CN111477533A - Apparatus for ion generation, transmission and mass spectrometry in low vacuum systems - Google Patents
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Abstract
本发明涉及分析测试技术领域,具体涉及一种用于低真空系统离子产生、传输与质谱联用的装置,包括离子源、一级离子传输系统、离子迁移谱、二级离子传输系统合离子质量分析器。该装置的真空系统具备多级真空差分功能;离子源置放在较低真空度的腔室中,由离子源产生的待测样品离子通过一级离子传输系统,高效传输到离子迁移谱,经离子迁移管分离后进入到二级离子传输系统实现高效率传输到离子质量分析器中;该装置系统可以提高离子产生效率,离子传输效率,并实现离子同分异构体的分离,从而提高离子分离效率和离子传输效率以及整个系统的检测灵敏度。
The invention relates to the technical field of analysis and testing, in particular to a device for ion generation, transmission and mass spectrometry in a low vacuum system, comprising an ion source, a primary ion transmission system, an ion mobility spectrum, and a secondary ion transmission system combined ion mass analyzer. The vacuum system of the device has a multi-stage vacuum differential function; the ion source is placed in a chamber with a lower vacuum degree, and the sample ions to be tested generated by the ion source pass through the primary ion transmission system and are efficiently transmitted to the ion mobility spectrum. After the ion transfer tube is separated, it enters the secondary ion transmission system to achieve high-efficiency transmission to the ion mass analyzer; the device system can improve ion generation efficiency, ion transmission efficiency, and realize the separation of ion isomers, thereby improving ion production efficiency. Separation efficiency and ion transmission efficiency and detection sensitivity of the entire system.
Description
技术领域technical field
本发明属于分析测试技术领域,特别涉及一种用于低真空系统离子产生、传输与质谱联用的装置。The invention belongs to the technical field of analysis and testing, and particularly relates to a device used for ion generation, transmission and mass spectrometry in a low vacuum system.
背景技术Background technique
离子迁移谱技术是指在低真空条件下,不同的离子在电场作用下具有不同的迁移率而进行分离,具有结构简单,分析速度快等优点,在线快速检测爆炸物、毒品等,主要用于机场、车站、出入境等场合。但是由于离子迁移谱的分辨能力较低,对于复杂混合物检测时,容易出现误报或漏报等问题。因此,出现一系列以提高离子迁移谱的分辨能力的各种联用仪技术,如气相色谱-离子迁移谱联用仪,离子迁移谱-质谱联用仪等仪器,充分发挥各个仪器的各自优势提高仪器的分辨率和准确性。Ion mobility spectrometry refers to the separation of different ions with different mobilities under the action of an electric field under low vacuum conditions. It has the advantages of simple structure and fast analysis speed. It can rapidly detect explosives, drugs, etc. on-line. Airports, stations, immigration and other occasions. However, due to the low resolving power of ion mobility spectrometry, problems such as false positives or false negatives are prone to occur when detecting complex mixtures. Therefore, a series of various hyphenated instrument technologies have emerged to improve the resolving power of ion mobility spectrometry, such as gas chromatography-ion mobility spectrometry, ion mobility spectrometry-mass spectrometry and other instruments, giving full play to the respective advantages of each instrument Improve instrument resolution and accuracy.
对于离子迁移谱与色谱或质谱或色谱-质谱联用来说,该联用技术提高了质量分辨和检测准确率,但对于一些痕量且复杂混合物质检测来说,仪器的高灵敏度是重要的技术指标,其中离子化效率和离子传输效率是影响仪器灵敏度重要因素之一,因此如何提高离子化效率和离子传输效率是未来分析检测技术中重要的发展方向之一。For ion mobility spectrometry combined with chromatography or mass spectrometry or chromatography-mass spectrometry, the combined technique improves mass resolution and detection accuracy, but for the detection of some trace and complex mixtures, the high sensitivity of the instrument is important Among them, ionization efficiency and ion transmission efficiency are one of the important factors affecting the sensitivity of the instrument. Therefore, how to improve the ionization efficiency and ion transmission efficiency is one of the important development directions in the future analysis and detection technology.
