Heated Concentrator Injection Device

Abstract

The present invention provides a heating and concentrating sample injection device. The heating and concentrating sample injection device comprises: a shell, a sample pad, a liquid adding part and a heating component. The shell has an inner cavity. The sample pad is partially arranged in the inner cavity of the shell, and the sample pad has a tip, and the tip extends from the shell. The liquid adding part is arranged in the upper surface of the shell. The heating component is arranged above and / or below the sample pad and is configured to heat the sample pad, and the heating component comprises one or more heating units. According to the scheme of the present invention, a heating component is arranged in the heating and concentrating sample injection device to heat the sample pad, especially to heat the portion of the sample pad close to the tip, so that the sample liquid volatilizes when flowing toward the tip, and the target object is enriched and concentrated at the tip of the sample pad or a portion close to the tip, thereby improving the concentration of the target object at the injection port, and improving the sensitivity and accuracy of mass spectrometry detection.

Description

Technical Field

[0001] The invention relates to the technical field of open mass spectrometer sample injection devices, and in particular to a heating and concentrating sample injection device. Background Art

[0002] Open mass spectrometry is a new type of mass spectrometry technology based on atmospheric pressure ionization technology. It requires no or only simple sample pretreatment and directly analyzes trace substance information in samples through mass spectrometry at room temperature and pressure. This technology greatly improves the efficiency of mass spectrometry analysis, making it possible to quickly analyze samples in situ in real time, and has been widely used in food safety, environmental monitoring, biomedicine and other fields.

[0003] There are many injection methods in open mass spectrometry, such as capillary injection, tip discharge injection, etc. Paper tip discharge has been reported in the literature. For example, Chinese invention patent application CN106370718A discloses a method for rapid determination of drug dissolution, wherein a mixture of the obtained dissolution solution and the internal standard solution is dropped on a triangular paper sheet, dried, an external voltage is applied to the sample paper sheet, and then a spray solvent is dropped on the paper sheet to perform paper spray ionization; a paper cone spray ionization mass spectrometry technique is disclosed in the literature (Purum Kim, Sangwon Cha. Paper cone spray ionization mass spectrometry (PCSI MS) for simple and rapid analysis of raw solid samples. The Analyst 2015, 140 (17), 5868-5872), wherein a triangular-pyramid paper tip is used instead of a flat triangular paper tip, and the three-dimensional paper tip is used as a sample container, an in-situ solid-liquid extraction chamber, an analyte transmission channel, and an electrospray tip. In some studies, electric fields are used to separate target objects. For example, the literature (Yaoyao Zhao, Zhenwei Wei, et al. In Situ Ion-Transmission Mass Spectrometry for Paper-Based Analytical Devices. Analytical Chemistry 2016, 88 (22), 10805–10810) discloses an in-situ ion transmission mass spectrometry technique, wherein before mass spectrometry analysis, samples can be separated by paper electrophoresis or paper chromatography and a variety of other functions provided by a paper analyzer. In the prior art solution, paper is only used as an ionization medium, and the target object is not further enriched and concentrated on the paper, and the target object concentration at the injection port is not increased. Therefore, the prior art solution does not improve the sensitivity and accuracy of mass spectrometry detection.

[0004] Therefore, it is necessary to provide a heating and concentrating sample injection device to at least partially solve the problems existing in the prior art. Summary of the invention

[0005] In order to solve the above technical problems, the present invention proposes a heating and concentration injection device, which aims to solve the problems in the prior art that the target object is not further enriched and concentrated on the paper, the target object concentration at the injection port is not increased, and the sensitivity and accuracy of mass spectrometry detection are not well improved.

[0006] According to an aspect of the present invention, a heating and concentrating sample injection device is provided. The heating and concentrating sample injection device comprises:

[0007] a housing having an inner cavity;

[0008] a sample pad, the sample pad being partially disposed in the inner cavity of the housing and having a tip extending from the housing;

[0009] a liquid adding portion, the liquid adding portion being disposed in an upper surface of the housing; and

[0010] A heating component is disposed above and / or below the sample pad and is configured to heat the sample pad, and the heating component includes one or more heating units.

