Portable solid-phase microextraction electrospray ionization mass spectrometry device for field analysis

Abstract

The utility model discloses a portable solid-phase micro-extraction electrospray ionization mass spectrometry device for field environment analysis. The portable solid-phase micro-extraction electrospray ionization mass spectrometry device comprises a solid-phase micro-extraction probe, a nano-spray needle capillary tube, a nano-spray needle base and a miniature mass spectrometer, through the structure, the portable solid-phase microextraction electrospray ionization mass spectrometry device can adapt to field detection work of toxic and harmful pollutants in various environments, and the solid-phase microextraction probe and the nano spray needle capillary are combined, so that rapid enrichment of trace pollutants in the field environment can be remarkably improved; and a miniature mass spectrometer is used for detecting and analyzing the pollutants on site, so that the detection sensitivity, the detection efficiency and the accuracy of the target compound are improved, and the device has very high application and popularization values in key fields such as environment emergency analysis, hazardous chemical substance management, food safety supervision and the like.

Description

Technical field:

[0001] The utility model relates to the field of separation and analysis devices and methods, in particular to a portable solid phase microextraction electrospray ionization mass spectrometry device for on-site analysis. Background technology:

[0002] On-site environmental pollutant analysis is of great significance for understanding the characteristics of pollutants. Mass spectrometry is a commonly used environmental analysis method. However, traditional laboratory mass spectrometers are difficult to use for the analysis of trace pollutants in the field environment due to their large size, heavy weight, and high requirements for the operating environment. This limitation means that in many emergency situations, such as environmental emergencies, on-site pollution monitoring, and rapid detection needs, traditional mass spectrometers cannot provide timely and effective analysis results. Portable mass spectrometers, with their small size, portability, and simple operation, provide new possibilities for the analysis of trace pollutants in the field environment.

[0003] Solid phase microextraction technology (SPME) is a commonly used sample pretreatment method, widely used in food, natural products, medicine and health, clinical chemistry, biochemistry, toxicology and forensic medicine. This technology overcomes the cumbersome and complex defects of traditional sample pretreatment methods. The coating on the quartz fiber adsorbs and enriches the analyte in the sample, and at the same time concentrates the analyte. The enriched solid phase microextraction probe can be combined with other analytical methods such as mass spectrometry to achieve sample detection. At present, the combination of solid phase microextraction (SPME) and nanoelectrospray ionization technology is considered to be an ideal method, which integrates the advantages of high desorption, high ionization efficiency, low solvent consumption and long-term continuous and stable operation. Therefore, it is very necessary to develop a solid phase microextraction enrichment and mass spectrometry detection analysis technology for field analysis to meet the needs of field analysis in complex environments.

[0004] To achieve the above objectives, a portable solid-phase microextraction electrospray ionization mass spectrometry device for on-site analysis is provided, comprising a solid-phase microextraction probe, a nanospray capillary, a nanospray base, and a miniature mass spectrometer for on-site analysis and identification. The nanospray capillary is inserted into the nanospray base, the solid-phase microextraction probe is inserted into the nanospray capillary prefilled with a desorption solvent of methanol / water (4 μL, 95 / 5, containing 0.1% formic acid and 12 mM ammonium acetate) to desorb the enriched substance, and the integrated nanospray kit is inserted into the front window of the miniature mass spectrometer for further analysis of the enriched sample. Utility model content:

[0005] In view of the shortcomings of existing technologies, the purpose of this utility model is to provide a portable solid-phase microextraction electrospray ionization mass spectrometry device for on-site analysis. This device combines a solid-phase microextraction probe with a nanospray capillary and utilizes a miniature mass spectrometer for analysis, breaking through the cumbersome and time-consuming on-site sampling and analysis methods used in traditional technologies.

[0006] According to the portable solid-phase microextraction electrospray ionization mass spectrometry device for on-site analysis, the solid-phase microextraction probe is used for the rapid enrichment of trace pollutants in the on-site environment. The probe diameter is 1 to 2 mm, and the length of the sampling part is 10 to 30 mm. The probe surface of the sampling part is pre-processed C18 coating, the coating material is 10 to 20 mm long, and the sampling part can be easily pushed and pulled out for sampling.

