公开(公告)号：US07507954B2

公开(公告)日：2009-03-24

申请号：US11939460

申请日：2007-11-13

Applicant: Edward B. McCauley ,  Scott T. Quarmby ,  George B. Guckenberger

Inventor： Edward B. McCauley ,  Scott T. Quarmby ,  George B. Guckenberger

IPC: H01J49/00

CPC classification number: H01J49/147 ,  H01J49/429

Abstract: A variable duty cycle ion source assembly is coupled to a continuous beam mass spectrometer. The duty cycle can be adjusted based on previous scan data or real time sampling of ion intensities during mass analysis. This provides the ability to control the total number of ions formed, mass analyzed and detected for each ion mass of interest. The frequency of the ion source can be sufficiently high (kHz range) so as to maintain accurate peak centroiding. The ion source assembly can be used for both electron ionization (EI) or chemical ionization (CI) modes of operation.

Abstract translation: 可变占空比离子源组件耦合到连续光束质谱仪。 可以根据先前的扫描数据或质谱分析中离子强度的实时采样来调整占空比。 这提供了控制每个离子质量所形成的离子总数，质量分析和检测的能力。 离子源的频率可以足够高（kHz范围），以保持准确的峰值重心。 离子源组件可用于电子电离（EI）或化学电离（CI）操作模式。

公开(公告)号：US20040159785A1

公开(公告)日：2004-08-19

申请号：US10780634

申请日：2004-02-19

Inventor： Yoshiaki Kato

IPC: H01J049/00 ,  B01D059/44

CPC classification number: H01J49/424 ,  H01J49/427 ,  H01J49/429

Abstract: An object of the present invention is to provide a method of discriminating singly-charged ions from multiply-charged ions by the use of an ion trap type mass spectrometer which is an inexpensive mass spectrometer. This object is achieved by a mass-analyzing method using an ion trap type mass spectrometer which is equipped with a ring electrode and one pair of end cap electrodes and temporarily traps ions in a three-dimensional quadrupole field to mass-analyze a sample, comprising a first step of applying a main high frequency voltage to said ring electrode to form a three-dimensional quadrupole field, a second step of generating ions in said mass analyzing unit or injecting ions from the outside and trapping ions of a predetermined mass-to-charge ratio range in said mass analyzing unit, a third step of applying a supplementary AC voltage having a plurality of frequency components between said end cap electrodes and scanning the frequency components of said supplementary AC voltage, and a fourth step of scanning said main high frequency voltage and ejecting ions from said mass analyzing unit and detecting thereof. With this, chemical noises can be reduced dramatically.

Abstract translation: 本发明的目的是提供一种通过使用廉价的质谱仪的离子阱型质谱仪来区分来自多电荷离子的单电荷离子的方法。 该目的通过使用离子阱型质谱仪的质量分析方法来实现，该离子阱型质谱仪装备有环形电极和一对端盖电极，并在三维四极场中临时捕获离子以质量分析样品，包括 将主高频电压施加到所述环形电极以形成三维四极场的第一步骤;在所述质量分析单元中产生离子或从外部注入离子并捕获预定质量 - 所述质量分析单元中的充电比范围，第三步骤，在所述端盖电极之间施加具有多个频率分量的辅助AC电压，并扫描所述辅助AC电压的频率分量，以及第四步骤，扫描所述主高频 电压并从所述质量分析单元喷射离子并进行检测。 因此，化学噪声可以大大降低。

公开(公告)号：US06649911B2

公开(公告)日：2003-11-18

申请号：US10198966

申请日：2002-07-22

Applicant: Eizo Kawato

Inventor： Eizo Kawato

IPC: B01D5944

CPC classification number: H01J49/429

Abstract: The present invention describes a method of selecting ions in an ion storage device with high resolution in a short time period while suppressing amplitude of ion oscillation immediately after the selection. In a method of selecting ions within a specific range of mass-to-charge ratio by applying an ion-selecting electric field in an ion storage space of an ion storage device, the method according to the present invention is characterized in that the ion-selecting electric field is produced from a waveform whose frequency is substantially scanned, and the waveform is made anti-symmetric by multiplying a weight function whose polarity reverses, or by shifting a phase of the waveform by odd multiple of &pgr;, at around a secular frequency of the ions to be left in the ion storage space. It is preferable that the frequency of the waveforms is scanned in a direction where the frequency decreases. It is also preferable that the weight function is linearly changed at the boundaries of the scanning range of the frequency.

