WO2013097659A1 - Mass analyzer with coil-shaped electric field - Google Patents

Mass analyzer with coil-shaped electric field Download PDF

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Publication number
WO2013097659A1
WO2013097659A1 PCT/CN2012/087243 CN2012087243W WO2013097659A1 WO 2013097659 A1 WO2013097659 A1 WO 2013097659A1 CN 2012087243 W CN2012087243 W CN 2012087243W WO 2013097659 A1 WO2013097659 A1 WO 2013097659A1
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Prior art keywords
electric field
mass
charged particles
electrodes
ring
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PCT/CN2012/087243
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French (fr)
Chinese (zh)
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邱永红
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Qiu Yonghong
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Publication of WO2013097659A1 publication Critical patent/WO2013097659A1/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/26Mass spectrometers or separator tubes
    • H01J49/34Dynamic spectrometers
    • H01J49/40Time-of-flight spectrometers
    • H01J49/408Time-of-flight spectrometers with multiple changes of direction, e.g. by using electric or magnetic sectors, closed-loop time-of-flight

Definitions

  • the invention relates to a mass analyzer for a mass spectrometer, which has various applications in mass spectrometry detection and belongs to the technical field of instrumentation. Background technique
  • Mass spectrometry has a wide range of applications in isotope analysis, chemical analysis, and life science analysis.
  • the basic principle is: Ionize the sample into charged particles in a vacuum, separate it by mass analyzer, and detect various mass ions. The quantity, thus obtaining qualitative and quantitative information of the sample.
  • the mass analyzer is the core component, and the mass spectrum can be divided into the following five types according to its type:
  • Magnetic mass spectrometry The charged particles are accelerated into the magnetic field, and the particles of different mass-to-charge ratios are deflected differently, and the particles of various mass-to-charge ratios are separated.
  • Ion trap mass spectrometry The charged particles are introduced into the ion trap, and only particles of a specific mass-to-charge ratio that resonate with the RF electric field applied to the well can oscillate stably in the trap to separate particles of various mass-to-charge ratios.
  • the charged particles are introduced into the interaction zone between the electric field and the magnetic field, and oscillate under the action of the RF electric field, and the generated image current signals are processed by Fourier transform to obtain particle signals of various mass-to-charge ratios.
  • Figure 3 is a schematic diagram of time-of-flight mass spectrometry.
  • time-of-flight mass spectrometry charged particles are accelerated and then enter the field-free region. Assuming that the accelerating voltage is ⁇ , the charged particle mass is ⁇ , and the electric quantity is ⁇ initial velocity is 0, then the charged particles are from When the accelerating electrode flies out, the work done by the electric field on the charged particles is equal to:
  • current time-of-flight mass spectrometry usually uses a reflective structure, as shown in Figure 4, the principle is the same as straight-line flight.
  • the charged particles are focused by the fan-shaped electric field energy, and are also focused by the direction of the fan-shaped magnetic field to reach the detector.
  • the principle of energy focusing is shown in Fig. 5.
  • the direction of the electric field at any point in the fan-shaped electric field points to the center of the fan shape, or opposite to this direction, the charged particles are accelerated and then fly into the fan-shaped electric field, which is subjected to circular motion by the electric field force.
  • the radius of the circular motion be; , the fan electric field strength is ⁇ , then the centrifugal force is equal to the electric field force of the charged particles: m
  • the invention relates to a novel mass analyzer for mass spectrometry, which aims to separate particles of different mass-to-charge ratios in a charged particle beam and separately detect them, and different mass-to-charge ratios can be obtained according to different motion characteristics of particles in the charged particle beam.
  • the particles are spatially separated or time separated.
  • the physical structure of the present invention is two curved electrodes which are sleeved together in a vacuum, and a certain voltage is applied between the two electrodes to form a ring-shaped electric field, and the charged particles are spirally moved when injected into the electric field in an appropriate manner.
  • the auxiliary electrode may be added to form an auxiliary electric field at the place where the charged particles fly in, or the auxiliary electrode may be formed at both ends of the ring cylinder to form an auxiliary electric field.
  • a typical example of the invention is the coincidence of two cylindrical electrode axes, as shown in Figure 1.
  • the implementation method of the invention is that the charged particles fly into the ring-shaped electric field at a certain angle, perform a spiral motion under the action of the electric field, and after a certain number of turns, lead out the ring-shaped electric field, enter the detector or enter the next-stage mass analyzer.
  • the ring-shaped electric field mass analyzer of the present invention can produce two kinds of results due to different motion characteristics of incident charged particles: First result: as shown in FIG. 2, all charged particles in the charged particle beam are accelerated for the same time. When the kinetic energy is different, the speed is
  • Quantity is the electric field force of the charged particles in the accelerating electric field, resulting in m
  • Electric field force / , where ⁇ is the accelerating electric field strength, and G is the amount of electricity charged by the charged particles.
  • Acceleration field strength , where is the acceleration voltage, which is the distance between the two accelerating electrodes. Dm
  • the incident direction is not perpendicular to the ring-shaped axis, but at a certain angle, the charged particles will change from a circular motion to a spiral motion.
  • the ring-shaped cylinder can also be drawn.
  • the electric field is detected or entered into the next stage mass analyzer. This results in a mass filter that allows only charged particles of a single mass-to-charge ratio to pass through, also called a mass analyzer, which is of the spatial separation type.
  • the charged particles conforming to (1) fly into the ring-shaped electric field in a direction perpendicular to the axis of the ring cylinder, the charged particles will make a circular motion.
  • the radius of motion conforms to equation (3).