[0007] According to the portable solid-phase microextraction electrospray ionization mass spectrometry device for on-site analysis, the nanospray needle capillary is made of borosilicate glass with specifications of: outer wall 100-200 mm, inner wall 50-100 mm, length 500-1000 mm, tip aperture 5-10 μm, and an iron wire embedded in the capillary for contact with the solvent for electrical conduction.

[0008] According to the portable solid phase microextraction electrospray ionization mass spectrometry device for on-site analysis, a metal ball is embedded in the nanospray needle base for inserting into the micro mass spectrometer window to contact high voltage electricity to electrospray ionize the solvent, and the high voltage electricity comes from the voltage provided by the micro mass spectrometer.

[0009] According to the portable solid-phase microextraction electrospray ionization mass spectrometry device for field analysis, the miniature mass spectrometer has a size of 33 cm (length) × 23 cm (width) × 15 cm (height) and weighs approximately 8.5 kg. It is easy to carry and can adapt to on-site field detection of toxic and harmful pollutants in a variety of environments; the voltage intensity is preferably 2000 V, and the optional voltage corresponding to different substances is 1800-2200 V; the mass range in the first-level full-scan positive and negative ion mode is 50-1000 Da; the CID in the second-level positive and negative ion mode is preferably 1.5 V, and the optional voltage corresponding to different substances is 0.8-2 V.

[0010] Compared with the existing technology, the beneficial effects of the utility model are: the combination of solid-phase microextraction probe and nanospray needle capillary can significantly improve the rapid enrichment of trace pollutants in the on-site environment, and use a miniature mass spectrometer to perform on-site pollutant detection and analysis, thereby improving the detection sensitivity, detection efficiency and accuracy of target compounds. This device can adapt to on-site field detection of toxic and harmful pollutants in a variety of environments, and has high application and promotion value in key areas such as environmental emergency analysis, hazardous chemicals management, and food safety supervision. Description of the drawings:

[0011] The present invention will be further described below with reference to the accompanying drawings and embodiments;

[0012] Figure 1 This is a schematic diagram of a portable solid phase microextraction electrospray ionization mass spectrometry device of the utility model;

[0013] Figure 2 This is a schematic diagram of the integrated nanospray needle test kit of the utility model;

[0014] Figure 3 This is a schematic diagram of solid phase microextraction coupled to electrospray ionization mass spectrometry analysis in the present invention;

[0015] Figure 4 This is the first-level mass spectrum of Example 1 of the present utility model;

[0016] Figure 5 This is the secondary mass spectrum of Example 1 of the present utility model;

[0017] Figure 6 This is the primary mass spectrum of Example 2 of the present utility model;

[0018] Figure 7 This is the secondary mass spectrum of Example 2 of the present utility model;

[0019] Figure 8 This is the first-level mass spectrum of Example 3 of the present utility model;

[0020] Figure 9 This is the secondary mass spectrum of Example 3 of the present utility model;

[0021] In the figure: 1. Micro mass spectrometer; 2. Solid-phase microextraction probe; 3. Nanospray capillary; 4. Nanospray base. Specific implementation method:

[0022] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the utility model, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the utility model.

[0023] Example 1

[0024] Detection of pesticide residues in fruit juice: The solid phase microextraction probe (2) that has been adjusted with methanol and water (1:1) for 30 minutes is used to sample and enrich the fruit juice containing dimethoate for 5 minutes. The enriched probe fiber is eluted with pure water for 20 seconds and then inserted into a nanospray capillary (3) pre-filled with desorption solvent methanol / water (4μL, 95 / 5, containing 0.1% formic acid and 12mM ammonium acetate) for desorption for 3 minutes. The nanospray kit is then installed on the nanospray base (4) and inserted into the front window of the mass spectrometer for ionization analysis. After the sample generates ions, it enters the front window injection port of the micro mass spectrometer (1) to obtain the mass spectrum of the sample as shown below. Figure 4 As shown, m / z 230 is the mass spectrum peak of protonated dimethoate. The mass spectrum peak of m / z 230 is identified by secondary mass spectrometry, and the secondary mass spectrum is as shown in FIG. Figure 5 As shown in the figure, the obtained fragment ion mass spectrum peaks completely match the fragment peaks of the dimethoate standard; these data indicate that dimethoate residues in fruit juice can be enriched and accurately detected and identified.

