WO2014075204A1

WO2014075204A1 - Apparatus and method for selectively ejecting, transmitting and concentrating ions and mass analyzer

Info

Publication number: WO2014075204A1
Application number: PCT/CN2012/001534
Authority: WO
Inventors: 徐伟; 熊行创; 江游; 黄泽建; 方向
Original assignee: 北京理工大学
Priority date: 2012-11-13
Filing date: 2012-11-13
Publication date: 2014-05-22
Also published as: CN105247654B; CN105247654A

Abstract

An apparatus and a method for selectively ejecting, transmitting and concentrating ions and a mass analyzer. A central line electrode (DC1), a top line electrode (DC2) and a bottom line electrode (DC3) are arranged on one end of a linear ion trap (1). The central line electrode (DC1) passes through a center of the linear ion trap. The central line electrode (DC1) is located between the top line electrode (DC2) and the bottom line electrode (DC3). A first direct current voltage is applied on the central line electrode (DC1). A second direct current voltage is applied on the top line electrode (DC2) and the bottom line electrode (DC3). The first direct current voltage and the second direct current voltage have opposite polarities. A double-polarity altering current voltage is applied on electrode y of the linear ion trap to excite ions whose resonance frequency matches a frequency of an alternating current signal. The exited ions are under an effect of the voltage applied on the top line electrode (DC2) and the bottom line electrode (DC3). After selected ions pass through the central line electrode (DC1), the top line electrode (DC2) and the bottom line electrode (DC3), excessive kinetic energy of the selected ions in directions y and z is removed.

Description

选择性离子弹射、传输和富集的 Selective ion ejection, transmission and enrichment

装置和方法以及质量分析器技术领域 Apparatus and method and mass analyzer

本发明涉及一种质谱仪，更具体地涉及选择性离子弹射、传输、富集的装置和方法以及质量分析器。 The present invention relates to a mass spectrometer, and more particularly to a device and method for selective ion ejection, transmission, enrichment, and a mass analyzer.

背景技术 Background technique

质谱法（MS ) 作为一种定性与定量的方法已经广泛应用于化学、生物、环境科学、制药行业、空间探测等领域。质谱仪不仅可以测量离子的质荷比（m/z) ，而且可以通过串联 MS检测离子结构。截止到目前为止，己经发明了若干质量分析仪器，例如，磁质谱（sector) ，飞行时间（TOF) ，四极离子阱，傅立叶变换离子回旋共振（FT-ICR) 单元（cell) 以及轨道离子阱（Orbitrap) 。除了用作质量分析器，四极离子阱还用作离子存储、离子导引以及离子反应装置，并与其它质量分析器组合使用从而构成功能强大的混合 MS仪器。 Mass spectrometry (MS) has been widely used in the fields of chemistry and biology, environmental science, pharmaceutical industry, space exploration, etc. as a qualitative and quantitative method. The mass spectrometer not only measures the mass-to-charge ratio (m/z) of ions, but also detects the ion structure by tandem MS. So far, several mass spectrometers have been invented, such as magnetic mass, time-of-flight (TOF), quadrupole ion trap, Fourier transform ion cyclotron resonance (FT-ICR) cells, and orbital ions. Well (Orbitrap). In addition to being used as a mass analyzer, the quadrupole ion trap is also used as an ion storage, ion guide, and ion reaction device, and is combined with other mass analyzers to form a powerful hybrid MS instrument.

MS应用的发展给 MS仪器带來了新的需求与挑战。当处理并分析离子时，空间电荷效应不可避免并且该效应己经在各种方面限制了 MS仪器的性能。首先，离子阱容量是空间电荷效应的直接结果。库仑力也可以在离子阱内展宽并漂移离子运动频率，这将导致质量漂移以及 MS分辨率降低。此外，由于离子阱饱和，有过量的离子，所以，线性动态范围将受到损失，以及可能检测不到低丰度离子。在一些离子 /离子和离子 /分子反应过程中，需要控制总的反应时间，从而可以最小化所需的子离子的进一歩的反应，由此将限制反应效率。 The development of MS applications has brought new demands and challenges to MS instruments. When dealing with and analyzing ions, the space charge effect is unavoidable and this effect has limited the performance of the MS instrument in various ways. First, the ion trap capacity is a direct result of the space charge effect. Coulomb force can also broaden and drift ion motion frequencies within the ion trap, which can result in mass drift and reduced MS resolution. In addition, due to ion trap saturation, there are excess ions, so the linear dynamic range will be lost, and low abundance ions may not be detected. In some ion/ion and ion/molecular reactions, the total reaction time needs to be controlled so that the desired reaction of the desired product ions can be minimized, thereby limiting the efficiency of the reaction.

为了最小化空间电荷效应，目前线性离子阱和离子阱阵列被广泛应用以便增加离子捕获能力。已经提出了具有双曲线形的电极以及圆形电极的线性离子阱并将其应用在商业离子阱质谱仪中，这在很大程度上改进了基于离子阱的 MS***的捕获能力和线性动态范围。为了增加单个离子阱的离子捕获能力，特别是小型化的离子阱的捕获能力，已经以阵列方式放置了多个几何形状相同的离子阱。阵列中的每 ·个离子阱在相同条件下正常工作，相同条件例如是相同的缓冲气压以及弹射（ejection) 条件。最近，已经开发了离子阱阵列，其中阵列中的每个组件发挥不同功能。双压力 (dual pressure)线性离子阱技术利用两个线性离子阱以便增加离子捕获效率和质量分析速度。已经应用双线性离子阱以便最小化对 MS分辨率产生影响的空间电荷效应。丌发了三维离子阱阵列，既，离子海绵设备，以及描述了设备内的有趣的功能，例如， 3D离子分布操纵以及离子色谱。但是,现有的线性离子阱和离子阱阵列还没有选择性离子富集的功能，尤其是连续性的选择性离子富集。此外，现有选择性离子弹射和传输方案的功耗大、效率低。发明内容 To minimize space charge effects, linear ion traps and ion trap arrays are currently widely used to increase ion trapping capability. Linear ion traps with hyperbolic electrodes and circular electrodes have been proposed and applied to commercial ion trap mass spectrometers, which greatly improves the capture capability and linear dynamic range of ion trap based MS systems. . In order to increase the ion trapping capability of a single ion trap, particularly the miniaturized ion trap capture capability, multiple ion traps of the same geometry have been placed in an array. Each ion trap in the array operates normally under the same conditions, for example the same buffer pressure and ejection conditions. Recently, ion trap arrays have been developed in which each component in the array performs a different function. Dual pressure linear ion trap technology utilizes two linear ion traps to increase ion capture efficiency and mass analysis speed. Bilinear ion traps have been applied to minimize the effects of space charge on MS resolution. Three-dimensional ion trap arrays, both ion sponge devices, and interesting features within the device, such as 3D ion distribution manipulation and ion chromatography, are described. However, existing linear ion traps and ion trap arrays do not yet have the function of selective ion enrichment, especially for continuous selective ion enrichment. In addition, existing selective ion ejection and transmission schemes consume large amounts of power and are inefficient. Summary of the invention

本发明所要解决的技术问题是克服现有技术的上述缺点，提供在离子阱阵列中选择性离子弹射、传输（selective ion transfer)和富集（accumulation)的方案以及质量分析器，，以便最小化空间电荷效应以及便于离子 /离子，离子 /分子反应。 The technical problem to be solved by the present invention is to overcome the above disadvantages of the prior art, to provide a selective ion transfer, selective ion transfer and accumulation scheme in an ion trap array, and a mass analyzer for minimizing Space charge effects and ease of ion/ion, ion/molecular reactions.

根据本发明的第一方面，提供了一种在线性离子阱中质量选择性弹射离子的装置，包括：设置在线性离子阱的一端的离子控制电极，离子控制电极包括中心线电极、顶部线电极和底部线电极，中心线电极、顶部线电极和底部线电极平行于 X轴，中心线电极位于顶部线电极与底部线电极之间，中心线电极通过线性离子阱的中心，顶部线电极与中心线电极的距离与底部线电极与中心线电极的距离相同，在中心线电极上施加第一直流电压，在顶部线电极和底部线电极上施加第二直流电压，第一直流电压与第二直流电压的极性相反；直流电压源，用于给所述中心线电极、顶部线电极和底部线电极提供直流电压；女流电压源，用于给线性离子阱的 y电极施加双极***流电压，以激发其共振频率与交流电压信号的频率匹配的离子，被激发的离子为选中的离子，选中的离子具有 y 方向上足够大的运动以感受到顶部线电极和底部线电极上施加的电压的作用，从而从 z 轴弹射选中的离子，使选中的离子离丌线性离子阱。 According to a first aspect of the present invention, there is provided an apparatus for mass selective ejection of ions in a linear ion trap, comprising: an ion control electrode disposed at one end of a linear ion trap, the ion control electrode including a center line electrode, a top line electrode And the bottom line electrode, the center line electrode, the top line electrode and the bottom line electrode are parallel to the X axis, the center line electrode is between the top line electrode and the bottom line electrode, the center line electrode passes through the center of the linear ion trap, the top line electrode and the center The distance between the wire electrode and the distance between the bottom wire electrode and the center wire electrode is the same, the first DC voltage is applied to the center wire electrode, and the second DC voltage is applied to the top wire electrode and the bottom wire electrode, the first DC voltage and the second DC voltage. The polarity of the voltage is opposite; a DC voltage source for supplying a DC voltage to the centerline electrode, the top line electrode, and the bottom line electrode; a female voltage source for applying a bipolar AC voltage to the y electrode of the linear ion trap, An ion that is excited to excite its resonant frequency and the frequency of the alternating voltage signal is excited For the selected ions, the selected ions have a sufficiently large motion in the y direction to sense the applied voltage on the top and bottom wire electrodes, thereby ejecting the selected ions from the z-axis, causing the selected ions to deviate from the linear ions. trap.

顶部线电极与中心线电极的距离或底部线电极与中心线电极的距离等于线性离子阱中心至 y电极距离 (y0 ) 。 The distance between the top line electrode and the center line electrode or the distance between the bottom line electrode and the center line electrode is equal to the linear ion trap center to y electrode distance (y0).

当捕获阳离子时，在中心线电极上施加正电压，在顶部线电极和底部线电极上施加负电压；当捕获阴离子时，在中心线电极上施加负电压，在顶部线电极和底部线电极上施加正电压；以便沿着 z轴进行阳离子或阴离子弹射。 When the cation is captured, a positive voltage is applied to the centerline electrode, and a negative voltage is applied to the top and bottom wire electrodes; when the anion is captured, a negative voltage is applied to the centerline electrode, at the top and bottom electrode A positive voltage is applied; for cation or anion ejection along the z-axis.

根据本发明的第二方面，提供了一种在线性离子阱中质量选择性弹射离子的方法，包括：在线性离子阱的一端设置平行于 X轴的中心线电极、顶部线电极和底部线电极，中心线电极位于顶部线电极与底部线电极之间，中心线电极通过线性离子阱的中心，顶部线电极与中心线电极的距离与底部线电极与中心线电极的距离相同，在中心线电极上施加第一直流电压，在顶部线电极和底部线电极上施加第二直流电压，第一直流电压第二直流电压的极性相反； According to a second aspect of the present invention, there is provided a method of mass selective ejection of ions in a linear ion trap, comprising: providing a centerline electrode, a top line electrode, and a bottom line electrode parallel to the X axis at one end of the linear ion trap The center line electrode is located between the top line electrode and the bottom line electrode, the center line electrode passes through the center of the linear ion trap, and the distance between the top line electrode and the center line electrode is the same as the distance between the bottom line electrode and the center line electrode, and the center line electrode Applying a first DC voltage, applying a second DC voltage on the top line electrode and the bottom line electrode, the second DC voltage of the first DC voltage being opposite in polarity;

给线性离子阱的 y电极施加双极***流电压信号，以激发其共振频率与交流电压信号的频率匹配的离子，被激发的离子为选中的离子，选中的离子具有 y方向上足够大的运动以感受到顶部线电极和底部线电极上施加的电压的作用，从而从 z轴弹射选中的离子，使选中的离子离丌线性离子阱。 Applying a bipolar AC voltage signal to the y electrode of the linear ion trap to excite ions whose resonant frequency matches the frequency of the AC voltage signal, the excited ions are selected ions, and the selected ions have sufficient motion in the y direction The effect of the voltage applied across the top and bottom wire electrodes is sensed to eject the selected ions from the z-axis, causing the selected ions to deviate from the linear ion trap.