  • the radius of deflection of charged particles in the electric field is independent of the mass-to-charge ratio. Charged particles of all mass-to-charge ratios move in a circular motion with the same radius. Adjusting the incident kinetic energy of the charged particles, or the strength of the ring-shaped electric field, can make the radius of the circular motion of the charged particles the same as the distance from the incident point to the ring-shaped axis, and the charged particles can continuously perform circular motion in the ring-shaped electric field. .
  • the mass analyzer which is much smaller than the fieldless and reflective fieldless mass analyzer, has energy focusing, reduces the deviation of the initial state of charged particles, and has higher resolution. This mass analyzer belongs to Time separation type.
  • the circular motion of the charged particles is to form a spiral motion, which can be used in three ways: 1.
  • the incident direction of the charged particles is not perpendicular to the axis of the ring-shaped electric field, forming an angle.
  • the incident direction of the charged particle is perpendicular to the axis of the ring-shaped electric field.
  • Two electrodes are added in front of the entrance of the ring-shaped electric field to form an electric field parallel to the axis of the ring cylinder, so that the charged particles have a certain velocity in the axial direction.
  • the applied electric field can be an electrostatic field or a varying electric field.
  • the incident direction of the charged particles is perpendicular to the axis of the ring-shaped electric field.
  • Two electrodes are added at both ends of the ring-shaped electric field, and an electric field parallel to the axis of the ring cylinder is superimposed to make the charged particles have a certain velocity in the axial direction.
  • the applied electric field can be an electrostatic field or a varying electric field.
  • the two mass analyzers of the present invention are simple in structure, small in size, easy to manufacture, and highly efficient in separation. DRAWINGS
  • Fig. 1 is a schematic view of the present invention, and 1 and 2 are cylindrical electrodes. For convenience of explanation 2, only half is drawn, the object is a complete cylindrical electrode, and 3 is an interface of a charged particle detector or a next-stage mass analyzer. The spiral line in the figure is the trajectory of the charged particles.
  • Figure 2 is a schematic view of the charged particle acceleration device of the present invention
  • 1 and 2 are accelerated electrodes of charged particles
  • electrodes 2 have small holes or slits for extracting charged particles
  • 3 and 4 are cylindrical electrodes, for convenience of explanation 4 Only half of it is drawn, the physical object is a complete cylindrical electrode
  • 5 is the interface of the charged particle detector or the next mass analyzer
  • 6 is the common axis of the cylindrical electrode 3 and 4
  • the spiral is charged particle Movement track.
  • Figure 3 is a schematic diagram of the current time-of-flight mass spectrometer, 1 and 2 are accelerated electrodes of charged particles, electrodes 2 have small holes or slits for extracting charged particles, 3 are detectors, and dashed lines indicate the motion trajectories of charged particles. .
  • Figure 4 is a schematic diagram of the existing reflective time-of-flight mass spectrometer, 1 and 2 are accelerated electrodes of charged particles, electrodes 2 have small holes or slits for extracting charged particles, 3 are a set of reflective electrodes, 4 is a After the group accelerates the electrode, 5 is the detector, and the broken line indicates the motion trajectory of the charged particles.
  • Figure 5 is a schematic diagram of the energy focusing portion of the existing dual focus mass spectrometer
  • 1 and 2 are accelerating electrodes of charged particles
  • electrodes 2 have small holes or slits for extracting charged particles
  • 3 and 4 are arc-shaped electrodes
  • 5 is a baffle with small holes or slits
  • 6 is a detector
  • a broken line indicates the trajectory of charged particles.
  • 1 is a smaller cylindrical surface electrode
  • 2 is a larger cylindrical surface electrode
  • 2 sets are outside 1
  • two cylindrical surface electrodes having different radii coincide with each other, and a certain voltage is applied to the electrodes 1 and 2
  • An electric field is formed between the two cylinders, and the shape of the electric field is a ring cylinder.
  • 1 and 2 are electrodes, a certain voltage is applied between them, and an accelerating electric field is formed between 1 and 2, and the charged particles are accelerated in the accelerated electric field, and are taken out from the small holes or slits in the electrode 2.
  • 3 is a smaller cylindrical electrode
  • 4 is a larger cylindrical electrode
  • 4 sets are outside 3
  • two columns An electric field is formed between the faces, and the shape of the electric field is a ring cylinder.
  • two charged particle beams of different motion characteristics can be obtained.
  • the first one is that the charged particles are accelerated for the same time, and the kinetic energy is different, then the ring-shaped electric field becomes the mass filter, and only one charged-charged charged particle can make a stable spiral motion, reaching the detector, and controlling the electrodes 3 and 4.
  • the applied voltage can change the intensity of the electric field of the ring cylinder, filter the charged particles with different mass-to-charge ratios, and perform mass scanning.
  • the second type is that the charged particles are accelerated at the same distance, and the kinetic energy is the same, then the ring-shaped electric field becomes a spiral-folded particle channel.
  • All the charged particles with mass-to-charge ratio can make a stable spiral motion and reach the detector, but reach the detector.
  • the time is arranged in the order of the mass-to-charge ratio, and the ring-shaped electric field realizes the time-of-flight mass analyzer with a small space.
  • the charged particle acceleration method can produce two new types of mass analyzers, which are used in mass spectrometry to generate a new type of mass spectrometer, which makes the mass spectrometer simple in structure, excellent in performance, and widely used.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
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Abstract

A mass analyzer for a mass spectrometer has many applications in mass spectrometry analysis and detection, and relates to the technical field of instrumentation. The physical structure of the mass analyzer is two electrodes sleeved together. A certain voltage is applied between the two electrodes to form a coil-shaped electric field. When shot at a certain angle into the coil-shaped electric field, charged particles carry out spiral motion in the coil-shaped electric field, and are introduced into a detector after moving for several circles. Depending on different speed characteristics of the charged particles when being shot into the coil-shaped electric field, two types of mass analyzers may be formed. One is a spatial-separation type, and the other is a temporal-separation type. The two types of mass analyzers both are simple in structure, small in volume, easy to manufacture, and highly efficient in separation.