[0025] Example 2

[0026] Detection of added Chinese and Western medicinal ingredients in herbal tea: A solid phase microextraction probe adjusted with methanol and water was used to sample and enrich herbal tea for treating insomnia. The probe fiber was eluted with pure water and then inserted into a nanospray capillary pre-filled with the desorption solvent methanol / water (4 μL, 95 / 5, containing 0.1% formic acid and 12 mM ammonium acetate) for desorption. The probe was then mounted on a nanospray base and inserted into the front window of a mass spectrometer for ionization analysis. After the sample generated ions, it entered the injection port of the front window of the micro mass spectrometer, and the mass spectrum of the sample was obtained as shown below. Figure 6 As shown, m / z 300 is the mass spectrum peak of protonated chlordiazepoxide. The mass spectrum peak of m / z 300 is identified by secondary mass spectrometry, and the secondary mass spectrum is as shown in FIG. Figure 7 As shown in the figure, the obtained fragment ion mass spectrum peaks completely match the fragment peaks of chlordiazepoxide standard; these data indicate that chlordiazepoxide added to herbal tea can be enriched and accurately detected and identified.

[0027] Example 3

[0028] Detection of malachite green residues in fish: A solid phase microextraction probe adjusted with methanol and water was inserted into the dorsal muscle of anesthetized live fish for sampling and enrichment. The probe fiber was eluted with pure water and then inserted into a nanospray capillary pre-filled with a desorption solvent of methanol / water (4 μL, 95 / 5, containing 0.1% formic acid and 12 mM ammonium acetate) for desorption. The probe was then mounted on a nanospray base and inserted into the front window of a mass spectrometer for ionization analysis. After the sample generated ions, it entered the injection port of the front window of the micro mass spectrometer to obtain the mass spectrum of the sample as shown below. Figure 8As shown, m / z 329 is the mass spectrum peak of protonated malachite green. The mass spectrum peak of m / z 329 is identified by secondary mass spectrometry, and the secondary mass spectrum is as shown in FIG. Figure 9 As shown in the figure, the obtained fragment ion mass spectrum peaks completely match the fragment peaks of the malachite green standard; these data indicate that malachite green residues in fish can be enriched and accurately detected and identified.

[0029] The above experiments prove that the utility model is not only suitable for on-site detection and analysis of fluid samples, but also for on-site detection and analysis of living samples such as fish and vegetables. It not only expands the application scope of solid-phase microextraction, but also can realize the enrichment and rapid and sensitive detection of trace pollutants in the on-site environment, and has broad market application prospects.

[0030] While the present invention has been described in detail above using general descriptions and specific embodiments, it will be apparent to those skilled in the art that modifications or improvements may be made to the present invention. Therefore, any such modifications or improvements that do not depart from the spirit of the present invention are intended to be within the scope of protection claimed herein.

Claims

1. A portable solid phase microextraction electrospray ionization mass spectrometry device for on-site analysis, characterized in that: include: A micro mass spectrometer (1), a solid phase microextraction probe (2), a nanospray capillary (3), and a nanospray base (4), wherein the solid phase microextraction probe (2) is inserted into the nanospray capillary (3) for desorbing the enriched sample, the nanospray capillary (3) is inserted into the nanospray base (4), and the nanospray base (4) is inserted into the front window of the micro mass spectrometer for analyzing the enriched sample.

2. The portable solid phase microextraction electrospray ionization mass spectrometry device for on-site analysis according to claim 1, characterized in that: The solid phase microextraction probe (2) is used for rapid enrichment of trace pollutants in an on-site environment. The probe has a diameter of 1 to 2 mm and a sampling portion length of 10 to 30 mm. The sampling portion has a probe surface with a pre-processed C18 coating, and the coating material is 10 to 20 mm long.

3. The portable solid phase microextraction electrospray ionization mass spectrometry device for on-site analysis according to claim 1, characterized in that: The nanospray needle capillary (3) is made of borosilicate glass, with specifications of: outer wall 100-200 mm, inner wall 50-100 mm, length 500-1000 mm, and tip aperture 5-10 μm.

4. The portable solid phase microextraction electrospray ionization mass spectrometry device for on-site analysis according to claim 1, characterized in that: A metal ball is embedded in the nanospray needle base (4) for connecting to a micro mass spectrometer to apply voltage for electrospray ionization.

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