根据本发明的第三方面，提供了一种在线性离子阱阵列中选择性离子传输和富集的装置，包括：线性离子阱阵列，该线性离子阱阵列包括第一线性离子阱（1 ) 和第二线性离子阱（2 ) ；第一端盖电极和第二端盖电极，第一端盖电极设置在线性离子阱阵列的一端，第二端盖电极设置在线性离子阱阵列的另一端；位于第一线性离子阱和第二线性离子阱之间的离子控制电极（3 ) ，离子控制电极包括中心线电极、顶部线电极和底部线电极，中心线电极、顶部线电极和底部线电极平行于 X轴，中心线电极位于顶部线电极与底部线电极之间，中心线电极通过线性离子阱的中心，顶部线电极与中心线电极的距离与底部线电极与中心线电极的距离相同，在中心线电极上施加第一直流电压，在顶部线电极和底部线电极上施加第二直流电压，第一直流电压与第二直流电压的极性相反；直流电压源，用于给第一线性离子阱、第二线性离子阱、中心线电极、顶部线电极和底部线电极提供直流电压；交流源，用于给线性离子阱的 y电极施加双极***流电压信号，以激发其共振频率与双极***流电压信号的频率匹配的离子，被激发的离子为选中的离子，选中的离子具有 y方向上足够大的运动以受到顶部线电极和底部线电极上施加的电压的作用，从而从 z轴弹射，离开第一线性离子阱；射频源给第一线性离子阱和第二线性离子阱提供射频电压；通过调整施加在第一线性离子阱和第二线性离子阱上的射频电压、交流电压和直流电压信号以及调整施加在中心线电极、顶部线电极和底部线电极上的直流电压实现选中的离子从第一线性离子阱传输到第二线性离子阱。 According to a third aspect of the invention, there is provided apparatus for selective ion transport and enrichment in a linear ion trap array, comprising: a linear ion trap array comprising a first linear ion trap (1) and a second linear ion trap (2); a first end cap electrode and a second end cap electrode, the first end cap electrode being disposed in one of the linear ion trap arrays a second end cap electrode disposed at the other end of the linear ion trap array; an ion control electrode (3) between the first linear ion trap and the second linear ion trap, the ion control electrode including a center line electrode and a top line electrode And the bottom line electrode, the center line electrode, the top line electrode and the bottom line electrode are parallel to the X axis, the center line electrode is between the top line electrode and the bottom line electrode, the center line electrode passes through the center of the linear ion trap, the top line electrode and the center The distance between the wire electrode and the distance between the bottom wire electrode and the center wire electrode is the same, the first DC voltage is applied to the center wire electrode, and the second DC voltage is applied to the top wire electrode and the bottom wire electrode, the first DC voltage and the second DC voltage. The polarity of the voltage is reversed; a DC voltage source for supplying a DC voltage to the first linear ion trap, the second linear ion trap, the center line electrode, the top line electrode, and the bottom line electrode; an AC source for the linear ion trap The y electrode applies a bipolar AC voltage signal to excite its resonant frequency to match the frequency of the bipolar AC voltage signal Ions, the excited ions are selected ions, and the selected ions have a sufficiently large motion in the y direction to be subjected to a voltage applied across the top and bottom wire electrodes, thereby ejecting from the z axis, leaving the first linear ion trap. The RF source provides a RF voltage to the first linear ion trap and the second linear ion trap; the RF voltage, the AC voltage, and the DC voltage signal applied to the first linear ion trap and the second linear ion trap are adjusted and applied to the center The DC voltage on the line electrode, the top line electrode, and the bottom line electrode enables selected ions to be transported from the first linear ion trap to the second linear ion trap.

可选择地，第一线性离子阱具有尺寸： x_Q =_y_Q = 5 mm， z₀ =40 mm;第二线性离子阱具有尺寸： x_Q = = 5 mm， z₀ = 80 mm_; 第一线性离子阱与第二线性离子阱之间的距离是 2 mm, 以及中心线电极、顶部线电极和底部线电极具有 0.2 mm的直径；顶部线电极和底部线电极离中心线电极的距离等于线性离子阱的尺寸或不等于 ¾; 其中表示线性离子阱中心至 X电极距离， ¾表示线性离子阱中心至 y电极距离， ζθ表示线性离子阱的纵向尺寸；在第一线性离子阱上施加恒定的射频电压和在第二线性离子阱上施加恒定的射频电压，第一线性离子阱上的射频电压和第二线性离子阱上的射频电压设置为 278 V；频率为 230 kHz、零一峰值为 0.2 V的双极***流电压施加在第一线性离子阱上，施加在第二线性离子阱上的双极***流电压 AC2为 =0;将 6V直流电压施加在中心线电极上，以及将 -2.5 V直流电压施加在顶部线电极与底部线电极上；将 -5 V偏置电压施加在第二线性离子阱上。 Alternatively, the first linear ion trap has dimensions: x _Q = _y _Q = 5 mm, z ₀ = 40 mm; the second linear ion trap has dimensions: x _Q = = 5 mm, z ₀ = 80 mm _; The distance between the linear ion trap and the second linear ion trap is 2 mm, and the center line electrode, the top line electrode, and the bottom line electrode have a diameter of 0.2 mm; the distance between the top line electrode and the bottom line electrode from the center line electrode is equal to linear The size of the ion trap may not be equal to 3⁄4; which represents the linear ion trap center to X electrode distance, 3⁄4 represents the linear ion trap center to y electrode distance, ζθ represents the longitudinal dimension of the linear ion trap; a constant applied to the first linear ion trap The RF voltage and a constant RF voltage applied to the second linear ion trap, the RF voltage on the first linear ion trap and the RF voltage on the second linear ion trap are set to 278 V; the frequency is 230 kHz, and the zero-to-peak value is 0.2. The bipolar AC voltage of V is applied to the first linear ion trap, the bipolar AC voltage AC2 applied to the second linear ion trap is =0; the 6V DC voltage is applied to the centerline electrode, and -2.5 V DC voltage is applied on top of the wire electrode and the bottom electrode wire; -5 V to the bias voltage applied to the second linear ion trap.

可选择地，第一线性离子阱具有尺寸： x。= ¾ = 5 mm, z₀ =40 mm;第二线性离子阱具有尺寸： x_Q =_y。 = 5 mm， z₀ = 80 mm_; 第一线性离子阱与第二线性离子阱之间的距离是 2 mm, 以及中心线电极、顶部线电极和底部线电极具有 0.2 mm的直径；顶部线电极和底部线电极离中心线电极的距离等于线性离子阱的尺寸 ¾或不等于 ¾; 其中 co表示线性离子阱中心至 X电极距离，： ^表示线性离子阱中心至 y电极距离， ζθ表示线性离子阱的纵向尺寸；在 y电极上施加频率为 230 kHz、零一峰值为 0.4V的双极***流电压的同时通过扫描施加在第一线性离子阱上的第一射频电压，从而在不同的时间传输不同质荷比的离子，施加在第一线性离子阱上的第一射频电压为 200V/S , 施加在第二线性离子阱上的第二射频电压和第一射频电压保持相同，施加在第二线性离子阱上的双极***流电压为 0，将 6V的直流电压施加在中心线电极上，以及将 -2.5 V直流电压施加在顶部线电极与底部线电极上，将 -5 V偏置电压施加在第二线性阱上。 Alternatively, the first linear ion trap has a size: x. = 3⁄4 = 5 mm, z ₀ = 40 mm; the second linear ion trap has dimensions: x _Q = _y. = 5 mm, z ₀ = 80 mm _; the distance between the first linear ion trap and the second linear ion trap is 2 mm, and the centerline electrode, the top wire electrode and the bottom wire electrode have a diameter of 0.2 mm; the top wire electrode The distance from the bottom wire electrode to the centerline electrode is equal to the size of the linear ion trap 3⁄4 or not equal to 3⁄4; where co represents the distance from the center of the linear ion trap to the X electrode, : ^ represents the distance from the center of the linear ion trap to the y electrode, and ζ θ represents the linear ion The longitudinal dimension of the well; applying a bipolar AC voltage having a frequency of 230 kHz and a zero-to-peak value of 0.4 V to the y-electrode while scanning the first RF voltage applied to the first linear ion trap, thereby at different times Transmitting ions of different mass-to-charge ratios, the first RF voltage applied to the first linear ion trap is 200V/s, applied to the second linear ion trap The second RF voltage remains the same as the first RF voltage, the bipolar AC voltage applied to the second linear ion trap is zero, the 6V DC voltage is applied to the centerline electrode, and the -2.5 V DC voltage is applied. Applied to the top line electrode and the bottom line electrode, a -5 V bias voltage is applied to the second linear well.

施加在第一线性离子阱上的交流电压为如下交流电压之一：单一频率的交流电压、宽频带的交流电压、多频带 /多频的交流电压。所述离子为母离子或子离子。 The AC voltage applied to the first linear ion trap is one of the following AC voltages: a single frequency AC voltage, a wide frequency AC voltage, a multi-band/multi-frequency AC voltage. The ions are parent ions or daughter ions.

中心线电极、顶部线电极和底部线电极为任何形状的导线或圆柱形导线，三个线电极位于两个离子阱之间的间隔的中间位置或者位于两个离子阱之间的任何位置。 The centerline electrode, the topline electrode, and the bottomline electrode are any shape of wire or cylindrical wire, and the three wire electrodes are located at an intermediate position between the two ion traps or at any position between the two ion traps.

所述在线性离子阱阵列中选择性离子传输和富集的装置还包括冷却离子装置，所述冷却离子装置用于在 y方向上和 /或 z方向上冷却沿 z轴从第一线性离子阱传输到第二线性离子阱的离子；所述冷却离子装置包括电压控制器和 /或缓冲气体供给装置，所述电压控制器调整脉冲或扫描直流和 /或 AC2，以便去除传输到线性离子阱的离子的动能能量，防止传输到第二线性离子阱的离子返回到第一线性离子阱；所述缓冲气体供给装置为线性离子阱提供缓冲气体，缓冲气体用于在离子弹回到离子控制电极之前在 y方向上和 /或 z方向上冷却传输到线性离子阱中的选中的离子。 The apparatus for selective ion transport and enrichment in a linear ion trap array further includes a cooling ion device for cooling the first linear ion trap along the z-axis in the y-direction and/or the z-direction An ion transported to a second linear ion trap; the cooled ion device includes a voltage controller and/or a buffer gas supply device, the voltage controller adjusting a pulse or scanning a direct current and/or an AC2 to remove the transmission to the linear ion trap The kinetic energy of the ions prevents ions transferred to the second linear ion trap from returning to the first linear ion trap; the buffer gas supply device provides a buffer gas for the linear ion trap, and the buffer gas is used to return the ion bomb to the ion control electrode before The selected ions transported into the linear ion trap are cooled in the y-direction and/or the z-direction.

施加在第二线性离子阱上的交流与施加在第一线性离子阱上的交流锁频，施加在第二线性离子阱上的交流与施加在第一线性离子阱上的交流相移 180度，通过施加在第二线性离子阱上的交流去除传输到第二线性离子阱的离子的动能能量，以便防止离子传输回到第一线性离子阱。 The alternating current applied to the second linear ion trap and the alternating current frequency applied to the first linear ion trap, the alternating current applied to the second linear ion trap and the alternating current applied to the first linear ion trap are shifted by 180 degrees, The kinetic energy of ions transported to the second linear ion trap is removed by alternating current applied to the second linear ion trap to prevent ion transport back to the first linear ion trap.