Abstract translation: 本发明描述了一种在短时间内以高分辨率选择离子存储装置中的离子的方法，同时在选择之后立即抑制离子振动的振幅。 在通过在离子存储装置的离子存储空间中施加离子选择电场来选择特定的质荷比范围内的离子的方法中，根据本发明的方法的特征在于， 从基本扫描频率的波形产生选择电场，并且通过将极性反转的加权函数相乘，或者通过将波形的相位除以奇数倍，在波长的周围频率使波形反对称 的离子留在离子存储空间中。 优选地，在频率降低的方向上扫描波形的频率。 还优选的是，在频率的扫描范围的边界处，权重函数是线性变化的。

公开(公告)号：US20030071211A1

公开(公告)日：2003-04-17

申请号：US10198966

申请日：2002-07-22

Applicant: Shimadzu Corporation

Inventor： Eizo Kawato

IPC: H01J049/00

CPC classification number: H01J49/429

Abstract: The present invention describes a method of selecting ions in an ion storage device with high resolution in a short time period while suppressing amplitude of ion oscillation immediately after the selection. In a method of selecting ions within a specific range of mass-to-charge ratio by applying an ion-selecting electric field in an ion storage space of an ion storage device, the method according to the present invention is characterized in that the ion-selecting electric field is produced from a waveform whose frequency is substantially scanned, and the waveform is made anti-symmetric by multiplying a weight function whose polarity reverses, or by shifting a phase of the waveform by odd multiple of null, at around a secular frequency of the ions to be left in the ion storage space. It is preferable that the frequency of the waveforms is scanned in a direction where the frequency decreases. It is also preferable that the weight function is linearly changed at the boundaries of the scanning range of the frequency.

公开(公告)号：US5679951A

公开(公告)日：1997-10-21

申请号：US691841

申请日：1996-08-01

Applicant: Paul E. Kelley ,  John N. Louris

Inventor： Paul E. Kelley ,  John N. Louris

IPC: H01J49/42

CPC classification number: H01J49/424 ,  H01J49/4265 ,  H01J49/429

Abstract: A mass spectrometry method in which an improved field comprising two or more trapping fields having substantially identical spatial form is established and at least one parameter of the improved field is changed to excite selected trapped ions sequentially for detection. The changing improved field (preferably with a supplemental field superimposed therewith) can sequentially eject selected ones of the trapped ions from the improved field for detection. An improved field comprising two quadrupole trapping fields can be established in a region defined by the ring and end electrodes of a three-dimensional quadrupole ion trap, and the amplitude of an RF (and/or DC) component (and/or the frequency of the RF component) of one or both trapping fields can be changed to sequentially excite trapped ions. Preferably, a trapping field capable of storing ions having mass to charge ratio within a selected range is established, an improved field is established by superimposing the trapping field with a second trapping field of substantially identical spatial form, and a supplemental field is also superimposed with the trapping field to cause at least some of the trapped ions in the trap region to move away from the center of the trap region.

Abstract translation: 一种质谱方法，其中建立了包括具有基本上相同的空间形式的两个或更多个俘获场的改进场，改变场的至少一个参数被改变以顺序地激发选定的捕获的离子用于检测。 改变的改变场（优选地与其叠加的补充场）可以顺序地从改进的场中排出被捕获的离子的所选择的一部分用于检测。 可以在由三维四极离子阱的环和端电极限定的区域以及RF（和/或DC）分量的振幅（和/或/或DC）的范围内建立包括两个四极捕获场的改进场 一个或两个捕获场的RF分量）可以改变以顺序地激发捕获的离子。 优选地，能够将具有质荷比的离子存储在选定范围内的俘获场被建立，通过将俘获场与基本上相同的空间形式的第二俘获场叠加来建立改进的场，并且补充场也与 捕获场引起捕获区域中的至少一些捕获的离子离开陷阱区域的中心。