目前在生物分子分析,如蛋白质分子,多肽等大分子领域分析中,使用的大都是在常压下离子源,如ESI、DESI、DART等离子源,但是由于离子传输系统及质量分析器工作都在具备一定的真空度条件下,在常压下的离子源与离子传输系统及离子质量分析器有个真空接口,由于保证离子质量分析器达到所要求的真空度,其真空接口必须是一个有一个限制气体流量的微小孔。此微孔产生的问题之一就是由常压下离子源产生的离子在进入真空之前,约90%以上的离子被挡在真空外而损失掉。另外,由于离子在常压情况下与环境分子的频繁碰撞也会造成的离子损失;还有掺和一些未去除的溶剂分子等杂质,直接会降低后期的分析检测灵敏度。At present, in the analysis of biomolecules, such as protein molecules, peptides and other macromolecules, ion sources are mostly used under normal pressure, such as ESI, DESI, DART plasma sources, but because the ion transmission system and mass analyzer work in Under the condition of a certain degree of vacuum, the ion source under normal pressure has a vacuum interface with the ion transmission system and the ion mass analyzer. To ensure that the ion mass analyzer can reach the required vacuum degree, its vacuum interface must be one with one. Tiny holes that restrict gas flow. One of the problems with this micropore is that more than 90% of the ions generated by the ion source at atmospheric pressure are lost out of the vacuum before they enter the vacuum. In addition, due to the frequent collision of ions with environmental molecules under normal pressure, ion loss will also be caused; and impurities such as some unremoved solvent molecules will also be mixed, which will directly reduce the later analysis and detection sensitivity.
在过去多年里,人们发明了很多种电喷雾的辅助去溶剂化的技术来提高离子化效率,如美国专利US4977320提出的加热毛细管去溶剂化技术,该技术在毛细管的外围加上一个金属的导热屏蔽筒,通过对导热屏蔽筒的加热,达到提高毛细管的温度,实现去溶剂化的效果,提高离子化效率,该技术目前在部分分析仪器公司的商业仪器上得到广泛的应用。美国专利US4861988提出的反吹鞘气方法去溶剂化技术,待测样品溶液在电喷雾电离后形成离子过程中,同时被鞘气稀释,形成带电雾滴,在质谱入口反方向气流的作用下,大部分的溶剂在到达质谱入口前就挥发了,形成更小的带电微滴荷气相离子。为了提高样品去溶剂的效果,在质谱进样口前吹入反向的气流,形成一个气帘,这个气帘能够使中性的组织成分偏移质谱进样的入口,还能够带走大部分的溶剂分子,具有很好的去溶剂化的作用。使用高纯N2作为辅助鞘气具有让已经离子化的气体去溶剂的效果更好,一定流速的氮气能够吹走大部分的中性粒子和特别大的液滴,能够显著的提高去溶剂化效率。In the past few years, many electrospray assisted desolvation technologies have been invented to improve the ionization efficiency, such as the heating capillary desolvation technology proposed in US patent US4977320, which adds a metal thermal conductivity to the periphery of the capillary. The shielding cylinder can increase the temperature of the capillary by heating the thermally conductive shielding cylinder, achieve the effect of desolvation, and improve the ionization efficiency. This technology is currently widely used in the commercial instruments of some analytical instrument companies. The backflushing sheath gas method proposed by U.S. Patent US4861988 desolvation technology, the sample solution to be tested is diluted by sheath gas in the process of forming ions after electrospray ionization, and at the same time is diluted by sheath gas to form charged mist droplets. Most of the solvent evaporates before reaching the mass spectrometer inlet, forming smaller charged droplets of gas-phase ions. In order to improve the desolvation effect of the sample, a reverse air flow is blown in front of the mass spectrometer injection port to form an air curtain. This air curtain can make the neutral tissue components offset the mass spectrometer injection port, and can also take away most of the solvent. Molecules with good desolvation effect. Using high-purity N2 as the auxiliary sheath gas has a better effect of desolvating the ionized gas. A certain flow rate of nitrogen can blow away most of the neutral particles and particularly large droplets, which can significantly improve the desolvation efficiency. .