根据本发明的第四方面，提供了一种在线性离子阱阵列中选择性离子传输和和富集的方法，包括：通过在线性离子阱的 y电极上施加双极性 AC信号以便在 y方向上激发具有特定质荷比 m/z的选中的离子，所述特定质荷比（m/z) 的离子的共振频率与在线性离子阱的 y电极 !：.施加双极性 AC信号的共振频率匹配；被激发的离子为选中的离子，选中的离子具有 y方向上足够大的运动以受到设置在线性离子阱之间的离子控制电极的顶部线电极 DC2和底部线电极上施加的电压的作用，从 z轴弹射选中的离子并使选中的离子离丌线性离子阱，在选中的离子通过离子控制电极之后，去除选中的离子在和2 方向上的过量的动能以便在第二线性离子阱 #2中捕获离子。 According to a fourth aspect of the present invention, there is provided a method of selective ion transport and enrichment in a linear ion trap array, comprising: applying a bipolar AC signal on a y electrode of a linear ion trap for y direction Exciting selected ions having a specific mass-to-charge ratio m/z, the resonance frequency of the ions of the specific mass-to-charge ratio (m/z) and the resonance of the bipolar AC signal applied to the y-electrode of the linear ion trap!: Frequency matching; the excited ions are selected ions, and the selected ions have a sufficiently large movement in the y direction to be applied by the voltage applied to the top line electrode DC2 and the bottom line electrode of the ion control electrode disposed between the linear ion traps. Acting, ejecting the selected ions from the z-axis and separating the selected ions from the linear ion trap. After the selected ions pass through the ion-control electrode, the excess kinetic energy of the selected ions in the 2 direction is removed to facilitate the second linear ion trap. Capture ions in #2.

根据本发明的第: £方面，提供了一种质量分析器，包括：线性离子阱阵列，线性离子阱阵列包括二个或者二个以上的线性离子阱；端盖电极，线性离子阱阵列的两端各设有一个端盖电极；离子控制电极，离子控制电极设置在线性离子阱之间，离子控制电极包括中心线电极、顶部线电极和底部线电极，中心线电极、顶部线电极和底部线电极平行于 X轴，中心线电极位于顶部线电极与底部线电极之间，中心线电极通过线性离子阱的中心，顶部线电极与中心线电极的距离与底部线电极与中心线电极的距离相同，在中心线电极上施加第一直流电压，在顶部线电极和底部线电极上施加第二直流电压，第一直流电压与第二直流电压的极性相反；射频电压源，用于给所述线性离子阱提供射频；直流电压源，用于给所述线性离子阱、中心线电极、顶部线电极和底部线电极提供直流电压；交流电压源，用于给线性离子阱的 Y电极施加双极***流电压电压，以激发其共振频率与双极***流电压的共振频率匹配的离子，被激发的离子为选中的离子，选中的离子具有 y方向上足够大的运动以受到顶部线电极和底部线电极上施加的电压的作用；通过调整施加在所述线性离子阱上的射频电压、交流电压和直流电压以及施加在中心线电极、顶部线电极和底部线电极的直流电压实现选中的离子从前一级线性离子阱沿 z轴传输到与前一级线性离子阱相邻的后一级线性离子阱。 According to the first aspect of the present invention, there is provided a mass analyzer comprising: a linear ion trap array, the linear ion trap array comprising two or more linear ion traps; an end cap electrode, two of the linear ion trap array Each end is provided with an end cap electrode; an ion control electrode, the ion control electrode is disposed between the linear ion traps, and the ion control electrode The center line electrode, the top line electrode and the bottom line electrode are included, the center line electrode, the top line electrode and the bottom line electrode are parallel to the X axis, the center line electrode is located between the top line electrode and the bottom line electrode, and the center line electrode passes through the linear ion trap Center, the distance between the top line electrode and the center line electrode is the same as the distance between the bottom line electrode and the center line electrode, a first DC voltage is applied to the center line electrode, and a second DC voltage is applied to the top line electrode and the bottom line electrode, The first DC voltage is opposite to the polarity of the second DC voltage; an RF voltage source for providing radio frequency to the linear ion trap; a DC voltage source for the linear ion trap, the center line electrode, the top line electrode, and The bottom line electrode provides a DC voltage; an AC voltage source is used to apply a bipolar AC voltage to the Y electrode of the linear ion trap to excite ions whose resonant frequency matches the resonant frequency of the bipolar AC voltage, the excited ion For the selected ion, the selected ion has a sufficiently large motion in the y direction to be subjected to the top wire electrode and the bottom The effect of the voltage applied to the line electrode; the selected ion is achieved by adjusting the RF voltage, the AC voltage and the DC voltage applied to the linear ion trap, and the DC voltage applied to the center line electrode, the top line electrode and the bottom line electrode. The primary linear ion trap is transported along the z-axis to a subsequent linear ion trap adjacent to the previous linear ion trap.

在所述质量分析器的线性离子阱阵列的后端可以增加轨道阱和 /或飞行时间（TOF) 设备。 An orbitrap and/or time of flight (TOF) device can be added to the back end of the linear ion trap array of the mass analyzer.

本发明具有以下优点和有益效果：本发明通过在线性离子阱的一端或在线性离子阱阵列之间设置离子控制电极并控制施加在线性离子阱上的射频电压、交流电压、直流偏置以及施加在离子控制电极的直流电压，能实现在线性离子阱阵列中选择性离子弹射、传输和富集，最小化了空间电荷效应以及便于离子 /离子，离子 /分子反应。此外，本发明的选择性离子弹射、传输和富集的方案比现有技术的功耗小并且比现有技术的效率高。 The present invention has the following advantages and benefits: The present invention provides an ion control electrode between one end of a linear ion trap or a linear ion trap array and controls RF voltage, AC voltage, DC bias, and application applied to the linear ion trap. The DC voltage at the ion-controlled electrode enables selective ion ejection, transmission, and enrichment in a linear ion trap array, minimizing space charge effects and facilitating ion/ion, ion/molecular reactions. Moreover, the selective ion ejection, transmission, and enrichment schemes of the present invention are less power consuming than prior art and more efficient than prior art techniques.

附图说明 DRAWINGS

应说明的是，下面描述中的附图仅示意地示出了一些实施例，并没有包括所有可能的实施例。 It should be noted that the drawings in the following description are only illustrative of some embodiments and do not include all possible embodiments.

图 la是根据本发明的实施例的具有从 z轴质量选择性弹射离子能力的线性离子阱的示意图；图 lb是根据本发明的实施例的离子控制电极在 x-y平面的结构示意图； Figure la is a schematic illustration of a linear ion trap having the ability to selectively eject ions from a z-axis mass in accordance with an embodiment of the present invention; Figure lb is a schematic illustration of the structure of an ion control electrode in the x-y plane in accordance with an embodiment of the present invention;

图 2是根据本发明实施例的具有离控制电极的线性离子阱阵列的结构示意图；图 3a是 ώ两个线性离子阱构成的离子阱阵列的示意图，其中在两个线性离子阱之间具有离子控制电极；图 3b表示势阱形成于阱阵列的中心；图 3c表示势阱形成于离丌阱阵列的轴的位置；图 4是连续离子传输的示意波形； 2 is a schematic view showing the structure of a linear ion trap array having a control electrode according to an embodiment of the present invention; FIG. 3a is a schematic diagram of an ion trap array composed of two linear ion traps, wherein ions are present between two linear ion traps. Control electrode; Figure 3b shows the potential well formed at the center of the well array; Figure 3c shows the potential well formed at the axis of the trap array; Figure 4 is a schematic waveform of continuous ion transport;

图 5a是 m/z为 180的连续离子传输的示例；图 5b是 m/z为 181的连续离子传输的示例；图 5c是 m/z为 184的连续离子传输的示例； Figure 5a is an example of continuous ion transport with m/z of 180; Figure 5b is an example of continuous ion transport with m/z of 181; Figure 5c is an example of continuous ion transport with m/z of 184;

图 6a是 m/z为 180的离散离子传输的示例；图 6b是 m/z为 181的离散离子传输的示例；图 6c是 m/z为 184的离散离子传输的示例； Figure 6a is an example of discrete ion transport with m/z of 180; Figure 6b is an example of discrete ion transport with m/z of 181; Figure 6c is an example of discrete ion transport with m/z of 184;

图 7是离散离子传输使用的示意波形； Figure 7 is a schematic waveform used for discrete ion transport;

图 8是不同离子传输和富集策略的示例； Figure 8 is an example of different ion transport and enrichment strategies;

图 9是在气相离子反应过程中稀疏的子离子富集的示例。 Figure 9 is an example of sparse daughter ion enrichment during gas phase ion reaction.

具体实施方式 detailed description

为使本发明的目的、技术方案和优点更加清楚，下面结合附图描述本发明的示例性实施例的技术方案。显然，所描述的实施例只是本发明的一部分实施例，而不是全部的实施例。所描述的实施例仅用于图示说明，而不是对本发明范围的限制。基于本发明的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。 In order to make the objects, the technical solutions and the advantages of the present invention more clear, the technical solutions of the exemplary embodiments of the present invention are described below with reference to the accompanying drawings. It is apparent that the described embodiments are only a part of the embodiments of the invention, and not all of the embodiments. The described embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.

为了叙述方便，本文中所称的 " X轴" 、 "y轴" 、 "z轴"与图 1、图 2和图 3a中的 For the convenience of description, the "X-axis", "y-axis", "z-axis" and the figures in Figure 1, Figure 2 and Figure 3a are referred to herein.

" X轴"、 "y轴" " z轴"方向一致， " X " 、 "y" "z"的定义与空间直角坐标系定义相同， y电极为线性离子阱的沿 y轴方向对称分布的一对电极， X电极为线性离子阱的沿 X轴方向对称分布的一对电极， V表示电压的单位 "伏"；但并不对本发明的结构起限定作用。从具有双曲线电极的线性离子阱的 Z轴质量选择性弹射离子 The "X-axis", "y-axis" and "z-axis" directions are the same. The definitions of "X", "y" and "z" are the same as the definition of the space rectangular coordinate system. The y-electrode is symmetrically distributed along the y-axis of the linear ion trap. A pair of electrodes, the X electrodes are a pair of electrodes symmetrically distributed along the X-axis direction of the linear ion trap, and V represents the unit of voltage "volt"; however, it does not limit the structure of the present invention. Z-axis mass selective ejection of ions from a linear ion trap with a hyperbolic electrode

离子在四极电场内具有特征运动频率 (characteristic motion frequencies) ，其中最低频率成分被称为共振频率（secular frequency) 。具有不同质荷比 m/z的离子将具有不同的共振频率。在线性离子阱中，在 x-y平面施加四极 RF电场， DC电场用于捕获 z轴方向上的离子。在线性离子阱中，离子将具有 x-y平面上的共振频率。因此，通常在 2D离子阱（具有双曲线电极的线性离子阱）和矩形离子阱（rectilinear ion trap) 的 x-y平面质量选择性弹射离子。借助使用边缘电场，从具有圆形电极的线性离子阱的 z轴质量选择性弹射离子。 Ions have characteristic motion frequencies in a quadrupole electric field, where the lowest frequency component is called the secular frequency. Ions with different mass to charge ratios m/z will have different resonance frequencies. In a linear ion trap, a quadrupole RF electric field is applied in the x-y plane, which is used to capture ions in the z-axis direction. In a linear ion trap, the ions will have a resonant frequency in the x-y plane. Therefore, the x-y plane quality is typically selectively ejected at the 2D ion trap (linear ion trap with hyperbolic electrodes) and the rectangular trap (rectilinear ion trap). Selective ejection of ions from the z-axis mass of a linear ion trap with a circular electrode by using a fringing electric field.