[0011] Preferably, the plurality of heating units are arranged above and / or below the sample pad in an interval manner along the length direction of the sample pad, and the plurality of heating units can heat different parts of the sample pad to different temperatures.

[0012] Preferably, the plurality of heating units are arranged so that the temperature of a portion of the sample pad closer to the tip is higher.

[0013] Preferably, the tip has a triangular shape.

[0014] Preferably, the shell includes an upper cover and a lower cover, a first sample pad protection block is provided at an end of the upper cover, a second sample pad protection block is provided at an end of the lower cover, a part of the sample pad away from the tip is provided between the first sample pad protection block and the second sample pad protection block, a length of one of the first sample pad protection block and the second sample pad protection block is greater than or equal to a length of an end of the sample pad opposite to the tip extending out of the shell, and a length of the other of the first sample pad protection block and the second sample pad protection block is less than a length of an end of the sample pad opposite to the tip extending out of the shell.

[0015] Preferably, a plurality of first connecting members are arranged on the inner surface of the upper cover, and a plurality of second connecting members cooperating with the first connecting members are arranged on the inner surface of the lower cover.

[0016] Preferably, a mounting structure is provided at one end of the housing, the mounting structure being configured to cooperate with an open mass spectrometer and connect the housing to the open mass spectrometer, and the tip is exposed from the mounting structure.

[0017] Preferably, the mounting structure is a U-shaped structure, and the tip is exposed from the U-shaped structure.

[0018] Preferably, the U-shaped structure is provided with a clamping portion on the outer side, and the clamping portion is configured to be clamped with the injection port of the open mass spectrometer.

[0019] Preferably, at least one end of the shell is provided with a protective cover detachably connected to the shell.

[0020] According to the solution of the present invention, a heating component is provided in the heating and concentrating sample injection device to heat the sample pad, especially to heat the portion of the sample pad close to the tip, so that the sample liquid evaporates when flowing toward the tip, and the target object is enriched and concentrated at the tip of the sample pad or a portion close to the tip, thereby increasing the concentration of the target object at the injection port and improving the sensitivity and accuracy of mass spectrometry detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Non-limiting and non-exhaustive embodiments of the present invention are described, by way of example, with reference to the following drawings, in which:

[0022] Figure 1 is an exploded perspective view of a heating and concentrating sample injection device according to an embodiment of the present invention;

[0023] Figure 2 is a top view of a heating and concentrating sample injection device according to an embodiment of the present invention;

[0024] Figure 3 is a front side view of a heating and concentrating sample feeding device according to an embodiment of the present invention; and

[0025] Figure 4 FIG. 4 is a schematic diagram of the arrangement of the heating unit of the heating component of the heating concentration sample injection device according to an embodiment of the present invention. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0027] In a first aspect of the present invention, a heating and concentrating sample feeding device is provided. Figure 1 1 is an exploded perspective view of a heating and concentrating sample injection device 100 according to an embodiment of the present invention. Figure 2 FIG. 1 is a top view of a heating and concentrating sample injection device 100 according to an embodiment of the present invention. Figure 3 2 is a front side view of a heating and concentrating sample injection device 100 according to an embodiment of the present invention. Figure 4 1 is a schematic diagram of the arrangement of heating units 1403 and 1404 of the heating component 140 of the heating and concentration sample injection device 100 according to an embodiment of the present invention.

[0028] The following will be combined Figures 1 to 4 The heating and concentrating sample feeding device 100 according to an embodiment of the present invention is described in detail.

[0029] like Figure 1 As shown, the heated and concentrated sample injection device 100 includes a housing 110 , a sample pad 120 , a liquid adding portion 130 and a heating component 140 .

[0030] The housing 110 has an inner cavity, and the sample pad 120 is partially disposed in the inner cavity of the housing 110. The sample pad 120 has a tip 1201, and the tip 1201 extends from the housing 110. Preferably, the tip 1201 has a triangular shape. The housing 110 can protect the sample pad 120 to prevent the sample pad 120 from being contaminated during operation, and make the heated concentration sample injection device 100 more convenient to use.