目前在离子迁移谱与质谱联用仪器中,一般都是离子源产生离子后直接进入到离子迁移谱,或在离子迁移谱前端放置一个离子透镜作为离子传输系统,但这种离子传输系统在离子传输过程中,离子只能做直线传输,无法受到射频电场的束缚,离子容易发散而丢失,从而造成大部分离子在传输过程中损失没有进入到离子迁移谱或质谱分析中,以致造成整个仪器装置写灵敏度低等不足。At present, in the combined ion mobility spectrometry and mass spectrometry instruments, the ion source generates ions and directly enters the ion mobility spectrum, or an ion lens is placed at the front of the ion mobility spectrum as an ion transmission system. During the transmission process, the ions can only be transmitted in a straight line and cannot be bound by the radio frequency electric field. The ions are easily scattered and lost, so that most of the ions are lost during the transmission process and do not enter the ion mobility spectrometry or mass spectrometry analysis, resulting in the entire instrument device. Insufficient writing sensitivity, etc.
在前期的调研中发现,在常压下的离子源产生离子后,在进入到低真空下的离子传输系统中,约90%的离子会在这个过程中丢失,从而直接影响到整个系统的检测灵敏度降低,离子信号弱等现象。In the previous investigation, it was found that after the ion source under normal pressure generates ions, about 90% of the ions will be lost in the process of entering the ion transmission system under low vacuum, which directly affects the detection of the entire system. Decreased sensitivity, weak ion signal, etc.
发明内容SUMMARY OF THE INVENTION
本发明的目的是克服现有技术存在的缺陷,提供一种以实现样品的实时高效快速分析,提高样品的离子化效率和离子传输效率,减少离子在传输过程中的损失,提高整个仪器系统的灵敏度的用于低真空系统离子产生、传输与质谱联用的装置。The purpose of the present invention is to overcome the defects existing in the prior art, to provide a real-time efficient and fast analysis of the sample, to improve the ionization efficiency and ion transmission efficiency of the sample, to reduce the loss of ions in the transmission process, and to improve the performance of the entire instrument system. Sensitive device for ion generation, transmission and mass spectrometry in low vacuum systems.
实现本发明目的的技术方案是:一种用于低真空系统离子产生、传输与质谱联用的装置,包括依次相连的初级真空室、二级真空室、三级真空室和四级真空室;所述初级真空室上设有用于产生待测样品离子的离子源、用于传输离子源所产生的待测样品离子的一级离子传输系统以及用于通入辅助气体的真空泵通气接口,该真空泵通气接口主要用于去溶剂化和辅助待测样品气相离子化;所述离子源上加载有去溶剂化装置;所述去溶剂化装置内贯穿设有毛细管;所述一级离子传输系统为离子漏斗;所述二级真空室内设有用于对待测样品离子的同分异构体进行分离的离子迁移谱,该离子迁移谱根据离子不同结构具有的迁移率不同将其分离;所述三级真空室内设有用于传输离子源所产生的待测样品离子的二级离子传输系统;所述四级真空室内设有离子探测器和用于对所测样品离子进行质量分析、得到质谱图的离子质量分析器;所述离子探测器和离子质量分析器上下相对应设置;所述初级真空室和二级真空室之间的通道位置固定有第一离子透镜;所述二级真空室和三级真空室之间的通道位置设有第二离子透镜;所述三级真空室和四级真空室之间的通道位置设有第三离子透镜;所述第一离子透镜、第二离子透镜、第三离子透镜的中间均开设有用于离子穿过的通孔。The technical scheme for realizing the object of the present invention is: a device for ion generation, transmission and mass spectrometry in a low vacuum system, comprising a primary vacuum chamber, a secondary vacuum chamber, a tertiary vacuum chamber and a fourth vacuum chamber which are connected in sequence; The primary vacuum chamber is provided with an ion source for generating sample ions to be tested, a primary ion transmission system for transmitting sample ions to be tested generated by the ion source, and a vacuum pump ventilation interface for introducing auxiliary gas. The ventilation interface is mainly used for desolvation and auxiliary gas phase ionization of the sample to be tested; the ion source is loaded with a desolvation device; the desolvation device is provided with a capillary tube; the primary ion transport system is an ion a funnel; the secondary vacuum chamber is provided with an ion mobility spectrum for separating the isomers of the sample ions to be tested, and the ion mobility spectrum separates the ions according to their different mobilities of different structures; the tertiary vacuum The chamber is provided with a secondary ion transmission system for transmitting the sample ions to be tested generated by the ion source; the 4-stage vacuum chamber is provided with an ion detector and an ion mass used for mass analysis of the measured sample ions and obtaining a mass spectrum analyzer; the ion detector and the ion mass analyzer are arranged correspondingly up and down; a first ion lens is fixed in the channel position between the primary vacuum chamber and the secondary vacuum chamber; the secondary vacuum chamber and the tertiary vacuum The channel position between the chambers is provided with a second ion lens; the channel position between the third-stage vacuum chamber and the fourth-stage vacuum chamber is provided with a third ion lens; the first ion lens, the second ion lens, the third ion lens A through hole for ions to pass through is opened in the middle of the ion lens.