为了便于在离子阱阵列中离子选择性传输，提出了从具有双曲线电极的线性离子阱的 z轴质量选择性弹射离子的一种方案。图 1示出了这种方案的一个实施例。如图 la所示，在离子阱 1的一端放置端盖电极 4，在离子阱 1的另一端放置离子控制电极 3，离子控制电极 3包括三个平行于 x轴的线电极，三个线电极分别为中心线电极 DC1、顶部线电极 DC2和底部线电极 DC3。中心线电极 DC1位于顶部线电极 DC2与底部线电极 DC3 之间，中心线电极 DC1通过离子阱的中心，顶部线电极 DC2与中心线电极 DC1的垂直距离与底部线电极 DC3与中心线电极 DC1的垂直距离相同，例如，顶部线电极 DC2与中心线电极 DC1的距离或底部线电极与中心线电极 DC1的距离等于线性离子阱中心至 y 电极 5距离（yO) 。在中心线电极上施加第一直流电压，在顶部线电极 DC2和底部线电极 DC3上施加第二直流电压，第一直流电压与第二直流电压的极性相反。例如，由直流电压源给中心线电极 DC1、顶部线电极 DC2和底部线电极 DC3提供直流电压。 In order to facilitate ion selective transport in an ion trap array, a scheme for z-axis mass selective ejection of ions from a linear ion trap with a hyperbolic electrode is proposed. Figure 1 shows an embodiment of such a solution. As shown in FIG. 1a, an end cap electrode 4 is placed at one end of the ion trap 1, and an ion control electrode 3 is placed at the other end of the ion trap 1, ion The control electrode 3 includes three line electrodes parallel to the x-axis, and the three line electrodes are a center line electrode DC1, a top line electrode DC2, and a bottom line electrode DC3, respectively. The center line electrode DC1 is located between the top line electrode DC2 and the bottom line electrode DC3, the center line electrode DC1 passes through the center of the ion trap, the vertical distance between the top line electrode DC2 and the center line electrode DC1, and the bottom line electrode DC3 and the center line electrode DC1 The vertical distance is the same, for example, the distance of the top line electrode DC2 from the center line electrode DC1 or the distance between the bottom line electrode and the center line electrode DC1 is equal to the distance from the linear ion trap center to the y electrode 5 (yO). A first DC voltage is applied to the centerline electrode, and a second DC voltage is applied to the top line electrode DC2 and the bottom line electrode DC3, the first DC voltage being opposite to the polarity of the second DC voltage. For example, a DC voltage is supplied to the center line electrode DC1, the top line electrode DC2, and the bottom line electrode DC3 by a DC voltage source.

当捕获阳离子时，可以在中心线电极 DC1上施加正电压，在顶部线电极 DC2和底部线电极 DC3上施加负电压。在没有激发的情况下，离子云将具有沿着离子阱 z轴的圆柱形，阳离子将受到中心线电极 DC1产生的捕获电势的作用。为了沿着 _ζ轴质量选择性弹射离子，可以在离子阱的 y电极上施加双极***流（AC ) 电压以便激发其共振频率与双极性 AC电压信号的频率匹配的离子。 y电极为线性离子阱的沿 y轴方向对称分布的一对电极。由交流电压源给离子阱的 y电极施加双极性 AC电压信号。被激发的离子为选中的离子。使用合适的激发电压，选中的离子将具有 y方向上足够大的运动以受到顶部线电极 DC2和底部线电极 DC3上施加的负电压的作用，从而从 _Z轴弹射选中的离子，使选中的离子离丌离子阱。离子检测器 7可以检测从 _Z轴弹射并离丌离子阱的离子。 When the cation is captured, a positive voltage may be applied to the center line electrode DC1, and a negative voltage may be applied to the top line electrode DC2 and the bottom line electrode DC3. Without excitation, the ion cloud will have a cylindrical shape along the z-axis of the ion trap, and the cation will be subjected to the trapping potential generated by the centerline electrode DC1. In order to be applied on the alternating current bipolar electrodes of the ion trap along the y axis _ζ mass-selective ion ejection (AC) voltage to the excitation frequency of the resonance frequency of the bipolar AC voltage signal matches ions. The y electrodes are a pair of electrodes of the linear ion trap symmetrically distributed along the y-axis direction. A bipolar AC voltage signal is applied to the y electrode of the ion trap from an alternating voltage source. The excited ions are selected ions. Using a suitable excitation voltage, the selected ions will have a sufficiently large motion in the y direction to be subjected to a negative voltage applied across the top line electrode DC2 and the bottom line electrode DC3, thereby ejecting the selected ions from the _Z axis, causing the selected ions Ion the ion trap. The ion detector 7 can detect ions ejected from the _Z- axis and separated from the helium ion trap.

当捕获阴离子时，可以在中心线电极 DC1上施加负电压，以及在顶部线电极 DC2 和底部线电极 DC3上施加正电压，以便沿着 z轴进行离子弹射。 When the anion is trapped, a negative voltage can be applied to the center line electrode DC1, and a positive voltage is applied to the top line electrode DC2 and the bottom line electrode DC3 to perform ion ejection along the z-axis.

在给定射频电压 RF或某一射频电压 RF的情况下，具有不同质荷比 m/z的离子具有不同的共振频率，，选中的离子的共振频率与施加在离子阱的 y电极上的 AC电压信号的共振频率匹配，所以可以沿着 z轴质量选择性弹射离子，即沿着 z轴弹射具有与施加在离子阱的 y电极上的 AC信号的共振频率对应的质荷比 m/z的离子。当改变射频电压 RF 时，同一质荷比 m/z的离子的共振频率会随之改变。 In the case of a given RF voltage RF or a certain RF voltage RF, ions having different mass-to-charge ratios m/z have different resonance frequencies, and the resonance frequency of the selected ions and the AC applied to the y-electrode of the ion trap The resonant frequency of the voltage signal is matched so that ions can be selectively ejected along the z-axis mass, i.e., along the z-axis, having a mass-to-charge ratio m/z corresponding to the resonant frequency of the AC signal applied to the y-electrode of the ion trap. ion. When the RF voltage RF is changed, the resonance frequency of ions of the same mass-to-charge ratio m/z changes.

在离子阱阵列中离子选择性传输和富集 Ion selective transport and enrichment in ion trap arrays

基于从线性离子阱的 z轴质量选择性弹射离子，可以实现在离子阱阵列中离子选择性传输和富集。图 2示出了离子阱阵列，该离子阱阵列包括两个线性离子阱和离子控制电极 3。离子控制电极 3位于线性离子阱之间，离子控制电极 3用于控制离子弹射和传输。两个线性离子阱包括第一线性离子阱 1和第二线性离子阱 2。图 2中的离子控制电极 3 的结构与图 1中的离子控制电极的结构相同，包括三个平行于 X轴的线电极，三个线电极分别为中心线电极 DC1、顶部线电极 DC2和底部线电极 DC3。如图 2所示，每一线性离子阱 1、 2包括 y电极 5和 X电极 6， y电极为线性离子阱的沿 y轴方向对称分布的一对电极， X电极为线性离子阱的沿 X轴方向对称分布的一对电极。 Selective ion transport and enrichment in an ion trap array can be achieved based on z-axis mass selective ejection of ions from a linear ion trap. Figure 2 shows an ion trap array comprising two linear ion traps and an ion control electrode 3. The ion control electrode 3 is located between the linear ion traps, and the ion control electrode 3 is used to control ion ejection and transmission. The two linear ion traps include a first linear ion trap 1 and a second linear ion trap 2. The structure of the ion control electrode 3 in FIG. 2 is the same as that of the ion control electrode in FIG. 1, and includes three line electrodes parallel to the X axis, and the three line electrodes are the center line electrode DC1, the top line electrode DC2, and the bottom, respectively. Line electrode DC3. As shown in FIG. 2, each linear ion trap 1, 2 includes a y electrode 5 and an X electrode 6, and the y electrode is a symmetrically distributed y-axis of the linear ion trap. For the counter electrode, the X electrode is a pair of electrodes of the linear ion trap symmetrically distributed along the X-axis direction.

图 3 ( a) 示出了图 2所示的离子阱阵列的截面视图和放置在离子阱阵列两端的端盖电极 4。在这种设置中，有两个端盖电极 4和在这两个离子阱之间的离子控制电极 3。 Figure 3 (a) shows a cross-sectional view of the ion trap array shown in Figure 2 and an end cap electrode 4 placed at both ends of the ion trap array. In this arrangement, there are two end cap electrodes 4 and an ion control electrode 3 between the two ion traps.

作为示例，第一离子阱 1具有尺寸： x_G = _y() = 5 mm， z₀ =40 mm; 第二离子阱 2 具有尺寸： x_G = ¾ = 5 mm， zo = 80 mn！。这两个离子阱之间的距离是 2 mm，其中 xo是离子阱中心至 X电极距离（即离子阱的尺寸），：₀是离子阱中心至 y电极距离， ζθ是离子阱的纵向尺寸。 "离子阱中心至 X电极距离"指的是 "离子阱中心至 X电极双曲面顶点的距离"， "离子阱中心至 y电极距离"指的是 "离子阱中心至 y电极双曲面顶点的距离。 As an example, the first ion trap 1 has dimensions: x _G = _y() = 5 mm, z ₀ = 40 mm; the second ion trap 2 has dimensions: x _G = 3⁄4 = 5 mm, zo = 80 mn! . The distance between the two ion traps is 2 mm, where xo is the ion trap center to X electrode distance (ie, the size of the ion trap), ₀ is the ion trap center to y electrode distance, and ζ θ is the longitudinal dimension of the ion trap. "Ion trap center to X electrode distance" refers to the "distance from the center of the ion trap to the apex of the X electrode hyperboloid", "the distance from the center of the ion trap to the y electrode" refers to the distance from the center of the ion trap to the apex of the y electrode hyperboloid .

例如，三个线电极可以位于两个离子阱之间的间隔的中间位置。可选择地，三个线电极也可以位于两个离子阱之间的任何位置。 For example, three wire electrodes can be located intermediate the spacing between the two ion traps. Alternatively, the three wire electrodes can also be located anywhere between the two ion traps.

作为实例，三个线电极可以是三根平行导线，线电极可以为任何形状，例如线电极可以为圆柱形，线电极具有 0.2 mm的直径。这三个线电极用作离子弹射和传输的控制电极，从而通过调整在这些电极上的适当的电压获得选择性离子传输。 As an example, the three wire electrodes may be three parallel wires, and the wire electrodes may be of any shape, for example, the wire electrodes may be cylindrical and the wire electrodes have a diameter of 0.2 mm. These three wire electrodes serve as control electrodes for ion ejection and transmission, thereby enabling selective ion transport by adjusting the appropriate voltage across these electrodes.

中心线电极 DC 1放在中间，顶部线电极 DC2和底部线电极 DC3离中心线电极的距离例如为离子阱的尺寸 x0，顶部线电极 DC2和底部线电极 DC3离中心线电极的距离也可以大于或小于离子阱的尺寸 χ0。 The center line electrode DC 1 is placed in the middle, and the distance between the top line electrode DC2 and the bottom line electrode DC3 from the center line electrode is, for example, the size x0 of the ion trap, and the distance between the top line electrode DC2 and the bottom line electrode DC3 from the center line electrode may also be greater than Or less than the size of the ion trap χ0.