Description

环柱形电场质量分析器 技术领域  Ring cylindrical electric field mass analyzer
本发明涉及一种用于质谱仪的质量分析器,在质谱分析检测方面有多种应用,属于仪器 仪表技术领域。 背景技术  The invention relates to a mass analyzer for a mass spectrometer, which has various applications in mass spectrometry detection and belongs to the technical field of instrumentation. Background technique
质谱技术在同位素分析、化学分析、 生命科学分析中有广泛的应用, 其基本原理是: 在 真空中, 将样品离子化变成带电粒子, 通过质量分析器进行分离, 检测出各种质量数离子的 数量, 从而得到样品的定性、 定量信息。  Mass spectrometry has a wide range of applications in isotope analysis, chemical analysis, and life science analysis. The basic principle is: Ionize the sample into charged particles in a vacuum, separate it by mass analyzer, and detect various mass ions. The quantity, thus obtaining qualitative and quantitative information of the sample.
在质谱技术中, 质量分析器是最核心的部件, 按其种类可将质谱分为以下五种: In mass spectrometry, the mass analyzer is the core component, and the mass spectrum can be divided into the following five types according to its type:
(1)磁质谱。 带电粒子被加速后进入磁场, 不同质荷比的粒子偏转情况不同, 使各种质 荷比的粒子分离。 (1) Magnetic mass spectrometry. The charged particles are accelerated into the magnetic field, and the particles of different mass-to-charge ratios are deflected differently, and the particles of various mass-to-charge ratios are separated.
(2)四极杆质谱。 带电粒子被引入四极杆滤质器, 只有与四极杆上所加射频电场发生共 振的特定质荷比的粒子可以通过, 使各种质荷比的粒子分离。  (2) Quadrupole mass spectrometry. Charged particles are introduced into the quadrupole mass filter, and only particles of a specific mass-to-charge ratio that are oscillated with the applied RF electric field on the quadrupole can pass through to separate particles of various mass-to-charge ratios.
(3)飞行时间质谱。 带电粒子被加速后, 不同质荷比的粒子速度不同, 经过一段无场飞 行, 到达检测器的时间不同, 使各种质荷比的粒子分离。  (3) Time-of-flight mass spectrometry. After the charged particles are accelerated, the particle velocities of different mass-to-charge ratios are different. After a period of no-field flight, the time to reach the detector is different, and the particles of various mass-to-charge ratios are separated.
(4)离子阱质谱。 带电粒子被引入离子阱, 只有与阱上所加射频电场发生共振的特定质 荷比的粒子可以在阱中稳定振荡飞行, 使各种质荷比的粒子分离。  (4) Ion trap mass spectrometry. The charged particles are introduced into the ion trap, and only particles of a specific mass-to-charge ratio that resonate with the RF electric field applied to the well can oscillate stably in the trap to separate particles of various mass-to-charge ratios.
(5)傅立叶变换-回旋振荡质谱。 带电粒子被引入电场和磁场共同作用区, 在射频电场 作用下回旋振荡, 产生的象电流信号用傅立叶变换处理, 得到各种质荷比的粒子信 号。  (5) Fourier transform-cyclotron oscillation mass spectrometry. The charged particles are introduced into the interaction zone between the electric field and the magnetic field, and oscillate under the action of the RF electric field, and the generated image current signals are processed by Fourier transform to obtain particle signals of various mass-to-charge ratios.
图 3是飞行时间质谱的原理图,在飞行时间质谱中,带电粒子被加速后进入无场区飞行, 假设加速电压为 ί 带电粒子质量为 ^, 电量为^ 初速度为 0, 则带电粒子从加速电极 飞出时, 电场对带电粒子所做的功等于 能:
Figure imgf000002_0001
Figure 3 is a schematic diagram of time-of-flight mass spectrometry. In time-of-flight mass spectrometry, charged particles are accelerated and then enter the field-free region. Assuming that the accelerating voltage is ί, the charged particle mass is ^, and the electric quantity is ^ initial velocity is 0, then the charged particles are from When the accelerating electrode flies out, the work done by the electric field on the charged particles is equal to:
Figure imgf000002_0001
带电粒子从加速电极射出时速度为:
Figure imgf000002_0002
设飞行长度为 ,则飞行时间 =一,将上式代入,可得飞行时间质谱中带电粒子飞行时间:
Figure imgf000002_0003
The velocity at which charged particles are emitted from the accelerating electrode is:
Figure imgf000002_0002
If the flight length is set, the flight time = one, and the above formula is substituted, and the flight time of the charged particles in the time-of-flight mass spectrum can be obtained:
Figure imgf000002_0003
为了降低带电粒子初始位置和初始速度引起的偏差,并减小飞行管的长度, 目前的飞行 时间质谱通常釆用反射式结构, 如图 4所示, 原理与直线飞行相同。  In order to reduce the deviation caused by the initial position and initial velocity of charged particles and reduce the length of the flight tube, current time-of-flight mass spectrometry usually uses a reflective structure, as shown in Figure 4, the principle is the same as straight-line flight.