[0031] The liquid adding portion 130 is disposed in the upper surface of the housing 110 and is configured to at least be used to add a mass spectrometry sample solution. It should be noted that, if necessary, the sample solution can also be added dropwise through the liquid adding portion 130. Figure 1 and Figure 2 As shown, the liquid adding portion 130 includes a liquid adding recess 131 and an injection hole 132 disposed at the bottom of the liquid adding recess 131. The horizontal cross-sections of the liquid adding recess 131 and the injection hole 132 may be any suitable shape such as a circle, a square, etc. Preferably, the injection hole 132 is disposed at the center of the bottom of the liquid adding recess 131. The liquid adding recess 131 is configured to store the test liquid (e.g., mass spectrometry loading liquid, sample liquid) when the test liquid is added, so that the test liquid flows into the injection hole 132 along the bottom of the liquid adding recess 131, thereby reducing the waste of the test liquid.

[0032] The heating component 140 is disposed above and / or below the sample pad 120 and is configured to heat the sample pad 120. The heating component 140 may be a heating source that can generate heat itself, or a heat conductor that heats the sample pad 120 by conducting heat from other heat sources. The heating component 140 may include one or more heating units. Figure 1 As shown, the heating component 140 includes two heating units 1401 and 1402, and the heating units 1401 and 1402 are respectively located above and below the sample pad 120. The heating unit 1401 located above the sample pad 120 is provided with a hollow portion 1411 for allowing liquid to pass through. The heating units 1401 and 1402 are in the shape of a square plate. However, in other embodiments not shown in the present invention, the heating unit can also be any other suitable shape. Preferably, the heating units 1401 and 1402 are arranged at a position close to the tip 1201 of the sample pad 120, and the position is heated so that the sample liquid evaporates at a position close to the tip 1201, and the target is enriched and concentrated at the tip 1201 of the sample pad 120 or at a position close to the tip 1201. At the same time, the liquid flow caused by evaporating the solvent can further increase the adsorption amount of the sample pad, thereby increasing the concentration of the target at the injection tip, and improving the sensitivity and accuracy of mass spectrometry detection.

[0033] In addition, the sample pad can be heated multiple times and in sections to enhance the volatilization effect of the sample liquid. Figure 4 As shown, the heating component 140 includes a plurality of heating units 1403, 1404, which are arranged above and / or below the sample pad 120 in an interval manner along the length direction of the sample pad 120 (the direction from the tip 1201 to the other end 1202 of the sample pad 120), and the heating units 1403, 1404 have different temperatures, so that different parts of the sample pad 120 can be heated to different temperatures, thereby making the solvent on the sample pad 120 evaporate at different speeds. Preferably, the plurality of heating units 1403, 1404 are configured so that the temperature of the part of the sample pad 120 closer to the tip 1201 is higher. For example, the temperature T1 of the heating unit 1403 is set lower than the temperature T2 of the heating unit 1404. When the sample liquid flows from the other end 1202 to the tip 1201, a part of the solvent will evaporate first when passing through the heating unit 1403, thereby performing the first concentration. When flowing through the heating unit 1404, the solvent will further evaporate or even completely evaporate, thereby enriching the target in the heating unit 1404 or a position slightly passing through the heating unit 1404, that is, enriching the target in the tip 1201 or a position close to the tip 1201. By setting different temperature points and controlling the speed and amount of liquid evaporation, the sample liquid evaporates at a certain position, thereby achieving fixed-point concentration of the target and improving the sensitivity and accuracy of mass spectrometry detection.

[0034] In an embodiment not shown in the present invention, the number, area, position and temperature of the heating units can be adjusted according to the boiling point of the solvent and the crawling speed of the solvent on the sample pad. If the solvent is difficult to volatilize, the number of heating units can be increased; if the crawling speed is fast, the temperature of the heating unit can be increased or the heating area of ​​the heating unit can be increased. In addition, if the crawling speed of the solvent on the sample pad is fast, the length of the sample pad can be increased, or a sample pad with a slower flow rate can be used.