为了获得來自第一离子阱 1 至第二离子阱 2的选择性离子传输，首先通过在第一离子阱 1 的 y电极上施加双极性 AC信号以便在 y方向上激发具有特定质荷比 m/z的选中的离子，所述特定质荷比 m/z的离子的共振频率与在第离子阱的 y电极上施加的双极性 AC信号的频率匹配，在中心线电极上施加第一直流电压，在顶部线电极 DC2和底部线电极 DC3上施加第二直流电压，第一直流电 H与第二直流电压的极性相反；之后沿着第一离子阱 1的 z轴向第二离子阱 2弹射选中的离子。在离子通过离子控制电极 3之后，去除离子在 y和 z方向上的过量动能以便在第二离子阱 2中捕获离子。 In order to obtain selective ion transport from the first ion trap 1 to the second ion trap 2, a bipolar AC signal is first applied on the y electrode of the first ion trap 1 to excite a specific mass to charge ratio m in the y direction. /z selected ions, the resonant frequency of the ions of the specific mass-to-charge ratio m/z is matched with the frequency of the bipolar AC signal applied on the y-electrode of the ion trap, and the first direct current is applied to the center line electrode a voltage, a second direct current voltage is applied to the top line electrode DC2 and the bottom line electrode DC3, the polarity of the first direct current H and the second direct current voltage are opposite; then the second ion trap 2 along the z-axis of the first ion trap 1 Eject the selected ions. After the ions pass through the ion control electrode 3, excess kinetic energy of the ions in the y and z directions is removed to capture ions in the second ion trap 2.

可以在离子阱 1和离子阱 2上施加不同 RF、 AC和 DC信号从而便于离子传输。将合适的 DC电压施加在离子阱上，可以获得如图 3 ( b ) 和（c ) 所示的势阱。图 3 ( b ) 表示在离子阱阵列的中心形成的势阱，图 3 ( c ) 表示在离开离子阱阵列的中心轴的位置形成的势阱。沿着离子阱阵列 (x = 0，y= 0)的中心轴，形成沿着 z轴的两个离子捕获区域，以及通过离子控制电极形成的势壁（potential wall ) 来分离该两个捕获区域。当离子具有 y方向 t的较大的运动时，离子将经受如图 3 ( c ) 所示的势阱，在该势阱条件下第一离子阱 1的离子可以传输到第二离子阱 2的内部。 Different RF, AC, and DC signals can be applied to ion trap 1 and ion trap 2 to facilitate ion transport. Applying a suitable DC voltage to the ion trap provides a potential well as shown in Figures 3(b) and (c). Figure 3 (b) shows the potential well formed at the center of the ion trap array, and Figure 3(c) shows the potential well formed at a position away from the central axis of the ion trap array. Along the central axis of the ion trap array (x = 0, y = 0), two ion trapping regions along the z-axis are formed, and a potential wall formed by the ion-control electrode is used to separate the two trapping regions . When the ions have a large motion in the y-direction t, the ions will undergo a potential well as shown in Figure 3(c), under which the ions of the first ion trap 1 can be transported to the second ion trap 2. internal.

可以按照两种方式实现离子传输：（1) 连续离子传输；（2) 离散离子传输。 Ion transport can be achieved in two ways: (1) continuous ion transport; (2) discrete ion transport.

( 1 )连续离子传输在连续离子传输模式中，通过在离子阱上设置合适的射频 (RF)电压，交流（AC ) 电压和直流（DC) 电压，只要选中的或关注的离子在第一离子阱 1出现，就将该离子传输到第二离子阱 2 。为了获得连续离子传输，可以在第一离子阱 1上施加恒定 (constant) 射频 (RF)电压 RF1，其中离子将具有固定的共振频率。通过在第一离子阱 1上施加双极 ***流电压 AC1以及在第二离子阱 2上施加直流偏置 DC以吸引离子向第二离子阱 2传输，将选中的离子传输到第二离子阱 2。 (1) Continuous ion transport In continuous ion transfer mode, by setting the appropriate radio frequency (RF) voltage, alternating current (AC) voltage and direct current (DC) voltage on the ion trap, as long as the selected or focused ion appears in the first ion trap 1, This ion is transmitted to the second ion trap 2. To achieve continuous ion transport, a constant radio frequency (RF) voltage RF1 can be applied to the first ion trap 1, where the ions will have a fixed resonant frequency. The selected ions are transported to the second ion trap 2 by applying a bipolar alternating voltage AC1 on the first ion trap 1 and applying a DC bias DC on the second ion trap 2 to attract ions to the second ion trap 2. .

图 4示出了可以用于连续离子传输的波形。在图 4中， RF1为在第一离子阱 1上施加的恒定射频电压 RF1， RF2为在第二离子阱 2上施加的恒定射频电压， AC1为在第一离子阱 1的 y电极上施加的双极***流电压， AC2为在第二离子阱 2的 y电极上施加的双极***流电压 AC2。 Figure 4 shows the waveforms that can be used for continuous ion transport. In FIG. 4, RF1 is a constant radio frequency voltage RF1 applied to the first ion trap 1, RF2 is a constant radio frequency voltage applied to the second ion trap 2, and AC1 is applied to the y electrode of the first ion trap 1. The bipolar alternating voltage, AC2, is the bipolar alternating voltage AC2 applied to the y electrode of the second ion trap 2.

在连续离子传输的模拟中，例如，将恒定的 RF1和 RF2设置为 278 V, AC1的频率为 230 kHz、零一峰值为 0.2 V; AC2 = 0; 将 6V (伏） DC电压施加在中心线电极上，以及将 -2.5 V的 DC 施加在顶部线电极与底部线电极上；将 -5 V偏置电压施加在第二离子阱 2上；将 20V的电压加到第一离子阱 1左侧的端盖电极 4和第二离子阱 2右侧的端盖电极 4上，端盖电极 4参见图 3a。将氦气用作缓冲气体，压力为 3 mTorr。图 5a、图 5b、图 5c示出了模拟结果，其中选择第一离子阱 1中的具有《1/₂为 180的离子以连续方式传输至第二离子阱 2。 In the simulation of continuous ion transport, for example, set constant RF1 and RF2 to 278 V, AC1 frequency is 230 kHz, zero-to-peak is 0.2 V; AC2 = 0; apply 6V (volt) DC voltage to the centerline On the electrode, and applying -2.5 V DC to the top line electrode and the bottom line electrode; applying a -5 V bias voltage to the second ion trap 2; applying a voltage of 20 V to the left side of the first ion trap 1 The end cap electrode 4 and the end cap electrode 4 on the right side of the second ion trap 2, and the end cap electrode 4 are shown in Fig. 3a. Helium was used as a buffer gas at a pressure of 3 mTorr. Figures 5a, 5b, 5c show simulation results, wherein selecting a first ion trap having a _"1/2 180 transmitted to the second ion trap 2 in a continuous manner.

图 5a是 m/z为 180的连续离子传输的示例；图 5b是 m/z为 181的连续离子传输的示例；图 5c是 m/z为 184的连续离子传输的示例。当 RF1 = 278 V时， m/z 为 180 的离子具有 30 kHz的共振频率，该共振频率与 AC1的频率匹配或者接近于 AC1的频率。因此，在施加 AC1时，如图 5 a底部所示， m/z 为 180 的这些离子将被激发到 y方向上的更大轨道上。在 y方向上具有小的离子运动幅度时，离子受到由中心线电极提供的捕获电压的作用，在本例中捕获电压（即施加在中心线电极上的电压）为 6V。当离子运动幅度增加时，离子将受到顶部线电极与底部线电极提供的引出电压（extractive voltage) 的作用并传输到第二离子阱 2。所以，在本例中，在第一离子阱的 m/z为 180的离子的共振频率与 AC1的频率匹配并被激发到 y方向上较大轨道，即 m/z为 180的离子具有 y方向上足够大的运动，从而， m/z为 180的离子可以受到顶部线电极 DC2和底部线电极 DC3上施加的 DC电压作用，从而从 z轴弹射，离开第离子阱，传输到第二离子阱 2。但是， m/z为 181的离子和 m/z为 184的离子的共振频率与 AC1的频率不匹配，在 y方向上只有小的离子运动幅度，没有受到 ώ顶部线电极与底部线电极上施加的作用作用，所以没有传输到第二离子阱。 Figure 5a is an example of continuous ion transport with m/z of 180; Figure 5b is an example of continuous ion transport with m/z of 181; Figure 5c is an example of continuous ion transport with m/z of 184. When RF1 = 278 V, an ion with an m/z of 180 has a resonant frequency of 30 kHz that matches or is close to the frequency of AC1. Therefore, when AC1 is applied, as shown at the bottom of Figure 5a, these ions with m/z of 180 will be excited to a larger orbit in the y direction. With a small amplitude of ion motion in the y-direction, the ions are subjected to a trapping voltage provided by the centerline electrode, which in this example captures the voltage (i.e., the voltage applied to the centerline electrode) to 6V. As the ion motion amplitude increases, the ions are subjected to an extractive voltage provided by the top and bottom wire electrodes and are transmitted to the second ion trap 2. Therefore, in this example, the resonance frequency of the ion having the m/z of 180 in the first ion trap matches the frequency of AC1 and is excited to a larger orbit in the y direction, that is, the ion having an m/z of 180 has the y direction. Sufficiently large motion, such that ions with an m/z of 180 can be subjected to a DC voltage applied across the top line electrode DC2 and the bottom line electrode DC3, thereby ejecting from the z-axis, leaving the ion trap, and transmitting to the second ion trap. 2. However, the resonance frequency of ions with m/z of 181 and ions of m/z of 184 does not match the frequency of AC1, and there is only a small amplitude of ion motion in the y direction, which is not applied by the top line electrode and the bottom line electrode. The role of the action, so no transmission to the second ion trap.

(2) 离散离子传输 (2) Discrete ion transmission

对于离散离子传输，可以将选屮的或关注的离子在不同的时间段传输到第二离子阱 2, 或者选择不同的离子在不同的时间段传输。在每一个时间段，可以按照与连续模式相似的方式实现离子传输。可选地，可以扫描双极性 AC信号和 /或离子共振频率以便根据离子的 m/z比顺序进行传输。或者，可选地，可以扫描 RF信号和 /或离子共振频率，以便根据离子的 m/z比顺序进行传输。图 7示出了离散离子传输实施例使用的示意波形。 For discrete ion transport, selected or focused ions can be transported to the second ion trap at different time periods 2, or choose different ions to transmit in different time periods. At each time period, ion transport can be achieved in a manner similar to continuous mode. Alternatively, the bipolar AC signal and/or the ion resonance frequency can be scanned for transmission in accordance with the m/z ratio of the ions. Alternatively, the RF signal and/or the ion resonance frequency may be scanned to be sequentially transmitted in accordance with the m/z ratio of the ions. Figure 7 shows a schematic waveform used in a discrete ion transport embodiment.

例如， AC1的频率 230 kHz, AC1的零一峰值为 0.4 V，在施加 AC1激发信号的同时通过 200V/S的扫描 RF1在不同的时间传输不同的离子，其中 AC2=0， RF1和 RF2保持相同，在端盖电极 4上的 DC信号和在离子控制电极上的 DC信号与图 5a、图 5b、图 5c中所使用的相同，图 6a、图 6b、图 6c示出在此情况下的离散离子传输的示例。图 6a 是 m/z为 180的离散离子传输的示例；图 6b是 m/z为 181的离散离子传输的示例；图 6c 是 m/z为 184的离散离子传输的示例。在这种情况下，通过扫描 RF1和 RF2将 m/z为 180 的离子和 m/z为 181的离子顺序传输到第二离子 2。 For example, the frequency of AC1 is 230 kHz, and the zero-to-peak value of AC1 is 0.4 V. Different voltages are transmitted at different times by 200V/S scanning RF1 while applying the AC1 excitation signal, where AC2=0, RF1 and RF2 remain the same. The DC signal on the cap electrode 4 and the DC signal on the ion control electrode are the same as those used in Figures 5a, 5b, 5c, and Figures 6a, 6b, 6c show the dispersion in this case. An example of ion transport. Figure 6a is an example of discrete ion transport with m/z of 180; Figure 6b is an example of discrete ion transport with m/z of 181; Figure 6c is an example of discrete ion transport with m/z of 184. In this case, ions having m/z of 180 and ions having m/z of 181 are sequentially transferred to the second ion 2 by scanning RF1 and RF2.

