano covalent organic framework material in starch solution, and then pouring the starch solution into a suction filtration funnel for suction filtration;
and (3) after the solution is drained, eluting the paper substrate with absolute ethyl alcohol to remove impurities, and airing.
Further, the starch solution is a boiled and cooled solution.
Further, the dried paper substrate is pressed between glass plates for standby.
In some embodiments, the electrospray generating end of the paper substrate has an included angle of 28-32 °.
In a second aspect, there is provided a paper spray mass spectrometry detection device for organic contaminants, comprising:
the adsorbent material;
a mass spectrometer;
one end of the metal clamp is connected with a high-voltage direct current power supply, and the other end of the metal clamp clamps the adsorption material, so that the tip of the adsorption material is aligned to a sample inlet of the mass spectrometer;
and the outlet end of the injection device is connected with one end of the pipeline, and the other end of the pipeline extends to the surface of the adsorption material and is used for injecting the eluent onto the adsorption material to desorb the target object adsorbed on the adsorption material.
In some embodiments, the voltage of the HVDC power source is-3-4 kV.
In some embodiments, the metal clip is a copper clip.
In some embodiments, the other end of the conduit is located above the adsorbent material.
In a third aspect, there is provided a paper spray mass spectrometry detection method of organic contaminants, comprising the steps of:
preparing an adsorption material, and adhering a covalent organic framework material to the surface of a paper substrate by adopting a starch adhesive;
placing an adsorption material into a water sample, and adsorbing a target object in the water sample;
clamping the adsorption material adsorbed with the target object by using a metal clamp, injecting an eluent on the adsorption material, simultaneously applying high-voltage electricity to the adsorption material, and forming electrospraying of the target object at the tip of the paper substrate while realizing desorption of the target object;
electrospray is received by a mass spectrometer for detection.
In some embodiments, the adsorbent material is placed in the water sample for a period of 4-10 minutes to adsorb the target in the water sample.
Further, the mass ratio of the adsorption material to the water sample is 1:40000-50000.
In some embodiments, the rate of injection of the eluent onto the adsorbent material is 20-30 μl/min.
In some embodiments, the eluent is an ethanol solution containing 0.1% ammonia (mass concentration).
In some embodiments, the voltage applied to the adsorbent material is-3-4 kV.
In order to enable those skilled in the art to more clearly understand the technical solutions of the present disclosure, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Examples
As shown in fig. 1, the device comprises a paper substrate 1, a syringe 2, a copper clamp 3 and a high-voltage direct-current power supply 4.
First, 0.3g of starch was dissolved in 100ml of ultrapure water and heated to boil, after cooling to room temperature, 10mg of a nano covalent organic framework material was added to the above starch solution, and the mixture was sonicated to uniformly disperse the same in the starch solution. The solution was then poured into a funnel with filter paper placed therein and filtered under reduced pressure. After the solution on the filter paper is basically drained, 25ml of absolute ethyl alcohol is evenly leached on the surface of the paper substrate to wash out impurities in the coating process, and finally the prepared paper substrate is dried in the air and pressed between glass plates for standby. Covalent organic framework (TpBD) materials were modified on filter papers by vacuum filtration with starch as binder to form paper-based materials for paper spray mass spectrometry detection.
The paper-based material is then immersed in a sample solution (5 min of immersion) containing tetrabromobisphenol a and an internal standard (2, 6-dibromo-4- {2- [3, 5-dibromo-4- (2-hydroxyethoxy) benzene ] propan-2-yl } phenol), and tetrabromobisphenol a can be effectively adsorbed onto the novel paper-based material to achieve extraction and enrichment thereof due to the matching of the pore channels of the covalent organic frameworks (tpbds) to the molecular size of tetrabromobisphenol a.
After the paper-based material was sufficiently dried, washing with ultrapure water was performed for 10 seconds to remove tetrabromobisphenol a adsorbed on the surface of the paper-based material. After the matrix material is sufficiently dried, tetrabromobisphenol A is eluted from the paper-based material by continuously dripping an eluting solvent, and finally, the object to be detected is ionized by the action of an external power supply and enters a mass spectrum for detection. By using the detection method disclosed by the invention, paper spray mass spectrum detection is carried out on sample solutions containing tetrabromobisphenol A with different concentrations (1 nM-800 nM) and internal standards with the same concentration (10 mu M), and a standard curve shown in figure 2 is obtained by taking the ratio of the concentrations of tetrabromobisphenol A to the internal standards as an abscissa and the ratio of the intensities of the detected tetrabromobisphenol A to the internal standards as an ordinate. The filter paper in fig. 2 refers to a paper matrix material to which a covalent organic framework material layer is not attached.
The actual samples are from spring water of Hei Huquan in the lower region of Jinan city calendar and tap water of Jinan water service group, and in order to remove floating impurities, the water samples are filtered by an aqueous filter membrane. The detection method disclosed by the invention is used for carrying out paper spray mass spectrum detection on tetrabromobisphenol A in an environmental sample, and the obtained results are shown in table 1.