上述技术方案所述真空泵通气接口位置设有辅助气体加热控温装置,以控制气体加热后通入离子源和传输系统所在的腔室中;所述的气体可以是无毒无害气体中的一种或二种以上的混合气体,如氧气,二氧化碳、六氟化硫、氩气,氙气等。In the above technical solution, an auxiliary gas heating and temperature control device is provided at the position of the vacuum pump ventilation interface, so as to control the gas to pass into the chamber where the ion source and the transmission system are located after heating; the gas can be one of the non-toxic and harmless gases. One or more mixed gases, such as oxygen, carbon dioxide, sulfur hexafluoride, argon, xenon, etc.
上述技术方案所述初级真空室上设有用于控制真空泵抽速的第一真空调节阀;所述二级真空室上设有用于控制二级真空室的真空度的第二真空调节阀;所述三级真空室上设有用于控制三级真空室的真空度的第三真空调节阀,根据实验需求实时调节离子源所在腔体的真空度。In the above technical solution, the primary vacuum chamber is provided with a first vacuum regulating valve for controlling the pumping speed of the vacuum pump; the secondary vacuum chamber is provided with a second vacuum regulating valve for controlling the vacuum degree of the secondary vacuum chamber; the The third-stage vacuum chamber is provided with a third vacuum regulating valve for controlling the vacuum degree of the third-stage vacuum chamber, and the vacuum degree of the cavity where the ion source is located can be adjusted in real time according to the experimental requirements.
上述技术方案所述离子源为置于初级真空室外部的电喷雾电离源;所述电喷雾电离源与贯穿去溶剂化装置的毛细管相连。In the above technical solution, the ion source is an electrospray ionization source placed outside the primary vacuum chamber; the electrospray ionization source is connected to a capillary running through the desolvation device.
上述技术方案所述离子源置于初级真空室内部,且对应贯穿去溶剂化装置的毛细管的位置设置,且该离子源的电极加载高压;所述毛细管与置于初级真空室外部的挥发性气体分子产生器相连。In the above technical solution, the ion source is placed inside the primary vacuum chamber, and is set at the position corresponding to the capillary tube running through the desolvation device, and the electrode of the ion source is loaded with high voltage; the capillary tube and the volatile gas placed outside the primary vacuum chamber are arranged. Molecular generators are connected.
上述技术方案所述去溶剂化装置以及毛细管位于初级真空室内部的一端均低于位于初级真空室外部的一端,其去溶剂化装置的下方设有角度和距离可调的三维移动平台;所述三维移动平台上对应毛细管位于初级真空室内部的一端端部位置设有待测样品。The end of the desolvation device and the capillary tube located inside the primary vacuum chamber in the above technical solution is lower than the end located outside the primary vacuum chamber, and a three-dimensional moving platform with adjustable angle and distance is arranged below the desolvation device; A sample to be tested is provided on the three-dimensional moving platform at one end of the corresponding capillary tube located inside the primary vacuum chamber.