为了将传输到第二离子阱 2中的离子富集，需要在离子弹回到图 2所示的离子控制电极之前在 y方向上和 /或 z方向上冷却传输到第二离子阱 2的离子。这在连续离子传输模式中非常关键，其中施加在第一离子阱 1上的 RF电压 RF1和施加在第二离子阱 2上的 RF电压 RF2是恒定的。在这些条件下，如果不冷却离子，离子将返回第一离子阱 1，这将降低它们的存留机会，诸如通过与离子控制电极的线电极的碰撞而消失。在图 5a、 5b、 5c和图 6a、 6b、 6c所示的模拟结果中，缓冲气体已经在冷却方面起到了非常重要的作用。除了缓冲气体，可以调整脉冲或扫描 DC和 /或 AC2，以便防止离子传输回第一离子阱 1。例如， AC2可以与 AC1锁频或频率相同，但是 AC2与 AC1相移 180度，参见图 4和图 7，从而利用 AC2去除传输到第二离子阱 2的离子的动能能量。需要仔细控制电信号，从而离子不会再次从 AC2获取动能能量。 In order to enrich the ions transported into the second ion trap 2, it is necessary to cool the ions transported to the second ion trap 2 in the y direction and/or the z direction before the ion bomb returns to the ion control electrode shown in FIG. . This is critical in the continuous ion transport mode in which the RF voltage RF1 applied to the first ion trap 1 and the RF voltage RF2 applied to the second ion trap 2 are constant. Under these conditions, if the ions are not cooled, the ions will return to the first ion trap 1, which will reduce their chance of retention, such as by collision with the wire electrode of the ion control electrode. In the simulation results shown in Figures 5a, 5b, 5c and Figures 6a, 6b, 6c, the buffer gas has played a very important role in cooling. In addition to the buffer gas, the pulse or sweep DC and / or AC2 can be adjusted to prevent ions from being transported back to the first ion trap 1 . For example, AC2 can be the same frequency or frequency as AC1, but AC2 is phase shifted by 180 degrees from AC1, see Figure 4 and Figure 7, to remove the kinetic energy of the ions transported to the second ion trap 2 using AC2. Careful control of the electrical signal is required so that the ions do not acquire kinetic energy from AC2 again.

在上述示例中，在离子阱阵列中存在两个离子阱，但本发明并不局限于此, 以包括更多的离子阱或质量分析器。例如，可以使用三个或者更多个线性离子阱，以及可以使用上述提出的相同方法在这些离子阱中弹射、传输、富集离子。此外，可以在离子阱阵列的后端（例如图 3 a所示第一.离子阱 2的右边）增加高性能的质量分析器用于高精度 / 分辨率分析，例如，轨道阱和飞行时间（TOF) 设备。 In the above example, there are two ion traps in the ion trap array, but the invention is not limited thereto to include more ion traps or mass analyzers. For example, three or more linear ion traps can be used, and ions can be ejected, transported, and enriched in these ion traps using the same methods set forth above. In addition, a high performance mass analyzer can be added at the back end of the ion trap array (eg, to the right of the first ion trap 2 shown in Figure 3a) for high precision/resolution analysis, for example, orbitrap and time of flight (TOF) ) Equipment.

基于不同应用的不同方案 Different solutions based on different applications

在离子阱阵列中的离子富集方法用于复杂样本分析，特别是用于复杂样本中的低丰度离子分析。生物样本通常含有富的化学成分，例如血液、尿样以及细胞样本，很多情况下化学物质之间的浓度会有很大的不同。在很多的例子中，低丰度离子可以携带重要信息。然而， ώ于动态范围局限，分辨率局限以及离子阱中的空间电荷效应，在质谱中可能观测不到低丰度离子。 Ion enrichment methods in ion trap arrays are used for complex sample analysis, especially for low abundance ion analysis in complex samples. Biological samples usually contain rich chemical components such as blood, urine, and cell samples. In many cases, the concentration between chemicals will vary greatly. In many cases, low abundance ions can carry important information. However, due to dynamic range limitations, resolution limitations, and space charge effects in the ion trap, low abundance ions may not be observed in the mass spectrum.

对于不同的应用，不同的离子传输和富集策略可以便于化学分析并提高分析精确度，灵敏度以及分辨率。例如，对于具有特定 m/z的离子，对于具有多个 m/z的离子组可以进行离子传输与富集。 For different applications, different ion transport and enrichment strategies can facilitate chemical analysis and improve analytical accuracy, sensitivity, and resolution. For example, for ions with a specific m/z, ion transport and enrichment can be performed for ion groups with multiple m/z.

图 8示出了不同离子传输和富集方案的示例，对于具有图 8所示的范围内的 m/z的离子组可以进行离子传输与富集。 Figure 8 shows an example of different ion transport and enrichment schemes for which ion transport and enrichment can be performed for an ion group having m/z within the range shown in Figure 8.

如图 8所示，当在第一离子阱的 y电极上施加单一频率的 AC信号时，在第一离子阱中的一种质荷比 m/z的离子传输到第二离子阱,这种质荷比 m/z的离子的共振频率与施加在离子阱的 y电极上的 AC信号的共振频率匹配，这种离子可以为低丰度离子。 As shown in FIG. 8, when a single frequency AC signal is applied to the y electrode of the first ion trap, a mass-to-charge ratio m/z ion in the first ion trap is transmitted to the second ion trap. The resonant frequency of the ion to mass-to-charge ratio m/z matches the resonant frequency of the AC signal applied to the y-electrode of the ion trap, which may be a low-abundance ion.

如图 8所示,当在第一离子阱的 y电极上施加宽频带的 AC信号时，在第一离子阱中的三种质荷比 m/z的离子传输到第二离子阱，宽频带的 AC信号中具有与这些质荷比 m/z的离子的共振频率匹配的频率分量，这些离子可以包括低丰度离子。 As shown in FIG. 8, when a wide-band AC signal is applied to the y-electrode of the first ion trap, ions of three mass-to-charge ratios m/z in the first ion trap are transmitted to the second ion trap, and the broadband is wide. The AC signal has frequency components that match the resonant frequencies of the ions of these mass-to-charge ratios m/z, and these ions may include low abundance ions.

如图 8所示,当在第一离子阱的 y电极上施加多频带 /多频的 AC信号时,在第一离子阱中的三种质荷比 m/z的离子传输到第二离子阱,所施加的 AC信号中具有与这些质荷比 m/z 的离子的共振频率匹配的频率分量，这些离子可以包括低丰度离子。 As shown in FIG. 8, when a multi-band/multi-frequency AC signal is applied to the y-electrode of the first ion trap, ions of three mass-to-charge ratios m/z in the first ion trap are transmitted to the second ion trap. The applied AC signal has frequency components that match the resonant frequencies of the ions of these mass-to-charge ratios m/z, and these ions may include low abundance ions.

本发明的另一应用在于：在碎裂与气相离子反应过程中富集信息性子离子，以便提高碎裂和反应速率。碎裂和反应是动态过程，在该动态过程中，子离子可能经历进一歩的碎裂或者反应。在一些其它的情况下，信息性子离子可能丰度较低。传输并富集这些子离子将保护这些离子免受进一歩裂解。如果不将子离子传输并富集，子离子会经历进一歩的反应，而消失。将子离子传输走，可使子离子可免受进一歩反应、裂解，从而对子离子进行了保护，可以长时间的对母离子进行反应，而不影响检测子离子。因此，可以完全执行母离子（前驱离子）的反应，这将增加反应速率并改进分析灵敏度。图 9描述了子离子富集的示意图，图 9示出的是在气相离子反应过程中稀疏的子离子富集的示例。如图 9所示，标记的子离从第一离子阱 1传输到了第二离子阱 2，所述标记的子离子的共振频率与施加在第一离子阱的 y电极上的 AC信号的频率匹配。例如，所述标记的子离子是第-一离子阱中的第二代子离子。 Another application of the present invention resides in the enrichment of informational product ions during fragmentation and gas phase ion reaction to increase fragmentation and reaction rates. Fragmentation and reaction are dynamic processes in which the daughter ions may undergo further fragmentation or reaction. In some other cases, informational ion ions may be less abundant. Transporting and enriching these daughter ions will protect these ions from further cleavage. If the daughter ions are not transported and enriched, the daughter ions will undergo a further reaction and disappear. By transporting the daughter ions away, the daughter ions can be protected from further reaction and cleavage, thereby protecting the daughter ions and reacting the precursor ions for a long time without affecting the detector ions. Therefore, the reaction of the parent ion (precursor ion) can be completely performed, which increases the reaction rate and improves the analysis sensitivity. Figure 9 depicts a schematic of daughter ion enrichment, and Figure 9 shows an example of sparse daughter ion enrichment during gas phase ion reaction. As shown in FIG. 9, the labeled sub-distribution is transmitted from the first ion trap 1 to the second ion trap 2, and the resonant frequency of the labeled sub-ion matches the frequency of the AC signal applied to the y-electrode of the first ion trap. . For example, the labeled daughter ions are second generation daughter ions in the first ion trap.

以上对本发明的实施例的描述仅用于说明本发明的技术方案，而不是对本发明范围的限制，本发明并不限于所公开的这些实施例，本领域的技术人员可以对前述各实施例所 id载的技术方案进行修改，或者对其中部分技术特征进行等同替换，而这些修改或替换都应落入本发明的保护范围。 The above description of the embodiments of the present invention is only intended to illustrate the technical solutions of the present invention, and is not to limit the scope of the present invention. The present invention is not limited to the disclosed embodiments, and those skilled in the art may The technical solutions contained in the id are modified, or some of the technical features are equivalently replaced, and these modifications or replacements are intended to fall within the scope of the present invention.

Claims

权利要求 Rights request

1. 一种在线性离子阱中质量选择性弹射离子的装置，包括： 1. A device for mass selective ejection of ions in a linear ion trap, comprising:

设置在线性离子阱的一端的离子控制电极，离子控制电极包括中心线电极（DC1) 、顶部线电极（DC2) 和底部线电极（DC3) ，中心线电极（DC1) 、顶部线电极（DC2) 和底部线电极（DC3)平行于 X轴，中心线电极（DC1)位于顶部线电极（DC2) 与底部线电极（DC3) 之间，中心线电极 DC1通过线性离子阱的中心，顶部线电极（DC2) 与中心线电极（DC1) 的距离与底部线电极（DC3) 与中心线电极（DC1) 的距离相同，在中心线电极（DC1) 上施加第一直流电压，在顶部线电极（DC2) 和底部线电极（DC3) 上施加第二直流电压，第一直流电压与第二直流电压的极性相反； An ion control electrode disposed at one end of the linear ion trap, the ion control electrode including a center line electrode (DC1), a top line electrode (DC2), and a bottom line electrode (DC3), a center line electrode (DC1), and a top line electrode (DC2) The bottom line electrode (DC3) is parallel to the X axis, the center line electrode (DC1) is between the top line electrode (DC2) and the bottom line electrode (DC3), the center line electrode DC1 passes through the center of the linear ion trap, and the top line electrode ( DC2) The distance from the center line electrode (DC1) is the same as the distance between the bottom line electrode (DC3) and the center line electrode (DC1), and the first DC voltage is applied to the center line electrode (DC1) at the top line electrode (DC2). And applying a second DC voltage to the bottom line electrode (DC3), the first DC voltage being opposite to the polarity of the second DC voltage;

直流电压源，用于给所述中心线电极（DC1) 、顶部线电极（DC2) 和底部线电极 (DC3) 提供直流电压； a DC voltage source for supplying a DC voltage to the center line electrode (DC1), the top line electrode (DC2), and the bottom line electrode (DC3);

交流电压源，用于给线性离子阱的 y电极施加双极***流电压，以激发其共振频率与交流电压信号的频率匹配的离子，被激发的离子为选中的离子，选中的离子具有 y方向上足够大的运动以感受到顶部线电极（DC2) 和底部线电极（DC3) 上施加的电压的作用，从而从 z轴弹射选中的离子，使选中的离子离开线性离子阱。 An alternating voltage source for applying a bipolar alternating voltage to the y electrode of the linear ion trap to excite ions whose resonant frequency matches the frequency of the alternating voltage signal, the excited ions are selected ions, and the selected ions have a y direction A large enough motion is felt to sense the voltage applied across the top wire electrode (DC2) and the bottom wire electrode (DC3), thereby ejecting the selected ions from the z-axis, leaving the selected ions out of the linear ion trap.