[0035] After the sample pad 120 is heated to volatilize the sample liquid near the tip 1201 and the target is enriched and concentrated at the tip 1201 or near the tip 1201 of the sample pad 120, the heated and concentrated sample injection device 100 is matched with the injection port of an open mass spectrometer to perform mass spectrometry detection. The target is enriched and concentrated by the small heated and concentrated sample injection device 100, thereby increasing the concentration of the target at the injection tip and improving the sensitivity and accuracy of mass spectrometry detection.

[0036] like Figure 1As shown, the housing 110 includes an upper cover 111 and a lower cover 112, and the liquid adding part 130 as described above can be arranged on the upper cover 111. A first sample pad protection block 121 is arranged at the end of the upper cover 111, and a second sample pad protection block 122 is arranged at the end of the lower cover 112. A portion of the sample pad 120 away from the tip 1201 is arranged between the first sample pad protection block 121 and the second sample pad protection block 122. The sample pad protection block is used to protect the sample pad 120 from being bent or damaged during production, transportation, and use, and to support the sample pad 120 during use. The length of the first sample pad protection block 121 is greater than or equal to the end of the sample pad 120 opposite to the tip 1201, that is, the other end 1202 of the sample pad 120, and extends out of the length of the shell 110. The purpose is: when the sample pad 120 is placed in the sample cup to absorb the sample liquid, the first sample pad protection block 121 can effectively support the sample pad 120 and bear the weight of the entire heating and concentration sampling device 100, thereby preventing the sample pad 120 from bending and deforming. The length of the second sample pad protection block 122 is smaller than the end of the sample pad 120 opposite to the tip 1201, i.e., the other end 1202 of the sample pad 120, and extends out of the length of the shell 110, so that the second sample pad protection block 122 will not completely cover the sample pad 120, and a portion of the sample pad 120 (e.g., the other end 1202 of the sample pad 120) can be exposed from the first shell 110. The purpose is: when the sample pad 120 is placed in the sample cup to absorb the sample liquid, the portion of the sample pad 120 exposed outside the second sample pad protection block 122 can fully contact the sample liquid, thereby improving the absorption efficiency of the sample liquid, and the portion of the sample pad 120 exposed outside the second sample pad protection block 122 can facilitate the application of high voltage to the sample pad 120 during tip discharge. For example, an alligator clip of a high-voltage DC power supply can be clamped on the portion of the sample pad 120 exposed outside the second sample pad protection block 122 to achieve the connection between the circuit and the sample pad 120.

[0037] In an embodiment not shown in the present invention, the length of the first sample pad protection block 121 may also be less than the end of the sample pad 120 opposite to the tip 1201, that is, the other end 1202 of the sample pad 120, extending out of the shell 110, and the length of the second sample pad protection block 122 may also be correspondingly greater than or equal to the end of the sample pad 120 opposite to the tip 1201, that is, the other end 1202 of the sample pad 120, extending out of the shell 110, and the sample pad 120 is exposed from the first sample pad protection block 121 above.

[0038] Preferably, the upper cover 111 and / or the lower cover 112 is provided with a positioning structure, and the positioning structure is configured to position the sample pad 120 and the heating component 140. The positioning structure can be any suitable positioning structure known in the art.

[0039] Preferably, if Figure 1 As shown, a plurality of first connectors 181 are provided on the inner surface of the upper cover 111, and a plurality of second connectors 182 cooperating with the first connectors 181 are provided on the inner surface of the lower cover 112. The first connectors 181 and the second connectors 182 are configured to combine the upper cover 111 and the lower cover 112 in a detachable manner, so that when the sample pad 120 is needed to adsorb the sample liquid, the sample pad 120 can be directly taken out of the shell 110 to adsorb the sample liquid, and after the sample liquid is adsorbed, the sample pad 120 can be assembled into the shell 110 to increase the adsorption rate of the sample liquid.