在磁质谱中, 同样为了降低带电粒子初始位置和初始速度引起的偏差,普遍釆用双聚焦 模式, 带电粒子要通过扇形电场能量聚焦, 还要通过扇形磁场方向聚焦才能到达检测器。能 量聚焦原理如图 5所示,扇形电场内任意点的电场方向指向扇形的圆心,或者与此方向相反, 带电粒子被加速后飞入扇形电场, 受电场力作用作圆周运动。 设圆周运动半径为;?, 扇形 电场强度为^, 则离心力等于带电粒子所受电场力: m In magnetic mass spectrometry, in order to reduce the deviation caused by the initial position and initial velocity of charged particles, it is common to use double focusing. In the mode, the charged particles are focused by the fan-shaped electric field energy, and are also focused by the direction of the fan-shaped magnetic field to reach the detector. The principle of energy focusing is shown in Fig. 5. The direction of the electric field at any point in the fan-shaped electric field points to the center of the fan shape, or opposite to this direction, the charged particles are accelerated and then fly into the fan-shaped electric field, which is subjected to circular motion by the electric field force. Let the radius of the circular motion be; , the fan electric field strength is ^, then the centrifugal force is equal to the electric field force of the charged particles: m
R  R
将上式与(1)式合并可得: Combine the above formula with (1) to obtain:
(3) (3)
R- E R - E
上式说明, 在能量聚焦中, 带电粒子在电场中偏转半径与质荷比无关, 各种质荷比的带电粒 子以相同的半径通过扇形电场,只有那些初始位置和初始速度有偏差,加速后运动能量有偏 差的带电粒子, 因运动半径不同而被滤除。 发明内容 The above equation shows that in energy focusing, the deflection radius of charged particles in the electric field is independent of the mass-to-charge ratio. Charged particles of various mass-to-charge ratios pass the fan-shaped electric field at the same radius, only those initial positions and initial velocity are deviated, after acceleration. Charged particles with varying kinetic energy are filtered out due to different kinetic radii. Summary of the invention
本发明是一种用于质谱的新型质量分析器,目的在于使带电粒子束中不同质荷比的粒子 分离, 得以分别检测, 根据带电粒子束中粒子运动特征的不同, 可对不同质荷比的粒子进行 空间分离或时间分离。  The invention relates to a novel mass analyzer for mass spectrometry, which aims to separate particles of different mass-to-charge ratios in a charged particle beam and separately detect them, and different mass-to-charge ratios can be obtained according to different motion characteristics of particles in the charged particle beam. The particles are spatially separated or time separated.
本发明的物理结构为真空中套在一起的两个曲面电极,两个电极之间加一定电压,形成 环柱形电场,带电粒子以适当的方式射入此电场时做螺旋运动。必要时可在带电粒子飞入的 地方增加辅助电极形成辅助电场,也可在环柱形两端增加辅助电极形成辅助电场。本发明的 典型实例为两个圆柱面电极轴线重合嵌套, 如图 1所示。  The physical structure of the present invention is two curved electrodes which are sleeved together in a vacuum, and a certain voltage is applied between the two electrodes to form a ring-shaped electric field, and the charged particles are spirally moved when injected into the electric field in an appropriate manner. If necessary, the auxiliary electrode may be added to form an auxiliary electric field at the place where the charged particles fly in, or the auxiliary electrode may be formed at both ends of the ring cylinder to form an auxiliary electric field. A typical example of the invention is the coincidence of two cylindrical electrode axes, as shown in Figure 1.
本发明的实现方法是:带电粒子以一定角度飞入环柱形电场,在电场作用下做螺旋运动, 旋转一定圈数后引出环柱形电场, 进入检测器或进入下一级质量分析器。  The implementation method of the invention is that the charged particles fly into the ring-shaped electric field at a certain angle, perform a spiral motion under the action of the electric field, and after a certain number of turns, lead out the ring-shaped electric field, enter the detector or enter the next-stage mass analyzer.
本发明所述环柱形电场质量分析器,因入射带电粒子的运动特征不同,可产生两种结果: 第一种结果:如图 2所示,带电粒子束中所有带电粒子被加速的时间相同,动能不同时, 速度为  The ring-shaped electric field mass analyzer of the present invention can produce two kinds of results due to different motion characteristics of incident charged particles: First result: as shown in FIG. 2, all charged particles in the charged particle beam are accelerated for the same time. When the kinetic energy is different, the speed is
其中 Q是带电粒子被加速的时间, 为常数。 又因为加速度《3 = , 其中 是带电粒子的质 Where Q is the time at which the charged particles are accelerated and is constant. And because the acceleration "3 = , which is the quality of charged particles
m  m
量, /是带电粒子在加速电场中所受的电场力, 得 m Quantity, / is the electric field force of the charged particles in the accelerating electric field, resulting in m
电场力 /= , 其中^是加速电场强度, G是带电粒子所带电量, 得 m Electric field force /= , where ^ is the accelerating electric field strength, and G is the amount of electricity charged by the charged particles.
加速场强 = , 其中 是加速电压, 是两加速电极间的距离, 得 dm Acceleration field strength = , where is the acceleration voltage, which is the distance between the two accelerating electrodes. Dm
上式表明, 带电粒子被加速的时间相同时, 速度与质荷比成反比。 当符合上式的带电粒子以 垂直于环柱体轴线的方向飞入环柱形电场时, 带电粒子将做圆周运动。 设圆周运动半径为 R, 环柱形电场强度为^, 则离心力等于带电粒子所受电场力:
Figure imgf000004_0001
The above equation shows that when the charged particles are accelerated for the same time, the velocity is inversely proportional to the mass-to-charge ratio. When the charged particles conforming to the above formula fly into the ring-shaped electric field in a direction perpendicular to the axis of the ring cylinder, the charged particles will make a circular motion. Let the circular motion radius be R, and the ring-shaped electric field strength be ^, then the centrifugal force is equal to the electric field force of the charged particles:
Figure imgf000004_0001
合并 (4)式和 (5)式, 可得环柱形电场质量分析器中带电粒子偏转半径:
Figure imgf000004_0002
Combining equations (4) and (5), the radius of deflection of charged particles in a ring-column electric field mass analyzer can be obtained:
Figure imgf000004_0002
从上式环柱形电场中带电粒子的偏转半径与质荷比的数学关系看,它们是反比关系,不同质 荷比的带电粒子圆周运动的半径不同,只有半径为入射点到环柱形轴线距离的带电粒子可以 连续地做圆周运动, 其它带电粒子将落在两个圆柱面电极上。 From the mathematical relationship between the deflection radius of charged particles and the mass-to-charge ratio in the cylindrical electric field of the upper ring, they are inversely proportional. The radius of the circular motion of charged particles with different mass-to-charge ratios is different, only the radius is the incident point to the ring cylinder axis. The charged particles of the distance can continuously move in a circular motion, and the other charged particles will fall on the two cylindrical surface electrodes.