TABLE 1
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A paper spray mass spectrum detection method of tetrabromobisphenol A as an organic pollutant is characterized by comprising the following steps: the method comprises the following steps:
preparing an adsorption material, and adhering a covalent organic framework material to the surface of a paper substrate by adopting a starch adhesive;
placing an adsorption material into a water sample, and adsorbing a target object in the water sample; the target is tetrabromobisphenol A;
clamping the adsorption material adsorbed with the target object by using a metal clamp, injecting an eluent on the adsorption material, simultaneously applying high-voltage electricity to the adsorption material, and forming electrospraying of the target object at the tip of the paper substrate while realizing desorption of the target object;
the electrospray is received by a mass spectrometer for detection;
the adsorption material comprises a paper substrate and a covalent organic framework material layer attached to the surface of the paper substrate;
the paper substrate is a paper substrate in paper spray ionization, and the shape of the paper substrate is triangular;
the included angle of the electrospray generating end of the paper substrate is 28-32 degrees;
the dosage of the covalent organic framework material layer is 1-20 mg;
the covalent organic framework material is TpBD.
2. The paper spray mass spectrometry detection method of claim 1, wherein: the preparation method of the adsorption material comprises the following steps:
placing a paper matrix material in a suction filtration funnel;
uniformly dispersing the nano covalent organic framework material in starch solution, and then pouring the starch solution into a suction filtration funnel for suction filtration;
after the solution is drained, eluting the paper substrate with absolute ethyl alcohol to remove impurities, and airing;
the starch solution is boiled and cooled;
pressing the dried paper substrate between glass plates for standby.
3. The paper spray mass spectrometry detection method of claim 1, wherein: the method is realized by a paper spray mass spectrum detection device of organic pollutants, and comprises the following steps:
the adsorbent material;
a mass spectrometer;
one end of the metal clamp is connected with a high-voltage direct current power supply, and the other end of the metal clamp clamps the adsorption material, so that the tip of the adsorption material is aligned to a sample inlet of the mass spectrometer;
and the outlet end of the injection device is connected with one end of the pipeline, and the other end of the pipeline extends to the surface of the adsorption material and is used for injecting the eluent onto the adsorption material to desorb the target object adsorbed on the adsorption material.
4. A paper spray mass spectrometry detection method according to claim 3, wherein: the voltage of the high-voltage direct current power supply is-3 to-4 kV.
5. A paper spray mass spectrometry detection method according to claim 3, wherein: the other end of the pipeline is positioned above the adsorption material.
6. The paper spray mass spectrometry detection method of claim 1, wherein: the method comprises the steps of (1) placing an adsorption material into a water sample, wherein the time for adsorbing a target object in the water sample is 4-10 minutes;
the mass ratio of the adsorption material to the water sample is 1:40000-50000.
7. The paper spray mass spectrometry detection method of claim 1, wherein: the speed of injecting the eluent on the adsorption material is 20-30 mu L/min.
8. The paper spray mass spectrometry detection method of claim 1, wherein: the eluent is ethanol solution containing 0.1% ammonia, and the% is mass concentration.
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| CN112378723A (en) * | 2020-11-19 | 2021-02-19 | 深圳市易瑞生物技术股份有限公司 | Sample pad for separating and concentrating target and application thereof |
| CN112958055B (en) * | 2021-01-29 | 2022-09-09 | 山东师范大学 | Adsorbing material for water pollutants, preparation method and mass spectrum detection application thereof |
| CN112946054A (en) * | 2021-02-04 | 2021-06-11 | 西安麦斯康生物科技有限公司 | Tubular paper ionization-mass spectrometry rapid analysis method |
| CN113109416B (en) * | 2021-04-20 | 2022-06-14 | 清华大学 | Rapid high-throughput mass spectrum detection device and method for hormone |
| CN113433267B (en) * | 2021-06-11 | 2023-12-15 | 青岛海尔空调器有限总公司 | Air abnormality early warning method, device, equipment, medium and program product |
| CN116381029B (en) * | 2023-04-14 | 2023-10-13 | 江南大学 | Probe-open type mass spectrum detection method based on covalent organic framework |
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| KR20170142673A (en) * | 2016-06-20 | 2017-12-28 | 한국과학기술연구원 | Direct quantitation method of ephedrines in urine using paper spray ionization and mass spectrometry |
| CN106404945A (en) * | 2016-08-30 | 2017-02-15 | 中山大学 | Slug flow microextraction-paper spray mass spectrometry technology |
| CN107091899B (en) * | 2017-06-05 | 2019-07-02 | 环境保护部华南环境科学研究所 | The rapid assay methods of tetrabromobisphenol A in a kind of environment water |
| CN206992048U (en) * | 2017-08-08 | 2018-02-09 | 浙江大学 | A kind of paper spraying ionization and mass spectrographic combined apparatus |
| CN109932410A (en) * | 2017-12-18 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of Mass Spectrometry detection method based on papery target piece |
| CN110240705B (en) * | 2019-05-10 | 2021-04-09 | 山东省分析测试中心 | Preparation method and application of nitrogen-rich covalent organic framework material |
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