2. 如权利要求 1所述的在线性离子阱中质量选择性弹射离子的装置，其特征在于- 顶部线电极（DC2)与中心线电极（DC1)的距离或底部线电极（DC3)与中心线电极（DC1) 的距离等于线性离子阱中心至 y电极距离（y0) 。 2. Apparatus for mass selective ejection of ions in a linear ion trap as claimed in claim 1 wherein - the distance between the top line electrode (DC2) and the center line electrode (DC1) or the bottom line electrode (DC3) and center The distance from the line electrode (DC1) is equal to the distance from the center of the linear ion trap to the y electrode (y0).

3. 如权利要求 1或 2所述的在线性离子阱中质量选择性弹射离子的装置，其特征在于：当捕获阳离子时，在中心线电极（DC1) 上施加正电压，在顶部线电极（DC2) 和底部线电极（DC3) 上施加负电压；当捕获阴离子时，在中心线电极（DC1) 上施加负电压，在顶部线电极（DC2)和底部线电极（DC3)上施加 ιΗ电压；以便沿着 z轴进行阳离子或阴离子弹射。 3. The apparatus for mass selective ejection of ions in a linear ion trap according to claim 1 or 2, wherein: when the cation is captured, a positive voltage is applied to the center line electrode (DC1) at the top line electrode ( A negative voltage is applied to the DC2) and the bottom line electrode (DC3); when the anion is trapped, a negative voltage is applied to the center line electrode (DC1), and a voltage is applied to the top line electrode (DC2) and the bottom line electrode (DC3); For cation or anion ejection along the z-axis.

4. 一种在线性离子阱中质量选择性弹射离子的方法，包括： 4. A method of mass selective ejection of ions in a linear ion trap, comprising:

在线性离子阱的 -端设置平行于 X轴的中心线电极 DC1、顶部线电极 DC2和底部线电极 DC3，中心线电极 DCl位于顶部线电极 DC2与底部线电极 DC3之间，中心线电极 DC1通过线性离子阱的中心，顶部线电极 DC2与中心线电极 DC1的距离与底部线电极与中心线电极 DC1的距离相同，在中心线电极上施加第一直流电压，在顶部线电极和底部线电极上施加第二直流电压，第 ·ίΐ流电压与第二直流电压的极性相反， A center line electrode DC1, a top line electrode DC2, and a bottom line electrode DC3 parallel to the X axis are disposed at the end of the linear ion trap, and the center line electrode DC1 is located between the top line electrode DC2 and the bottom line electrode DC3, and the center line electrode DC1 passes At the center of the linear ion trap, the distance between the top line electrode DC2 and the center line electrode DC1 is the same as the distance between the bottom line electrode and the center line electrode DC1, and a first DC voltage is applied to the center line electrode, on the top line electrode and the bottom line electrode. Applying a second DC voltage, the voltage of the first DC voltage is opposite to the polarity of the second DC voltage,

给线性离子阱的 y电极施加双极***流电压信号，以激发其共振频率与交流电压信号的频率匹配的离子，被激发的离子为选中的离子，选中的离子具有 y方向上足够大的运动以感受到顶部线电极 DC2和底部线¾极上施加的电压的作用，从而从 z轴弹射选中的离子，使选中的离子离开线性离子阱。 Applying a bipolar AC voltage signal to the y electrode of the linear ion trap to excite ions whose resonant frequency matches the frequency of the AC voltage signal, the excited ions are selected ions, and the selected ions have sufficient motion in the y direction To sense the voltage applied to the top line electrode DC2 and the bottom line 3⁄4 pole, thereby selecting from the z-axis ejection The ions that cause the selected ions to leave the linear ion trap.

5. 一种在线性离子阱阵列中选择性离子传输和富集的装置，包括： 5. A device for selective ion transport and enrichment in a linear ion trap array, comprising:

线性离子阱阵列，该线性离子阱阵列包括第一线性离子阱（1 )和第二线性离子阱 (2) , 第一端盖电极和第二端盖电极，第一端盖电极设置在线性离子阱阵列的一端，第二端盖电极设置在线性离子阱阵列的另一端， a linear ion trap array comprising a first linear ion trap (1) and a second linear ion trap (2), a first end cap electrode and a second end cap electrode, the first end cap electrode being disposed in the linear ion One end of the well array, and the second end cap electrode is disposed at the other end of the linear ion trap array.

位于第一线性离子阱和第二线性离子阱之间的离子控制电极（3 ) ，离子控制电极包括中心线电极（DC1 )、顶部线电极（DC2)和底部线电极（DC3 )，中心线电极（DC1 )、顶部线电极（DC2)和底部线电极（DC3 )平行于 X轴，中心线电极（DC1 )位于顶部线电极（DC2) 与底部线电极（DC3 ) 之间，中心线电极（DC1 ) 通过线性离子阱的中心，顶部线电极（DC2)与中心线电极（DC1 )的距离与底部线电极（DC3 )与中心线电极（DC1 ) 的距离相同，在中心线电极上施加第一直流电压，在顶部线电极和底部线电极上施加第二直流电压，第一直流电压与第二直流电压的极性相反； An ion control electrode (3) between the first linear ion trap and the second linear ion trap, the ion control electrode including a center line electrode (DC1), a top line electrode (DC2), and a bottom line electrode (DC3), the center line electrode (DC1), the top line electrode (DC2) and the bottom line electrode (DC3) are parallel to the X axis, and the center line electrode (DC1) is located between the top line electrode (DC2) and the bottom line electrode (DC3), and the center line electrode (DC1) Through the center of the linear ion trap, the distance between the top line electrode (DC2) and the center line electrode (DC1) is the same as the distance between the bottom line electrode (DC3) and the center line electrode (DC1), and the first DC is applied to the center line electrode. a second DC voltage applied to the top line electrode and the bottom line electrode, the first DC voltage being opposite to the polarity of the second DC voltage;

直流电压源，用于给第一线性离子阱、第二线性离子阱、中心线电极、顶部线电极和底部线电极提供直流电压；交流源，用于给线性离子阱的 y电极施加双极***流电压信号，以激发其共振频率与双极***流电压信号的频率匹配的离子，被激发的离子为选中的离子，选中的离子具有 y方向上足够大的运动以受到顶部线电极和底部线电极上施加的电压的作用，从而从 z轴弹射，离开第一线性离子阱；射频源给第一线性离子阱和第二线性离子阱提供射频电压；通过调整施加在第一线性离子阱和第二线性离子阱上的射频电压、交流电压和直流电压信号以及调整施加在中心线电极（DC1 ) 、顶部线电极 (DC2) 和底部线电极（DC3 ) 上的直流电压实现选中的离子从第一线性离子阱传输到第二线性离子阱。 a DC voltage source for supplying a DC voltage to the first linear ion trap, the second linear ion trap, the center line electrode, the top line electrode, and the bottom line electrode; an AC source for applying bipolarity to the y electrode of the linear ion trap An alternating voltage signal to excite ions whose resonant frequency matches the frequency of the bipolar alternating voltage signal, the excited ions being selected ions, and the selected ions having sufficient motion in the y direction to be subjected to the top and bottom lines The voltage applied to the electrode acts to eject from the z-axis, leaving the first linear ion trap; the RF source supplies the RF voltage to the first linear ion trap and the second linear ion trap; is applied to the first linear ion trap by adjusting RF voltage, AC voltage and DC voltage signals on the two linear ion traps and adjusting the DC voltage applied to the center line electrode (DC1), the top line electrode (DC2) and the bottom line electrode (DC3) to achieve selected ions from the first The linear ion trap is transferred to a second linear ion trap.

6. 如权利要求 5所述的在线性离子阱阵列中选择性离子传输和富集的装置，其特征在于：第一线性离子阱具有尺寸： xO = yO = 5 mm， ζθ =40 mm;第二线性离子阱具有尺 f-_: xO = yO = 5 mm, ζθ = 80 mm;第一线性离子阱与第二线性离子阱之间的距离是 2 mm, 以及中心线电极（DC1 ) 、顶部线电极（DC2)和底部线电极（DC3 )具有 0.2 mm的直径；顶部线电极（DC2) 和底部线电极（DC3 ) 离中心线电极的距离等于线性离子阱的尺寸 y0或不等于 yO; 其中 χθ表示线性离子阱中心至 X电极距离， y0表示线性离子阱中心至 y电极距离， ζθ表示线性离子阱的纵向尺寸； 6. The apparatus for selective ion transport and enrichment in a linear ion trap array according to claim 5, wherein: the first linear ion trap has a size: xO = yO = 5 mm, ζ θ = 40 mm; The bilinear ion trap has a ruler f- _: xO = yO = 5 mm, ζ θ = 80 mm; the distance between the first linear ion trap and the second linear ion trap is 2 mm, and the center line electrode (DC1), the top line The electrode (DC2) and the bottom wire electrode (DC3) have a diameter of 0.2 mm; the distance between the top wire electrode (DC2) and the bottom wire electrode (DC3) from the centerline electrode is equal to the size of the linear ion trap y0 or not equal to yO; wherein χθ Indicates the distance from the center of the linear ion trap to the X electrode, y0 represents the distance from the center of the linear ion trap to the y electrode, and ζθ represents the longitudinal dimension of the linear ion trap;

在第一线性离子阱上施加恒定的射频电压（RF1 )和在第二线性离子阱上施加恒定的射频电压（RF2) ，第一线性离子阱上的射频电压（RF1 )和第二线性离子阱上的射频电压（RF2) 设置为 278V; 频率为 230 kHz、零一峰值为 0.2 V的双极***流电压（AC1 ) 施加在第一线性离子阱上，施加在第二线性离子阱上的双极***流电压（AC2) 为 =0;将 6V直流电压施加在中心线电极上，以及将 -2.5 V直流电压施加在顶部线电极与底部线电极上；将 -5 V偏置电压施加在第二线性离子阱上。 Applying a constant RF voltage (RF1) on the first linear ion trap and applying a constant RF voltage (RF2) on the second linear ion trap, the RF voltage (RF1) on the first linear ion trap and the second linear ion trap The upper RF voltage (RF2) is set to 278V; the bipolar AC voltage (AC1) with a frequency of 230 kHz and a zero-to-peak value of 0.2 V is applied to the first linear ion trap, and the double applied to the second linear ion trap Polar AC voltage (AC2) is =0; 6V DC voltage is applied to the centerline electrode, and -2.5 V DC voltage is applied to the top and bottom wires On the pole; apply a -5 V bias voltage to the second linear ion trap.