当带电粒子飞入环柱形电场, 入射方向与环柱形轴线不垂直, 而是成一定角度时, 带电 粒子将从圆周运动变成螺旋运动,在适当的位置检测,也可以引出环柱形电场进行检测或者 进入下一级质量分析器。这样就形成了只允许单一质荷比的带电粒子通过的质量过滤器,也 叫质量分析器, 此种质量分析器属于空间分离类型。  When the charged particles fly into the ring-shaped electric field, the incident direction is not perpendicular to the ring-shaped axis, but at a certain angle, the charged particles will change from a circular motion to a spiral motion. When detected at an appropriate position, the ring-shaped cylinder can also be drawn. The electric field is detected or entered into the next stage mass analyzer. This results in a mass filter that allows only charged particles of a single mass-to-charge ratio to pass through, also called a mass analyzer, which is of the spatial separation type.
第二种结果:如图 2所示,带电粒子束中所有带电粒子被加速的距离相同,动能相同时, 运动速度符合 (1)式, 与质荷比的平方根成反比。  The second result: as shown in Fig. 2, all charged particles in the charged particle beam are accelerated at the same distance. When the kinetic energy is the same, the velocity of motion conforms to equation (1), which is inversely proportional to the square root of the mass-to-charge ratio.
当符合 (1)式的带电粒子以垂直于环柱体轴线的方向飞入环柱形电场时, 带电粒子将做 圆周运动。 运动半径符合 (3)式, 带电粒子在电场中偏转半径与质荷比无关, 所有质荷比的 带电粒子以相同的半径做圆周运动。调节带电粒子的入射动能, 或者环柱形电场的强度, 可 使带电粒子圆周运动的半径与入射点到环柱形轴线的距离相同,则带电粒子在环柱形电场中 可以连续地做圆周运动。  When the charged particles conforming to (1) fly into the ring-shaped electric field in a direction perpendicular to the axis of the ring cylinder, the charged particles will make a circular motion. The radius of motion conforms to equation (3). The radius of deflection of charged particles in the electric field is independent of the mass-to-charge ratio. Charged particles of all mass-to-charge ratios move in a circular motion with the same radius. Adjusting the incident kinetic energy of the charged particles, or the strength of the ring-shaped electric field, can make the radius of the circular motion of the charged particles the same as the distance from the incident point to the ring-shaped axis, and the charged particles can continuously perform circular motion in the ring-shaped electric field. .
当带电粒子飞入环柱形电场, 入射方向与环柱形轴线不垂直, 而是成一定角度时, 带电 粒子将从圆周运动变成螺旋运动,在适当的位置检测,也可以引出环柱形电场进行检测或者 进入下一级质量分析器。设带电粒子螺旋运动和引入、引出电场总的运动距离为 , 则其运 动时间符合 (2)式, 各种质荷比的带电粒子按时间顺序依次到达, 这样就形成螺旋形折叠路 径的飞行时间质量分析器, 比无场飞行和反射式无场飞行质量分析器大幅度地缩小体积, 同 时具有能量聚焦作用, 减小了带电粒子初始状态的偏差, 分辨率较高, 此种质量分析器属于 时间分离类型。  When the charged particles fly into the ring-shaped electric field, the incident direction is not perpendicular to the ring-shaped axis, but at a certain angle, the charged particles will change from a circular motion to a spiral motion. When detected at an appropriate position, the ring-shaped cylinder can also be drawn. The electric field is detected or entered into the next stage mass analyzer. Let the spiral motion of charged particles and the total moving distance of the incoming and outgoing electric fields be (2), and the charged particles of various mass-to-charge ratios arrive in chronological order, thus forming the flight time of the spiral folding path. The mass analyzer, which is much smaller than the fieldless and reflective fieldless mass analyzer, has energy focusing, reduces the deviation of the initial state of charged particles, and has higher resolution. This mass analyzer belongs to Time separation type.
以上两种质量分析器中, 带电粒子的圆周运动要形成螺旋运动, 可以釆用三种方式: 1. 带电粒子入射方向与环柱形电场的轴线不垂直, 成一定角度。 2. 带电粒子入射方向与环柱 形电场的轴线垂直,在环柱形电场的入射口前加两个电极,形成一个与环柱形轴线平行的电 场, 使带电粒子在轴线方向具有一定速度, 所加电场可以是静电场或者变化的电场。 3. 带 电粒子入射方向与环柱形电场的轴线垂直,在环柱形电场的两端加两个电极, 叠加一个与环 柱形轴线平行的电场,使带电粒子在轴线方向具有一定速度,所加电场可以是静电场或者变 化的电场。  In the above two mass analyzers, the circular motion of the charged particles is to form a spiral motion, which can be used in three ways: 1. The incident direction of the charged particles is not perpendicular to the axis of the ring-shaped electric field, forming an angle. 2. The incident direction of the charged particle is perpendicular to the axis of the ring-shaped electric field. Two electrodes are added in front of the entrance of the ring-shaped electric field to form an electric field parallel to the axis of the ring cylinder, so that the charged particles have a certain velocity in the axial direction. The applied electric field can be an electrostatic field or a varying electric field. 3. The incident direction of the charged particles is perpendicular to the axis of the ring-shaped electric field. Two electrodes are added at both ends of the ring-shaped electric field, and an electric field parallel to the axis of the ring cylinder is superimposed to make the charged particles have a certain velocity in the axial direction. The applied electric field can be an electrostatic field or a varying electric field.