上述技术方案所述四级真空室内还设有离子门、飞行时间质谱仪和第二离子探测器;所述离子门对应离子质量分析器的下方位置设置;所述第二离子探测器设置于离子质量分析器的远离三级真空室的一侧;所述飞行时间质谱仪设置于离子门和第二离子探测器的下方,并与离子门和第二离子探测器呈倒“品”字形设置。In the above technical solution, the fourth-stage vacuum chamber is also provided with an ion gate, a time-of-flight mass spectrometer and a second ion detector; the ion gate is arranged at a position below the ion mass analyzer; the second ion detector is arranged in the ion mass analyzer. The side of the mass analyzer away from the tertiary vacuum chamber; the time-of-flight mass spectrometer is arranged below the ion gate and the second ion detector, and is arranged in the shape of an inverted "pin" with the ion gate and the second ion detector.
上述技术方案所述离子迁移谱为差分离子迁移谱或迁移管离子迁移谱或高场不对称波形迁移谱。The ion mobility spectrum described in the above technical solution is a differential ion mobility spectrum or a migration tube ion mobility spectrum or a high-field asymmetric waveform mobility spectrum.
上述技术方案所述二级离子传输系统为离子透镜、多极杆、离子漏斗中的一种或多种,其中,多极杆为四极杆、六极杆、八极杆、十极杆、十二极杆、十六极杆等。The secondary ion transmission system described in the above technical solution is one or more of an ion lens, a multipole, and an ion funnel, wherein the multipole is a quadrupole, hexapole, octopole, Twelve poles, sixteen poles, etc.
上述技术方案所述离子质量分析器为四极杆质量分析器、飞行时间质量分析器、离子阱质量分析器、磁质量分析器、傅里叶回旋共振质量分析器、轨道离子阱质量分析器中的一种或多种。The ion mass analyzer described in the above technical solution is a quadrupole mass analyzer, a time-of-flight mass analyzer, an ion trap mass analyzer, a magnetic mass analyzer, a Fourier cyclotron resonance mass analyzer, and an orbital ion trap mass analyzer. one or more of.
采用上述技术方案后,本发明具有以下积极的效果:After adopting above-mentioned technical scheme, the present invention has following positive effect:
(1)本发明可以实现多级真空差分功能,可以实现样品的实时高效快速分析,待测样品由离子源在低真空环境中离子化,提高了离子化效率,同时产生离子后,直接在真空条件下直接进入到离子传输系统中,这样的结构设计可以提高离子产生效率,降低离子传输过程中的损失,从而提高离子传输效率和整个系统的检测灵敏度;还可以省去繁琐的样品前处理过程,提高分析速度和准确性,简化分析手续。(1) The present invention can realize the multi-stage vacuum differential function, and can realize the real-time, high-efficiency and rapid analysis of the sample. The sample to be tested is ionized by the ion source in a low vacuum environment, which improves the ionization efficiency. It can directly enter the ion transmission system under the condition of such a structure design, which can improve the ion generation efficiency and reduce the loss during the ion transmission process, thereby improving the ion transmission efficiency and the detection sensitivity of the whole system; it can also save the tedious sample pretreatment process. , improve the analysis speed and accuracy, and simplify the analysis procedures.
(2)本发明的离子源与样品装置,可以是一种离子源,也可以是多种不同离子源的任意排列组合,实现多个离子源对多个同类样品或者对不同样品进行同时分析,实现高通量高灵敏检测。(2) The ion source and sample device of the present invention can be one type of ion source, or can be any combination of multiple different ion sources, so that multiple ion sources can simultaneously analyze multiple samples of the same type or different samples, Achieve high-throughput and high-sensitivity detection.
(3)本发明将敞开式常压下的离子源在低真空条件下产生离子,在保持该离子源应用领域的情况下,提高离子化效率和离子传输效率,提高整个分析仪器的灵敏度,特别是在生物医学领域检测中,高灵敏度对于痕量检测起着重要的作用,提高了仪器的使用领域和效率,同时也降低该仪器的维护成本。(3) The present invention generates ions from an open ion source under normal pressure under low vacuum conditions, improves the ionization efficiency and ion transmission efficiency while maintaining the application field of the ion source, and improves the sensitivity of the entire analytical instrument, especially In the field of biomedical detection, high sensitivity plays an important role in trace detection, which improves the field of use and efficiency of the instrument, and also reduces the maintenance cost of the instrument.