7. 如权利要求 5所述的在线性离子阱阵列中选择性离子传输和富集的装置，其特征在于：第一线性离子阱具有尺寸： x0 = y0 = 5 mm， z0 =40 mm;第二线性离子阱具有尺

5 mm, ζθ = 80 mm;第一线性离子阱与第二线性离子阱之间的距离是 2 mm, 以及中心线电极（DC1 ) 、顶部线电极（DC2)和底部线电极（DC3 )具有 0.2 mm的直径；顶部线电极（DC2) 和底部线电极（DC3 ) 离中心线电极的距离等于线性离子阱的尺寸 y0或不等于 yO; 其中 χθ表示线性离子阱中心至 X电极距离， y0表示线性离子阱中心至 y电极距离， ζθ表示线性离子阱的纵向尺寸； 7. The apparatus for selective ion transport and enrichment in a linear ion trap array according to claim 5, wherein: the first linear ion trap has a size: x0 = y0 = 5 mm, z0 = 40 mm; Bilinear ion trap with ruler

5 mm, ζθ = 80 mm; the distance between the first linear ion trap and the second linear ion trap is 2 mm, and the center line electrode (DC1), the top line electrode (DC2), and the bottom line electrode (DC3) have 0.2 The diameter of the mm; the top line electrode (DC2) and the bottom line electrode (DC3) are at a distance from the centerline electrode equal to the linear ion trap size y0 or not equal to yO; where χθ represents the linear ion trap center to X electrode distance, y0 represents linear The distance from the center of the ion trap to the y electrode, ζθ represents the longitudinal dimension of the linear ion trap;

在 y电极上施加频率为 230 kHz、零一峰值为 0.4V的双极***流电压的同时通过扫描施加在第一线性离子阱上的第一射频电压（RF1 )，从而在不同的时间传输不同质荷比的离子，施加在第一线性离子阱上的第一射频电压（RF1 ) 为 200V/S , 施加在第二线性离子阱上的第二射频电压（RF2)和第一射频电压（RF1 )保持相同，施加在第二线性离子阱上的双极***流电压（AC2) 为 0，将 6V的直流电压施加在中心线电极上，以及将 -2.5 V直流电压施加在顶部线电极与底部线电极上，将 -5 V偏置电压施加在第二线性阱上。 Applying a bipolar AC voltage having a frequency of 230 kHz and a zero-to-peak value of 0.4 V to the y electrode while scanning the first radio frequency voltage (RF1) applied to the first linear ion trap, thereby transmitting different at different times The mass-to-charge ratio ion, the first radio frequency voltage (RF1) applied to the first linear ion trap is 200V/s, the second radio frequency voltage (RF2) applied to the second linear ion trap, and the first radio frequency voltage (RF1) Keeping the same, the bipolar AC voltage (AC2) applied to the second linear ion trap is 0, a DC voltage of 6V is applied to the centerline electrode, and a DC voltage of -2.5 V is applied to the top line electrode and the bottom. On the line electrode, a -5 V bias voltage is applied to the second linear well.

8.如权利要求 5— 7中的任一权利要求所述的在线性离子阱阵列中选择性离子传输和富集的装置，其特征在于：施加在第一线性离子阱上的交流电压（AC1 ) 为如下交流电压之一：单一频率的交流电压、宽频带的交流电压、多频带 /多频的交流电压。 8. Apparatus for selective ion transport and enrichment in a linear ion trap array according to any of claims 5-7, characterized by: an alternating voltage applied to the first linear ion trap (AC1) ) is one of the following AC voltages: AC voltage of a single frequency, AC voltage of a wide frequency band, AC voltage of a multi-band/multi-frequency.

9.如权利要求 5— 7中的任一权利要求所述的在线性离子阱阵列中选择性离子传输和富集的装置，其特征在于：所述离子为母离子或子离子。 9. Apparatus for selective ion transport and enrichment in a linear ion trap array according to any of claims 5-7, wherein: said ions are parent ions or daughter ions.

10. 如权利要求 5— 7所述的在线性离子阱阵列中选择性离子传输和富集的装置，其特征在于：中心线电极（DC1 ) 、顶部线电极（DC2)和底部线电极（DC3 ) 为任何形状的导线或圆柱形导线，三个线电极位于两个离子阱之间的间隔的中间位置或者位于两个离子阱之间的任何位置。 10. Apparatus for selective ion transport and enrichment in a linear ion trap array according to claims 5-7, characterized by: a center line electrode (DC1), a top line electrode (DC2) and a bottom line electrode (DC3) As a wire of any shape or a cylindrical wire, the three wire electrodes are located in the middle of the interval between the two ion traps or at any position between the two ion traps.

11 .如权利要求 5— 7中的任一权利要求所述的在线性离子阱阵列中选择性离子传输和富集的装置，其特征在于还包括冷却离子装置，所述冷却离子装置用于在 y方向上和 / 或 z方向上冷却沿 _Z轴从第一线性离子阱传输到第二线性离子阱的离子；所述冷却离子装置包括电压控制器和 /或缓冲气体供给装置，所述电压控制器调整脉冲或扫描直流和 / 或 AC2，以便去除传输到线性离子阱的离子的动能能量，防止传输到第二线性离子阱的离子返回到第一线性离子阱；所述缓冲气体供给装置为线性离子阱提供缓冲气体，缓冲气体用于在离子弹回到离子控制电极之前在 y方向上和 /或 z方向上冷却传输到线性离子阱中的选中的离子。 11. Apparatus for selective ion transport and enrichment in a linear ion trap array according to any of claims 5-7, further comprising a cooling ion device for Cooling ions transported from the first linear ion trap to the second linear ion trap along the _Z- axis in the y-direction and/or the z-direction; the cooled ion device includes a voltage controller and/or a buffer gas supply device, the voltage control Adjusting the pulse or scanning DC and / or AC2 to remove the kinetic energy of the ions transported to the linear ion trap, preventing ions transferred to the second linear ion trap from returning to the first linear ion trap; the buffer gas supply is linear The ion trap provides a buffer gas for cooling the selected ions transported into the linear ion trap in the y-direction and/or the z-direction before the ion bomb returns to the ion control electrode.

12. 如权利要求 11所述的在线性离子阱阵列中选择性离子传输和富集的装置，其特征在于施加在第二线性离子阱上的交流（AC2 )与施加在第一线性离子阱上的交流（AC1 ) 锁频，施加在第二线性离子阱上的交流（AC2 )与施加在第一线性离子阱上的交流（AC 1 ) 相移 180度，通过施加在第二线性离子阱上的交流（AC2 ) 去除传输到第二线性离子阱的离子的动能能量，以便防止离子传输回到第一线性离子阱。 12. Apparatus for selective ion transport and enrichment in a linear ion trap array according to claim 11 The alternating current (AC2) applied to the second linear ion trap and the alternating current (AC1) frequency applied to the first linear ion trap, the alternating current (AC2) applied to the second linear ion trap and applied to the first The alternating current (AC 1 ) on the linear ion trap is phase shifted by 180 degrees, and the kinetic energy of the ions transported to the second linear ion trap is removed by alternating current (AC2) applied to the second linear ion trap to prevent ion transport back to the first A linear ion trap.

13. 一种在线性离子阱阵列中选择性离子传输和富集的方法，包括： 13. A method of selective ion transport and enrichment in a linear ion trap array, comprising:

通过在线性离子阱的 y电极上施加双极性 AC信号以便在 y方向上激发具有特定质荷比 m/z的选中的离子，所述特定质荷比（m/z ) 的离子的共振频率与在线性离子阱的 y 电极上施加双极性 AC信号的共振频率匹配；被激发的离子为选中的离子，选中的离子具有 y方向上足够大的运动以受到设置在线性离子阱之间的离子控制电极的顶部线电极 DC2和底部线电极上施加的电压的作用，从 _Z轴弹射选中的离子并使选中的离子离开线性离子阱，在选中的离子通过离子控制电极之后，去除选中的离子在 y和 _Z方向上的过量的动能以便在第二线性离子阱 #2中捕获离子。 Applying a bipolar AC signal to the y-electrode of the linear ion trap to excite selected ions having a specific mass-to-charge ratio m/z in the y-direction, the resonant frequency of the ions of the specific mass-to-charge ratio (m/z) Matching the resonant frequency of the bipolar AC signal applied to the y electrode of the linear ion trap; the excited ions are selected ions, and the selected ions have a sufficiently large motion in the y direction to be placed between the linear ion traps The action of the voltage applied to the top line electrode DC2 and the bottom line electrode of the ion control electrode, ejecting the selected ions from the _Z axis and leaving the selected ions out of the linear ion trap, and removing the selected ions after the selected ions pass through the ion control electrode Excess kinetic energy in the y and _Z directions to capture ions in the second linear ion trap #2.

14. 一种质量分析器，包括： 14. A quality analyzer, comprising:

线性离子阱阵列，线性离子阱阵列包括二个或者二个以上的线性离子阱； a linear ion trap array, the linear ion trap array comprising two or more linear ion traps;

端盖电极，线性离子阱阵列的两端各设有一个端盖电极； End cap electrode, one end cap electrode is disposed at each end of the linear ion trap array;

离子控制电极，离子控制电极设置在线性离子阱之间，离子控制电极包括中心线电极 DC1、顶部线电极 DC2和底部线电极 DC3，中心线电极 DC 1、顶部线电极 DC2和底部线电极 DC3平行于 X轴，中心线电极 DC 1位于顶部线电极 DC2与底部线电极 DC3 之间，中心线电极 DC 1通过线性离子阱的中心，顶部线电极 DC2与中心线电极 DC 1的距离与底部线电极与中心线电极 DC 1的距离相同，在中心线电极上施加第一直流电压，在顶部线电极和底部线电极上施加第— 直流电压，第一直流电压与第二直流电压的极性相反； The ion control electrode is disposed between the linear ion traps, and the ion control electrode comprises a center line electrode DC1, a top line electrode DC2 and a bottom line electrode DC3, and the center line electrode DC1, the top line electrode DC2 and the bottom line electrode DC3 are parallel On the X-axis, the center line electrode DC 1 is located between the top line electrode DC2 and the bottom line electrode DC3, the center line electrode DC 1 passes through the center of the linear ion trap, the distance between the top line electrode DC2 and the center line electrode DC 1 and the bottom line electrode The distance from the center line electrode DC 1 is the same, a first DC voltage is applied to the center line electrode, and a first DC voltage is applied to the top line electrode and the bottom line electrode, the first DC voltage being opposite to the polarity of the second DC voltage;

射频电压源，用于给所述线性离子阱提供射频；直流电压源，用于给所述线性离子阱、中心线电极 DC 1、顶部线电极 DC2和底部线电极 DC3提供直流电压；交流电压源，用于给线性离子阱的 Y电极施加双极***流电压电压，以激发其共振频率与双极***流电压的共振频率匹配的离子，被激发的离子为选中的离子，选中的离子具有 y方向上足够大的运动以受到顶部线电极 DC2和底部线电极上施加的电压的作用；通过调整施加在所述线性离子阱上的射频电压、交流电 11和直流电压以及施加在中心线电极 DC 1、顶部线电极 DC2和底部线电极 DC3的直流电 ίΚ实现选中的离子从^ 级线性离子阱沿 Ζ轴传输到与^一级线性离子阱相邻的后一级线性离 f阱。 a radio frequency voltage source for supplying radio frequency to the linear ion trap; a DC voltage source for supplying a DC voltage to the linear ion trap, the center line electrode DC 1, the top line electrode DC2, and the bottom line electrode DC3; , for applying a bipolar alternating voltage voltage to the Y electrode of the linear ion trap to excite ions whose resonant frequency matches the resonant frequency of the bipolar alternating voltage, the excited ions are selected ions, and the selected ions have y a sufficiently large movement in the direction to be subjected to the voltage applied to the top wire electrode DC2 and the bottom wire electrode; by adjusting the radio frequency voltage, the alternating current 11 and the direct current voltage applied to the linear ion trap and applying to the center line electrode DC 1 The DC voltage of the top line electrode DC2 and the bottom line electrode DC3 enables the selected ions to be transported from the linearized ion trap along the x-axis to the subsequent linear off-f-well adjacent to the first-order linear ion trap.

15、如权利要求 14所述的质量分析器，其特征在于：在线性离子阱阵列的后端增加轨道阱和 /或飞行时间（TOF ) 设备。 15. The mass analyzer of claim 14 wherein: an orbitrap and/or time of flight (TOF) device is added to the rear end of the linear ion trap array.