[0040] Preferably, the upper cover 111 and / or the lower cover 112 may be provided with one or more ventilation holes (not shown), and the ventilation holes are configured to help the solvent on the sample pad 120 to evaporate, accelerate the enrichment and concentration of the target on the sample pad 120, and thus improve the sensitivity and accuracy of mass spectrometry detection.

[0041] One end of the housing 110 is provided with a mounting structure, which is used to cooperate with the open mass spectrometer and connect the housing 110 to the open mass spectrometer. The tip of the sample pad 120 is exposed from the mounting structure to perform tip discharge when the heated concentration injection device cooperates with the open mass spectrometer. Figure 2 As shown, one end of the housing 110 has a U-shaped structure 150 for cooperating with an open mass spectrometer, and the U-shaped structure constitutes a mounting structure for connecting the housing 110 to the open mass spectrometer. The tip 1201 is exposed from the U-shaped structure 150 to perform tip discharge when the heating concentration injection device 100 cooperates with the open mass spectrometer. The U-shaped structure also plays a role in protecting the tip 1201, preventing the tip 1201 from bending and deforming during use. Of course, the mounting structure can also be any other suitable structure. For example, the mounting structure can be a frame structure such as a rectangular frame or a circular ring frame, and the tip 1201 is exposed from the middle of the frame structure. For another example, the mounting structure can be a mounting plate, and the tip 1201 of the sample pad 120 is supported on the mounting plate, and from the top of the mounting plate, the tip 1201 is not covered and thus exposed.

[0042] Preferably, the U-shaped structure 150 is provided with a clamping portion 160 on the outside, and the clamping portion 160 is configured to be clamped with the injection port of the open mass spectrometer. Specifically, in the present embodiment, the clamping portion 160 is a protrusion, which is clamped with the recess of the injection port of the open mass spectrometer. It can be understood that when the mounting structure is other structures such as a frame-type structure and a mounting plate, a clamping portion can also be provided on the outside of the mounting structure. Preferably, a mounting seat for mounting the heated and concentrated injection device 100 is provided at the injection port of the open mass spectrometer to ensure that the heated and concentrated injection device 100 is placed in the same position each time. When the heating and concentrating injection device 100 of the present invention cooperates with the injection port of an open mass spectrometer for injection, the U-shaped structure 150 plays a certain positioning and guiding role, so that the heating and concentrating injection device 100 extends along the mounting seat at the injection port and is clamped with the mounting seat at the injection port through the clamping portion 160 of the U-shaped structure 150, thereby positioning the distance between the tip 1201 and the mass spectrometer injector.

[0043] Preferably, at least one end of the housing 110 is provided with a protective cover (not shown) detachably connected to the housing 110. As described above, the tip 1201 of the sample pad 120 extends out of the housing 110 at one end of the housing 110 and is exposed in the U-shaped structure 150, and the other end 1202 of the sample pad 120 is exposed through the second sample pad protection block 122 at the other end of the housing 110. Therefore, the protective cover is configured to protect the tip 1201 and / or the other end 1202 of the sample pad 120 from contamination, and the protective cover can be removed when in use.

[0044] A specific embodiment of mass spectrometry detection using the heated concentration sample injection device 100 of the present invention will be described below.

[0045] Example 1

[0046] The sample cup is placed in the heater, 0.5 mL of the pesticide residue extract in vegetables is added to the sample cup, and the heating concentration injection device 100 of the present invention is placed in the sample cup, so that the portion of the sample pad 120 exposed outside the second sample pad protection block 122 is immersed in the extract, and the heater heats the heating component 140 in the heating concentration injection device 100 by electromagnetic induction, and then the heating component 140 heats the sample pad 120, and at the same time, the sample pad 120 can absorb the extract from the sample cup, wait for 10 minutes, so that the target is enriched and concentrated at the tip 1201 of the sample pad 120 or the part close to the tip 1201. The dried heating concentration injection device 100 is inserted into the mounting seat pre-fixed at the injection port of the open mass spectrometer, the alligator clip of the high-voltage DC power supply is clamped on the portion of the sample pad 120 exposed outside the second sample pad protection block 122, and then 100 μL of mass spectrometry loading liquid is dripped through the liquid adding part 130 for mass spectrometry detection.