本发明所述的两种质量分析器结构简单、 体积小巧、 制做容易、 分离高效。 附图说明 The two mass analyzers of the present invention are simple in structure, small in size, easy to manufacture, and highly efficient in separation. DRAWINGS
图 1是本发明的示意图, 1和 2是圆柱面电极, 为了方便说明 2只画出了一半, 实物是 完整的圆柱面电极, 3是带电粒子检测器或下一级质量分析器的接口, 图中螺旋线是带电粒 子的运动轨迹。  BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of the present invention, and 1 and 2 are cylindrical electrodes. For convenience of explanation 2, only half is drawn, the object is a complete cylindrical electrode, and 3 is an interface of a charged particle detector or a next-stage mass analyzer. The spiral line in the figure is the trajectory of the charged particles.
图 2是本发明加入带电粒子加速装置的示意图, 1和 2是带电粒子的加速电极, 电极 2 上有用于引出带电粒子的小孔或狭缝, 3和 4是圆柱面电极,为了方便说明 4只画出了一半, 实物是完整的圆柱面电极, 5是带电粒子检测器或下一级质量分析器的接口, 6是圆柱面电 极 3和 4共同的轴线, 图中螺旋线是带电粒子的运动轨迹。  Figure 2 is a schematic view of the charged particle acceleration device of the present invention, 1 and 2 are accelerated electrodes of charged particles, electrodes 2 have small holes or slits for extracting charged particles, and 3 and 4 are cylindrical electrodes, for convenience of explanation 4 Only half of it is drawn, the physical object is a complete cylindrical electrode, 5 is the interface of the charged particle detector or the next mass analyzer, 6 is the common axis of the cylindrical electrode 3 and 4, the spiral is charged particle Movement track.
图 3是目前已有的飞行时间质谱原理图, 1和 2是带电粒子的加速电极, 电极 2上有用 于引出带电粒子的小孔或狭缝, 3是检测器, 虚线表示带电粒子的运动轨迹。  Figure 3 is a schematic diagram of the current time-of-flight mass spectrometer, 1 and 2 are accelerated electrodes of charged particles, electrodes 2 have small holes or slits for extracting charged particles, 3 are detectors, and dashed lines indicate the motion trajectories of charged particles. .
图 4是目前已有的反射式飞行时间质谱原理图, 1和 2是带电粒子的加速电极, 电极 2 上有用于引出带电粒子的小孔或狭缝, 3是一组反射电极, 4是一组后加速电极, 5是检测 器, 虚线表示带电粒子的运动轨迹。  Figure 4 is a schematic diagram of the existing reflective time-of-flight mass spectrometer, 1 and 2 are accelerated electrodes of charged particles, electrodes 2 have small holes or slits for extracting charged particles, 3 are a set of reflective electrodes, 4 is a After the group accelerates the electrode, 5 is the detector, and the broken line indicates the motion trajectory of the charged particles.
图 5是目前已有的双聚焦质谱能量聚焦部分原理图, 1和 2是带电粒子的加速电极, 电 极 2上有用于引出带电粒子的小孔或狭缝, 3和 4是圆弧形电极, 5是具有小孔或狭缝的挡 板, 6是检测器, 虚线表示带电粒子的运动轨迹。 具体实施方式  Figure 5 is a schematic diagram of the energy focusing portion of the existing dual focus mass spectrometer, 1 and 2 are accelerating electrodes of charged particles, electrodes 2 have small holes or slits for extracting charged particles, and 3 and 4 are arc-shaped electrodes, 5 is a baffle with small holes or slits, 6 is a detector, and a broken line indicates the trajectory of charged particles. detailed description
本发明的具体实施方式如图 1和图 2所示, 装置整体置于真空中。  DETAILED DESCRIPTION OF THE INVENTION As shown in Figures 1 and 2, the device is placed in a vacuum.
图 1中 1是较小的圆柱面电极, 2是较大的圆柱面电极, 2套在 1外, 两个半径不同的 圆柱面电极轴线重合, 在 1和 2两个电极上加一定电压, 两个柱面之间就形成电场, 电场的 形状为环柱体。当有带电粒子以一定角度射入环柱形电场中时,带电粒子将会在环柱体内做 螺旋运动, 运动一定时间或距离后引出电场, 进行检测, 或者进入下一级质量分析器。  In Fig. 1, 1 is a smaller cylindrical surface electrode, 2 is a larger cylindrical surface electrode, 2 sets are outside 1 , and two cylindrical surface electrodes having different radii coincide with each other, and a certain voltage is applied to the electrodes 1 and 2, An electric field is formed between the two cylinders, and the shape of the electric field is a ring cylinder. When charged particles are injected into the ring-shaped electric field at a certain angle, the charged particles will spiral in the ring cylinder, and the electric field will be extracted after a certain time or distance to detect, or enter the next-stage mass analyzer.
