CN-114636751-B - Integrated mass spectrum ionization device for separating and ionizing zearalenone toxins and application thereof

CN114636751BCN 114636751 BCN114636751 BCN 114636751BCN-114636751-B

Abstract

The invention discloses a zearalenone toxin separation ionization integrated mass spectrum ionization device and application thereof, wherein the mass spectrum ionization device comprises a sample object stage, a detachable extraction element, an extraction element and a high-voltage power supply, wherein the sample object stage comprises a support frame, one end of the detachable extraction element is connected with the support frame, the extraction element comprises a conductive layer which is formed by stainless steel, the extraction layer is positioned on at least part of the surface of the conductive layer, the extraction layer is formed by organic covalent polymers, the covalent organic polymers are formed by 1,3, 5-tri (4-aminophenyl) benzene (TAPB) and 1,3, 5-trimethyl phloroglucinol (Tp) through polymerization, and the high-voltage power supply is connected with the extraction element. The extraction layer of the extraction element of the device is formed by covalent organic polymers, and has selective adsorption capacity to zearalenone mycotoxins and strong adsorption capacity.

Inventors

ZHANG FENG
LIU TONG
HE MUYI
GUO WEI

Assignees

中国检验检疫科学研究院
中国检验检疫科学研究院

Dates

Publication Date: 20260421
Application Date: 20220302
Priority Date: 20220302

Claims (10)

1. A separation and ionization integrated mass spectrometry ionization device for detecting zearalenone toxins, comprising: A sample stage, the sample stage comprising: A support frame; the extraction element can be dismantled, the one end of extraction element with the support frame links to each other, extraction element includes: A conductive layer formed of stainless steel; an extraction layer on at least a portion of the surface of the conductive layer, the extraction layer being formed of a covalent organic polymer formed by polymerization of 1,3, 5-tris (4-aminophenyl) benzene and 1,3, 5-trimethylphloroglucinol, and A high voltage power supply connected to the extraction element, Wherein the method of preparing the extraction element comprises: acidizing the stainless steel sheet to obtain an acidized steel sheet, wherein the acidizing condition is that the stainless steel sheet is treated by 2 mol/L sulfuric acid for 2 hours in an ultrasonic mode; contacting the acidified steel sheet with a pre-polymerization solution for pre-reaction, wherein the pre-polymerization solution is a tetrahydrofuran solution containing 1,3, 5-tris (4-aminophenyl) benzene with the concentration of 6 mL to 5 mg/mL, and Mixing a secondary reaction solution, acetic acid and the pre-polymerized solution after pre-reaction for polymerization reaction so as to form an adsorption layer on the surface of the acidified steel sheet to obtain an integrated extraction device, wherein the secondary reaction solution is a tetrahydrofuran solution containing 30.0 mg of 1,3, 5-trimethylphloroglucinol in a concentration of 2 mL; Wherein the thickness of the conductive layer is 0.1-0.5 mm, and the thickness of the extraction layer is 5-30 μm.
2. The device of claim 1, wherein the extraction element has the shape of an isosceles triangle having a waist length of 1.5-2.5 cm and a base of 0.5-1.5 cm.
3. The apparatus as recited in claim 1, further comprising: the conductive sample fixing clamp is arranged on the supporting frame and is connected with the extraction element and the high-voltage power supply.
4. The apparatus as recited in claim 1, further comprising: The movable insulating isolation ruler is connected with the supporting frame, is positioned at the upper end of the extraction element, and is adjustable in length, and the projection of the full length of the insulating isolation ruler in the horizontal direction is longer than the projection of the extraction element in the horizontal direction.
5. A mass spectrometer, comprising: A mass spectrum detector including a sample inlet, and The separation and ionization integrated mass spectrometry ionization device for detecting zearalenone compounds according to any one of claims 1-4, wherein the extraction element of the mass spectrometry ionization device is disposed opposite to the sample inlet.
6. Use of a mass spectrometry ionization device according to any one of claims 1 to 4 and a mass spectrometer according to claim 5 for detecting zearalenone content.
7. The use according to claim 6, wherein the zearalenone toxin is at least one of Zearalenone (ZEA), alpha-zearalenol (alpha-ZEL), beta-zearalenol (beta-ZEL), alpha-zearalenol (alpha-ZAL) and beta-zearalenol (beta-ZAL).
8. A method for detecting the content of zearalenone compounds in a sample to be detected, comprising: Contacting the sample to be tested with an extraction element of the mass spectrometer of claim 5 so as to extract zearalenone compounds in the sample to be tested; mounting the above extraction element on a support frame, dripping spray desorption solvent on the surface of the extraction element, desorbing the extracted zearalenone compounds, and And applying high-voltage power supply to the extraction element, ionizing the target object, and detecting the target object in a mass spectrum detector to obtain the content of the zearalenone compounds in the sample to be detected.
9. The method of claim 8, wherein the extraction is performed under shaking at 1200 rpm for 20-50 minutes; The volume of the sample to be detected is 5-25 mL; The distance between the tip of the extraction element and the sample inlet of the mass spectrum detector is 3-8 mm; The mass spectrum ionization condition of the integrated mass spectrum ionization device is that the spraying voltage of the high-voltage power supply is-2.0 to-4.0 kV; the spray desorption solvent is methanol solution containing 0-0.4% formic acid, and the volume of the desorption solvent is 10-30 mu L; the detection conditions of the mass spectrum detector are as follows: detection mode: multiple Reaction Monitoring (MRM); The atomization air pressure is 55 psi; auxiliary air pressure is 50 psi; The air pressure of the air curtain is 20 psi; Ion source temperature 550 ℃; residence time 100 ms.
10. The method of claim 9, wherein the extraction is performed under shaking at 1200rpm for 30 minutes; The volume of the sample to be detected is 10 mL; The distance between the tip of the extraction element and the sample inlet of the mass spectrum detector is 5 mm; The mass spectrum ionization condition of the integrated mass spectrum ionization device is that the spraying voltage of the high-voltage power supply is-3.5 kV; The spray desorption solvent is methanol solution containing 0-0.4% formic acid, and the volume of the desorption solvent is 20 mu L; the detection conditions of the mass spectrum detector are as follows: detection mode: multiple Reaction Monitoring (MRM); The atomization air pressure is 55 psi; auxiliary air pressure is 50 psi; The air pressure of the air curtain is 20 psi; Ion source temperature 550 ℃; residence time 100 ms.