[0047] Beneficial effects of the present invention: the heating and concentrating sample injection device of the present invention is small and convenient, and has a simple structure; a heating component is provided in the heating and concentrating sample injection device to heat the sample pad, especially to heat the portion of the sample pad close to the tip, so that the sample liquid volatilizes when flowing toward the tip, and the target is enriched and concentrated at the tip of the sample pad or a portion close to the tip, thereby increasing the concentration of the target at the injection port, and improving the sensitivity and accuracy of mass spectrometry detection; in addition, in a preferred embodiment, by performing multiple and segmented heating on the sample pad, the volatilization effect of the sample liquid can be improved, and the gradient concentration of the target on the sample pad can be achieved, thereby enriching and concentrating the target at the tip of the sample pad, thereby improving the sensitivity and accuracy of mass spectrometry detection; thirdly, by using a sample pad instead of paper for tip injection, the sample pad absorbs more liquid than traditional paper, and has modifiable ductility, which can give more sample pretreatment functions, thereby promoting the enrichment and concentration of the target on the sample pad, thereby improving the sensitivity and accuracy of mass spectrometry detection.

[0048] The technical features of the above embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0049] Although the present invention has been described in conjunction with the embodiments, it should be understood by those skilled in the art that the above description and the accompanying drawings are only exemplary and non-restrictive, and the present invention is not limited to the disclosed embodiments. Various modifications and variations are possible without departing from the spirit of the present invention.

Claims

1. A heating and concentrating sample injection device, characterized in that: include: a housing having an inner cavity; a sample pad, the sample pad being partially disposed in the inner cavity of the housing and having a tip extending from the housing; a liquid adding portion, the liquid adding portion being arranged in the upper surface of the shell; as well as a heating component, which is disposed above and / or below the sample pad and is configured to heat the sample pad, and includes one or more heating units; Wherein, the shell includes an upper cover and a lower cover, a first sample pad protection block is provided at the end of the upper cover, a second sample pad protection block is provided at the end of the lower cover, a part of the sample pad away from the tip is provided between the first sample pad protection block and the second sample pad protection block, a length of one of the first sample pad protection block and the second sample pad protection block is greater than or equal to a length of an end of the sample pad opposite to the tip extending out of the shell, and a length of the other of the first sample pad protection block and the second sample pad protection block is less than a length of an end of the sample pad opposite to the tip extending out of the shell.

2. The heating and concentrating sample feeding device according to claim 1, characterized in that: The plurality of heating units are arranged above and / or below the sample pad in an interval manner along the length direction of the sample pad, and the plurality of heating units can heat different parts of the sample pad to different temperatures.

3. The heating and concentrating sample feeding device according to claim 2, characterized in that: The plurality of heating units are configured so that the temperature of a portion of the sample pad closer to the tip is higher.

4. The heating and concentrating sample feeding device according to any one of claims 1 to 3, characterized in that: The tip has a triangular shape.

5. The heating and concentrating sample feeding device according to claim 1, characterized in that: A plurality of first connecting members are arranged on the inner surface of the upper cover, and a plurality of second connecting members cooperating with the first connecting members are arranged on the inner surface of the lower cover.

6. The heating and concentrating sample feeding device according to claim 1, characterized in that: A mounting structure is disposed at one end of the housing, the mounting structure being configured to cooperate with and connect the housing to an open mass spectrometer, and the tip is exposed from the mounting structure.

7. The heating and concentrating sample feeding device according to claim 6, characterized in that: The mounting structure is a U-shaped structure, and the tip is exposed from the U-shaped structure.

8. The heating and concentrating sample feeding device according to claim 7, characterized in that: The U-shaped structure is provided with a clamping portion on the outer side, and the clamping portion is configured to be clamped with the injection port of the open mass spectrometer.

9. The heating and concentrating sample feeding device according to claim 1, characterized in that: At least one end of the shell is provided with a protective cover detachably connected to the shell.

Images