(4)本发明的真空系统为多级差分真空结构,根据离子源、离子传输系统、质量分析器所要求的真空度进行实时控制调节,达到最佳工作条件。(4) The vacuum system of the present invention is a multi-stage differential vacuum structure, which is controlled and adjusted in real time according to the vacuum degree required by the ion source, ion transmission system and mass analyzer to achieve the best working conditions.
(5)本发明的离子源可以用作气态、固态或液态的样品分析中,离子源与样品装置,可以是一种离子源,也可以是多种不同离子源的任意排列组合,实现多个离子源对多个同类样品或者对不同样品进行同时分析,实现高通量高灵敏检测。(5) The ion source of the present invention can be used for gaseous, solid or liquid sample analysis. The ion source and the sample device can be one type of ion source or any combination of various ion sources to achieve multiple ion sources. The ion source analyzes multiple samples of the same type or different samples simultaneously to achieve high-throughput and high-sensitivity detection.
(6)本发明中的离子迁移管具有离子分离功能,离子在受到气压的碰撞过程中,不同的离子在电场作用下具有不同的迁移率而进行分离,具有同分异构体分离功能。(6) The ion transfer tube in the present invention has the function of ion separation. During the collision process of the ions under pressure, different ions are separated with different mobilities under the action of the electric field, and has the function of separation of isomers.
附图说明Description of drawings
为了使本发明的内容更容易被清楚地理解,下面根据具体实施例并结合附图,对本发明作进一步详细的说明,其中In order to make the content of the present invention easier to understand clearly, the present invention will be described in further detail below according to specific embodiments and in conjunction with the accompanying drawings, wherein
图1为本发明实施例1的结构示意图。FIG. 1 is a schematic structural diagram of Embodiment 1 of the present invention.
图2为本发明实施例2的结构示意图。FIG. 2 is a schematic structural diagram of
图3为本发明实施例3的结构示意图。FIG. 3 is a schematic structural diagram of Embodiment 3 of the present invention.
图4为本发明实施例4的结构示意图。FIG. 4 is a schematic structural diagram of Embodiment 4 of the present invention.
图5为本发明实施例5的结构示意图。FIG. 5 is a schematic structural diagram of Embodiment 5 of the present invention.
图6为本发明实施例6的结构示意图。FIG. 6 is a schematic structural diagram of Embodiment 6 of the present invention.
附图中标记为:101为毛细管,102为去溶剂化装置,103为辅助气体加热控温装置,104为真空泵通气接口,105为一级离子传输系统,106为离子迁移谱,107为二级离子传输系统;108为离子质量分析器,109为离子探测器,110为第一真空调节阀,111为第二真空调节阀,112为第三真空调节阀,113为第一离子透镜,114为第二离子透镜,115为第三离子透镜,116为初级真空室,117为二级真空室,118为三级真空室,119为四级真空室,120为三维移动平台,121为待测样品,122为飞行时间质谱仪,123为第二离子探测器,124为离子门,125为电极加载高压的离子源。The drawings are marked as follows: 101 is a capillary tube, 102 is a desolvation device, 103 is an auxiliary gas heating and temperature control device, 104 is a vacuum pump ventilation interface, 105 is a primary ion transmission system, 106 is an ion mobility spectrum, and 107 is a secondary Ion transmission system; 108 is an ion mass analyzer, 109 is an ion detector, 110 is a first vacuum regulating valve, 111 is a second vacuum regulating valve, 112 is a third vacuum regulating valve, 113 is a first ion lens, and 114 is a The second ion lens, 115 is the third ion lens, 116 is the primary vacuum chamber, 117 is the secondary vacuum chamber, 118 is the third vacuum chamber, 119 is the fourth vacuum chamber, 120 is the three-dimensional moving platform, and 121 is the sample to be tested , 122 is a time-of-flight mass spectrometer, 123 is a second ion detector, 124 is an ion gate, and 125 is an ion source with electrodes loaded with high voltage.