图 2中 1和 2是电极, 它们之间加一定电压, 在 1和 2之间形成加速电场, 带电粒子在 加速成电场中被加速, 从电极 2上的小孔或狭缝中引出。 3是较小的圆柱面电极, 4是较大 的圆柱面电极, 4套在 3外, 两个半径不同的圆柱面电极轴线重合, 在 3和 4两个电极上加 一定电压, 两个柱面之间就形成电场, 电场的形状为环柱体。 当电极 1和 2加速的带电粒子 以一定角度射入环柱形电场中时,带电粒子将会在环柱体内做螺旋运动,运动一定时间或距 离后引出电场, 进行检测, 或者进入下一级质量分析器。  In Fig. 2, 1 and 2 are electrodes, a certain voltage is applied between them, and an accelerating electric field is formed between 1 and 2, and the charged particles are accelerated in the accelerated electric field, and are taken out from the small holes or slits in the electrode 2. 3 is a smaller cylindrical electrode, 4 is a larger cylindrical electrode, 4 sets are outside 3, two cylindrical electrode electrodes with different radii coincide with each other, and a certain voltage is applied to the two electrodes of 3 and 4, two columns An electric field is formed between the faces, and the shape of the electric field is a ring cylinder. When the charged particles accelerated by the electrodes 1 and 2 are incident into the ring-shaped electric field at a certain angle, the charged particles will spiral in the ring cylinder, and the electric field is extracted after a certain time or distance to detect, or enter the next stage. Mass analyzer.
控制图 2中电极 1和 2上所加的电压,可以得到两种不同运动特征的带电粒子束。第一 种是带电粒子被加速的时间相同, 动能不同, 则环柱形电场成为质量过滤器, 只有一种质荷 比的带电粒子可以做稳定的螺旋运动, 到达检测器, 控制电极 3和 4上所加的电压, 可以改 变环柱体电场的强度, 过滤不同质荷比的带电粒子, 进行质量扫描。第二种是带电粒子被加 速的距离相同, 动能相同, 则环柱形电场成为螺旋折叠的粒子通道, 所有质荷比的带电粒子 可以做稳定的螺旋运动, 到达检测器, 但是到达检测器的时间按质荷比的顺序排列, 环柱形 电场以很小的空间实现了飞行时间质量分析器。  By controlling the voltage applied to electrodes 1 and 2 in Figure 2, two charged particle beams of different motion characteristics can be obtained. The first one is that the charged particles are accelerated for the same time, and the kinetic energy is different, then the ring-shaped electric field becomes the mass filter, and only one charged-charged charged particle can make a stable spiral motion, reaching the detector, and controlling the electrodes 3 and 4. The applied voltage can change the intensity of the electric field of the ring cylinder, filter the charged particles with different mass-to-charge ratios, and perform mass scanning. The second type is that the charged particles are accelerated at the same distance, and the kinetic energy is the same, then the ring-shaped electric field becomes a spiral-folded particle channel. All the charged particles with mass-to-charge ratio can make a stable spiral motion and reach the detector, but reach the detector. The time is arranged in the order of the mass-to-charge ratio, and the ring-shaped electric field realizes the time-of-flight mass analyzer with a small space.
带电粒子以垂直于的轴线方向射入环柱电场时,将会做圆周运动,要使带电粒子做螺旋 运动, 还要使粒子在环柱形轴线方向具有一定速度。 实现方法有三种: 1.带电粒子入射方向 与环柱形轴线不垂直, 成一定角度。 2.在环柱电场入射口之前加两个与轴线垂直的电极, 形 成与环柱形轴线平行的电场, 对带电粒子轴向加速。 3.在环柱电场两端加两个与轴线垂直的 电极, 形成与环柱形轴线平行的电场, 叠加在环柱形电场上, 对带电粒子轴向加速。 工业实用性 When the charged particles are incident on the electric field of the ring column in the direction perpendicular to the axis, circular motion will be performed, and the charged particles should be spirally moved, and the particles should have a certain velocity in the direction of the ring-shaped axis. There are three ways to achieve this: 1. The incident direction of the charged particles is not perpendicular to the ring-shaped axis, forming a certain angle. 2. Add two electrodes perpendicular to the axis before the electric field entrance of the ring column to form an electric field parallel to the axis of the ring cylinder, and accelerate the axial direction of the charged particles. 3. Add two electrodes perpendicular to the axis at both ends of the electric field of the ring column to form an electric field parallel to the axis of the ring cylinder, superimposed on the ring-shaped electric field, and accelerate the axial direction of the charged particles. Industrial applicability
目前已经存在的几种质量分析器在商品化的质谱仪器中获得了广泛的应用,在全球范围 内用于科学研究、 化学分析、 环境保护、 食品安全、 地质矿产、 能源资源等, 本发明所述的 带电粒子加速方法可产生两种新型的质量分析器, 用于质谱仪器时产生新类型的质谱仪器, 使质谱仪器结构简单, 性能优良, 获得更广泛的应用。  Several mass analyzers that have existed at present have been widely used in commercial mass spectrometry instruments, and are used worldwide for scientific research, chemical analysis, environmental protection, food safety, geological mineral resources, energy resources, etc., the present invention. The charged particle acceleration method can produce two new types of mass analyzers, which are used in mass spectrometry to generate a new type of mass spectrometer, which makes the mass spectrometer simple in structure, excellent in performance, and widely used.

Claims

权 利 要 求 书 Claim
1. 一种用于质谱的质量分析器, 其特征在于: 两个电极大小不同, 小电极在大电极内, 两 电极之间形成环柱形或者环椎形空间,在两电极上加一定电压,则形成环柱形或者环椎形电 场。 当带电粒子束以合适的角度射入此电场时, 在电场中做螺旋运动, 不同质荷比的带电粒 子在螺旋运动中分离。  A mass spectrometer for mass spectrometry, characterized in that: two electrodes are different in size, a small electrode is in a large electrode, a ring-shaped or ring-shaped space is formed between the two electrodes, and a certain voltage is applied to the two electrodes Then, a ring-shaped or ring-shaped electric field is formed. When the charged particle beam is incident on the electric field at a suitable angle, the spiral motion is performed in the electric field, and the charged particles of different mass-to-charge ratios are separated in the spiral motion.