Description

Integrated mass spectrum ionization device for separating and ionizing zearalenone toxins and application thereof Technical Field The invention relates to the field of analytical chemistry, in particular to a separation and ionization integrated mass spectrum ionization device for detecting zearalenone toxins and application thereof. Background Zearalenone toxins are a toxic secondary metabolite produced by filamentous fungi and are extremely prone to produce pollution to agricultural products and feeds, leading to serious health problems in humans and animals. When animals ingest feed contaminated with zearalenone toxins, these zearalenone toxins are metabolized to more toxic secondary products and transferred to animal products (milk, eggs, etc.), thereby increasing the risk of human ingestion of zearalenone toxins. Currently, the detection method of zearalenone toxins mainly comprises an enzyme-linked immunosorbent assay (ELISA), a sensing technology, a chromatographic method, a liquid chromatography-mass spectrometry method and the like. Although the ELISA detection method has high detection speed, most of the detection methods are semi-quantitative or qualitative analysis, and the detection method has the defects of higher false positive, poor repeatability and the like. Sensing techniques typically have poor stability, repeatability and accuracy in practical applications. Furthermore, most sensing technologies are generally only able to detect 1 zearalenone toxin. The chromatographic method has the advantages of high sensitivity, strong separation capability, difficult substrate interference and the like, but has certain defects such as incapability of simultaneously analyzing various zearalenone toxins and complicated derivatization treatment of target zearalenone toxins. In contrast, the liquid chromatography-mass spectrometry method combines the high-efficiency separation capacity of liquid chromatography with the high sensitivity of a mass spectrum detector, and can realize the accurate and rapid detection of trace zearalenone toxins in food. However, zearalenone toxins are low in concentration in foods and are easily combined with complex food matrix components, matrix interference seriously affects the sensitivity of detection, efficient sample pretreatment techniques are required to separate and purify them, and detection by a chromatography-mass spectrometry combined system takes longer. Thus, the technology for analyzing and detecting zearalenone toxins to detect compounds needs to be improved. Disclosure of Invention The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, one purpose of the invention is to provide a separation and ionization integrated mass spectrum ionization device for detecting zearalenone toxins, wherein an extraction element of the device is detachable, can be placed in a sample solution to adsorb the zearalenone toxins, is then arranged on a support frame of the mass spectrum ionization device, realizes ionization and ionization of the zearalenone toxins through high voltage electricity, further realizes extraction separation and ionization of target objects, reduces external pollution and sample loss, avoids the use of liquid chromatography, obviously shortens detection time, and is suitable for rapid extraction and direct mass spectrum detection of the zearalenone mycotoxins in complex samples. The present invention has been completed based on the following work of the inventors: Compared with the conventional liquid quality detection method, the method has the advantages that the sample pretreatment is simpler, even the sample pretreatment is not needed, the separation by a chromatographic column is not needed, the detection time can be greatly saved, and the detection of one sample usually only needs tens of seconds. The basic structure of an open mass spectrum ion source is to use a sample injection device to introduce an elution solution into the sample injection device, apply high-voltage electricity on the elution solution or the sample injection device to form electrospray, ionize under atmospheric pressure, and then enter a mass spectrometer for analysis. The current common sample injection device of the open mass spectrum ion source is mainly developed on the basis of a paper spray ion source, and an electrospray mass spectrum technology using a Solid Substrate as a carrier can be called Solid Substrate-electrospray mass spectrum (Solid-Substrate ESI-MS), and the currently adopted Solid Substrate is made of inert materials such as toothpicks, bamboo tips, porous films, glass rods and the like, and has the defects of difficult preparation, small adsorption capacity, weak enrichment capacity and the like, so that selective adsorption and detection of a certain or a certain class of compounds with similar structures are difficult to realize. In addition, when the inert material is used as a solid substrat