具体实施方式Detailed ways
(实施例1)(Example 1)
见图1,本发明包括依次相连的初级真空室116、二级真空室117、三级真空室118和四级真空室119;初级真空室116上设有用于产生待测样品离子的离子源、用于传输离子源所产生的待测样品离子的一级离子传输系统105以及用于通入辅助气体的真空泵通气接口104;离子源上加载有去溶剂化装置102,提高离子化效率;去溶剂化装置102内贯穿设有毛细管101;一级离子传输系统105为离子漏斗;二级真空室117内设有用于对待测样品离子的同分异构体进行分离的离子迁移谱106;三级真空室118内设有用于传输离子源所产生的待测样品离子的二级离子传输系统107;四级真空室119内设有离子探测器109和用于对所测样品离子进行质量分析、得到质谱图的离子质量分析器108;离子探测器109和离子质量分析器108上下相对应设置。初级真空室116和二级真空室117之间的通道位置固定有第一离子透镜113;二级真空室117和三级真空室118之间的通道位置设有第二离子透镜114;三级真空室118和四级真空室119之间的通道位置设有第三离子透镜115;第一离子透镜113、第二离子透镜114、第三离子透镜115的中间均开设有用于离子穿过的通孔。1, the present invention includes a
真空泵通气接口104位置设有辅助气体加热控温装置103。An auxiliary gas heating and
初级真空室116上设有用于控制真空泵抽速的第一真空调节阀110;二级真空室117上设有用于控制二级真空室117的真空度的第二真空调节阀111;三级真空室118上设有用于控制三级真空室118的真空度的第三真空调节阀112。The
本实施例中,离子质量分析器108具体为离子阱质量分析器,离子源选用最常用的敞开式常压下的电喷雾电离离子源产生带电喷雾液滴和离子的混合物,电喷雾电离源与贯穿去溶剂化装置102的毛细管101相连;根据实验需求,需要通入一些辅助气体,如二氧化碳、六氟化硫、氩气,氙气等,在初级真空室116侧面有一个真空泵通气接口104和第一真空调节阀110来控制初级真空室116的气压,根据具体实验真空需求进行调节。In this embodiment, the
在本实施具体实验过程中,在初级真空室116中,由电喷雾电离源产生的带电喷雾液滴待测样品离子通过一级离子传输系统105(离子漏斗)进入到离子迁移谱106中,样品离子根据其结构不同在离子迁移谱的电场作用下具有不同的迁移率而进行分离,根据需求,可以通过控制第二真空调节阀111来调节二级真空室117的真空度,通过离子迁移谱106分离后的离子依次进入到二级离子传输系统107(离子漏斗)中,进行高效的传输和聚焦,再次提高传输效率,减少分离后的样品离子在传输中损失,样品离子通过二级离子传输系统107依次传输到四级真空室119中的离子质量分析器108中进行分析,样品中不同质荷比的离子依次从离子质量分析器108中弹出,被离子探测器109检测。In the specific experimental process of this implementation, in the
在初级真空室116的离子漏斗工作过程中,为了提高离子漏斗的传输效率,通过真空泵通气接口104通入二氧化碳或六氟化硫等气体到离子漏斗所在的初级真空室116中,同时连接一个可控制温度调节的辅助气体加热控温装置103,在通入气体二氧化碳的时候,给该辅助气体控温加热,避免因真空腔体116的气压过低,造成电喷雾电离源的毛细管101尖端的液滴凝固而损坏。During the working process of the ion funnel in the
(实施例2)(Example 2)
本实施例与实施例1基本相同,其区别在于:在二级离子传输系统107中采用了多级杆作为离子传输系统,该多级杆为四极杆、六极杆、八极杆、十极杆、十二极杆、十六极杆等。This embodiment is basically the same as Embodiment 1, and the difference lies in that: in the secondary
离子迁移谱106为差分离子迁移谱或迁移管离子迁移谱或高场不对称波形迁移谱。The
离子质量分析器108为四极杆质量分析器、飞行时间质量分析器、离子阱质量分析器、磁质量分析器、傅里叶回旋共振质量分析器、轨道离子阱质量分析器中的一种或多种。The
(实施例3)(Example 3)
本实施例与实施例1基本相同,其区别在于:在二级离子传输系统107为离子漏斗和多级杆的组合,通过不同的离子传输系统来提高离子传输效率,去除中性分子,提高仪器系统的灵敏度。This embodiment is basically the same as Embodiment 1, the difference is that: the secondary
(实施例4)(Example 4)
本实施例与实施例1基本相同,其区别在于:离子源置于初级真空室116内部,且对应贯穿去溶剂化装置102的毛细管101的位置设置,且该离子源为电极加载高压的离子源125;毛细管101与置于初级真空室116外部的挥发性气体分子产生器相连。样品为挥发性气体分子通过毛细管101通入到初级真空室116中,离子源的电极加载高压,针尖端与样品之间产生放电,产生待测样品离子。This embodiment is basically the same as Embodiment 1, the difference is that: the ion source is placed inside the