2. 如权利要求 1所述质量分析器, 其特征在于: 两个电极可以是满足要求的任意材料、 尺 寸、 形状。 也可以省略其中一个电极, 仅用一个电极形成的电场使带电粒子做螺旋运动。 2. The mass analyzer of claim 1 wherein: the two electrodes are of any material, size, shape that meets the requirements. It is also possible to omit one of the electrodes, and the electric field formed by only one electrode causes the charged particles to perform a helical motion.
3. 如权利要求 1所述质量分析器, 其特征在于: 两个电极的相对位置可变, 两电极轴线重 合形成对称环形电场,也可以轴线不重合形成不对称电场。带电粒子的入射方向与出射方向 可以成任意角度。 3. The mass analyzer according to claim 1, wherein: the relative positions of the two electrodes are variable, and the two electrode axes are coincident to form a symmetrical annular electric field, or the axes may not coincide to form an asymmetric electric field. The incident direction and the outgoing direction of the charged particles can be at any angle.
4. 如权利要求 1所述质量分析器, 其特征在于: 两个电极上所加的电压是满足要求的任意 电压, 可以是恒定电压, 也可以是脉冲电压, 可以是任意波形的电压。  4. The mass analyzer according to claim 1, wherein: the voltage applied to the two electrodes is any voltage that satisfies the requirements, and may be a constant voltage or a pulse voltage, and may be an arbitrary waveform voltage.
5. 如权利要求 1、 2、 3、 4所述质量分析器, 其特征在于: 当入射的带电粒子被加速的时 间相同, 动量相同而动能不同时, 其速度与质荷比成反比, 不同质荷比的粒子在环柱形电场 中螺旋运动半径不同,只有半径与入射点到环柱形轴线距离相同的带电粒子可以稳定地做螺 旋运动, 实现质量过滤。 改变两个圆柱面电极之间的电压, 使环柱形电场的强度改变, 可实 现质量扫描。  5. The mass analyzer according to claim 1, 2, 3, and 4, wherein: when the incident charged particles are accelerated for the same time, the momentum is the same, and the kinetic energy is different, the speed is inversely proportional to the mass-to-charge ratio, different The mass-to-charge ratio particles have different spiral motion radii in the ring-shaped electric field, and only the charged particles with the same radius from the incident point to the ring-shaped axis can stably perform spiral motion to achieve mass filtration. The mass sweep can be achieved by changing the voltage between the two cylindrical electrodes to change the intensity of the ring-shaped electric field.
6. 如权利要求 1、 2、 3、 4所述质量分析器, 其特征在于: 当入射的带电粒子被加速的距 离相同, 动量不同而动能相同时, 其速度与质荷比的平方根成反比, 不同质荷比的粒子在环 柱形电场中螺旋运动半径相同, 运动轨迹相同, 速度不同, 不同质荷比的粒子到达运动终点 的时间不同, 实现时间分离。  6. The mass analyzer according to claim 1, 2, 3, and 4, wherein: when the incident charged particles are accelerated by the same distance, the momentum is different and the kinetic energy is the same, the speed is inversely proportional to the square root of the mass-to-charge ratio. The particles with different mass-to-charge ratios have the same radius of motion in the ring-shaped electric field, the same trajectory, different speeds, and the time at which the particles with different mass-to-charge ratios reach the end of the motion are different, achieving time separation.
7. 如权利要求 1所述质量分析器, 其特征在于: 在环柱形电场的带电粒子入射位置前加两 个电极, 与环柱形轴线垂直, 形成与轴线平行的电场, 使入射的带电粒子具有轴向速度, 形 成螺旋运动。 两电极间所加电压为任意波形电压。  7. The mass analyzer according to claim 1, wherein: two electrodes are added in front of the incident position of the charged particles of the ring-shaped electric field, perpendicular to the axis of the ring cylinder, forming an electric field parallel to the axis to electrify the incident. The particles have an axial velocity that creates a helical motion. The voltage applied between the two electrodes is an arbitrary waveform voltage.
8. 如权利要求 1所述质量分析器, 其特征在于: 在环柱形电场的两端加两个电极, 与环柱 形轴线垂直, 形成与轴线平行的电场, 使入射的带电粒子具有轴向速度, 形成螺旋运动。两 电极间所加电压为任意波形电压  8. The mass analyzer according to claim 1, wherein: two electrodes are added at both ends of the ring-shaped electric field, perpendicular to the axis of the ring cylinder, forming an electric field parallel to the axis, so that the incident charged particles have an axis. To the speed, a spiral motion is formed. The voltage applied between the two electrodes is an arbitrary waveform voltage.
9. 串联质量分析器, 其特征在于: 应用权利要求 1、 2、 3、 4、 5、 6、 7、 8所述的质量分 析器, 与各种质量分析器串联使用成为多级质量分析器。  9. A tandem mass analyzer, characterized in that: the mass analyzer described in claims 1, 2, 3, 4, 5, 6, 7, 8 is used in series with various mass analyzers to become a multi-stage mass analyzer .
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CN111867224B (en) * 2020-07-27 2021-09-28 上海交通大学 E B probe
CN113223919B (en) * 2021-03-31 2023-05-30 杭州谱育科技发展有限公司 Annular TOF mass analyzer and working method thereof

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