(实施例5)(Example 5)
本实施例与实施例1基本相同,其区别在于:去溶剂化装置102以及毛细管101位于初级真空室116内部的一端均低于位于初级真空室116外部的一端,其去溶剂化装置102的下方设有角度和距离可调的三维移动平台120;三维移动平台120上对应毛细管101位于初级真空室116内部的一端端部位置设有待测样品121。This embodiment is basically the same as Embodiment 1, the difference is that the end of the
由电喷雾电离源产生的带电喷雾液滴溅射到待测样品121上,待测样品121在高速液滴碰撞后发生溅射产生气相离子,待测样品离子通过离子漏斗进行高效传输,其中待测样品121通过三维移动平台120进行角度和距离的调整,在实验过程中,可以根据不同待测样品的离子化条件的不同,进行实时观测具体的信号强度来实施调节待测样品121与电喷雾电离源、离子漏斗的距离及角度,使得实验条件达到最优。The charged spray droplets generated by the electrospray ionization source are sputtered on the sample to be tested 121, and the sample to be tested 121 sputters after the collision of the high-speed droplets to generate gas-phase ions, and the sample ions to be tested are efficiently transmitted through the ion funnel, wherein the The angle and distance of the
(实施例6)(Example 6)
本实施例与实施例1基本相同,其区别在于:四级真空室119内还设有离子门124、飞行时间质谱仪122和第二离子探测器123;离子门124对应离子质量分析器108的下方位置设置;第二离子探测器123设置于离子质量分析器108的远离三级真空室118的一侧;飞行时间质谱仪122设置于离子门124和第二离子探测器123的下方,并与离子门124和第二离子探测器123呈倒“品”字形设置。This embodiment is basically the same as Embodiment 1, except that: the fourth-
为了能够在痕量样品领域分析,提高仪器的灵敏度,样品离子在离子质量分析器108中存储一定的时间,随后对离子进行激发,激发的离子一部分进入到离子检测器109中,可以直接分析,另外一部分离子通过离子门124进入到飞行时间质谱仪122的飞行管中,最终到达第二离子探测器123中,该结构的变化,主要是对于待测样品中微量成分的离子进行分析,需要对离子进行储存,提高灵敏度,另一方面,根据检测需求,需要待测样品高分辨检测的时候,可以采用该仪器结构中的飞行时间质谱来进行高分辨检测。In order to analyze in the field of trace samples and improve the sensitivity of the instrument, the sample ions are stored in the
在本发明的内容中以及具体实施例中,在低真空中,离子源产生离子后,直接进入到一级离子传输系统中,离子可以几乎100%的效率到达离子漏斗中,从而提高了离子化效率和离子传输效率,进一步提高了整个装置的灵敏度。In the content of the present invention and in the specific embodiments, in the low vacuum, after the ion source generates ions, it directly enters the primary ion transport system, and the ions can reach the ion funnel with almost 100% efficiency, thereby improving the ionization rate. efficiency and ion transmission efficiency, further improving the sensitivity of the entire device.
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The specific embodiments described above further describe the purpose, technical solutions and beneficial effects of the present invention in further detail. It should be understood that the above descriptions are only specific embodiments of the present invention, and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
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