公开(公告)号：US5572025A

公开(公告)日：1996-11-05

申请号：US450464

申请日：1995-05-25

Applicant: Robert J. Cotter ,  Vladimir M. Doroshenko

Inventor： Robert J. Cotter ,  Vladimir M. Doroshenko

IPC: H01J49/16 ,  H01J49/42 ,  B01D59/44 ,  H01J49/00

CPC classification number: H01J49/424 ,  H01J49/0009 ,  H01J49/429

Abstract: A method of operation of an ion trap mass spectrometer having a ring electrode and pair of end-cap electrodes in a resonance ejection mode is disclosed. The method includes producing ions from a plurality of biomolecules, applying a trapping RF voltage to the ring electrode, applying an excitation voltage to the end-cap electrodes, scanning the trapping RF voltage in order to sequentially eject the ions, controlling a ration of the amplitude of the trapping RF voltage to the amplitude of the excitation voltage in order that the ratio is generally constant, and determining a ratio of mass to charge of the ejected ions. In one embodiment, a feedback voltage which is proportional to the trapping RF voltage is sensed, and the amplitude of the excitation voltage is controlled as a function of the amplitude of the feedback voltage. In another embodiment, a first value related to the amplitude of the trapping RF voltage and a second value, which is proportional to the first value and related to the amplitude of the excitation voltage, are determined. The amplitude of the trapping RF voltage is modulated employing the first value and the amplitude of the excitation voltage is modulated employing the second value. Preferably, the determined mass-to-charge ratio (m/z) of the ejected ions is equal to a constant (.alpha.) times the trapping RF voltage (V). Associated apparatus and method of calibration are also disclosed.

Abstract translation: 公开了一种具有环形电极和一对端帽电极的共振喷射模式的离子阱质谱仪的操作方法。 该方法包括从多个生物分子产生离子，向环形电极施加捕获RF电压，向端帽电极施加激发电压，扫描捕获RF电压以顺序地喷射离子，控制 将捕获的RF电压的幅度调节到激励电压的幅度，以使该比率基本上恒定，并且确定所排出的离子的质量与电荷的比率。 在一个实施例中，感测与捕获RF电压成比例的反馈电压，并且激励电压的幅度被控制为反馈电压的幅度的函数。 在另一个实施例中，确定与捕获RF电压的幅度相关的第一值和与第一值成比例并且与激励电压的幅度相关的第二值。 使用第一值调制捕获RF电压的幅度，并且使用第二值调制激励电压的幅度。 优选地，所确定的喷射离子的质荷比（m / z）等于捕获RF电压（V）的常数（α）。 还公开了相关装置和校准方法。

公开(公告)号：US5451782A

公开(公告)日：1995-09-19

申请号：US399097

申请日：1995-03-03

Applicant: Paul F. Kelley

Inventor： Paul F. Kelley

IPC: H01J49/42 ,  B01D59/44 ,  H01J49/00

CPC classification number: H01J49/424 ,  H01J49/4275 ,  H01J49/429

Abstract: A mass spectrometry method in which a combined field (comprising a trapping field and a supplemental field) is established and at least one parameter of the combined field is changed to excite ions trapped in the combined field sequentially (such as for detection). The supplemental field is a periodically varying field having an off-resonance frequency, in the sense that the supplemental field frequency nearly matches (but differs from) a frequency of motion of an ion stably trapped by the trapping field alone. Sequential ion excitation in accordance with the invention can rapidly eject a sequence of ions from a trap, or rapidly excite each ion to a degree sufficient for a desired purpose but insufficient for ejection from the trap, because the supplemental field will increase the trajectory of each ion in the sequence and because the supplemental field can have a sufficiently large peak-to-peak amplitude to increase each ion trajectory to a desired magnitude within a desired short time period. The trapped ions can be sequentially excited by holding the supplemental field fixed while changing at least one parameter of the trapping field, or by changing (such as scanning) at least one parameter of the supplemental field while holding the trapping field fixed. The amplitude of the supplemental field is kept sufficiently high to excite ions (via an off-resonance excitation mechanism) before they undergo resonant excitation.

Abstract translation: 建立了组合场（包括捕获场和补充场）并且组合场的至少一个参数被改变以顺序地（例如用于检测）捕获在组合场中的离子的质谱法。 辅助场是具有非共振频率的周期性变化的场，在辅助场频几乎匹配（但不同于）被捕获场单独稳定地捕获的离子的运动频率的意义上。 根据本发明的顺序离子激发可以快速地从捕获器中排出一系列离子，或者快速地将每个离子激发到足以满足期望目的的程度，但不足以从捕获器喷射，因为补充场将增加每个离子的轨迹 并且因为补充场可以具有足够大的峰 - 峰幅度，以将每个离子轨迹在期望的短时间段内增加到期望的幅度。 通过在改变捕获场的至少一个参数的同时保持补充场固定，或者通过在保持捕获场固定的同时改变（诸如扫描）补充场的至少一个参数来顺序地激发捕获的离子。 补充场的振幅保持足够高，以在它们经历共振激发之前激发离子（经由非共振激发机制）。

公开(公告)号：US5298746A

公开(公告)日：1994-03-29

申请号：US997284

申请日：1992-12-23

Applicant: Jochen Franzen ,  Reemt-Holger Gabling

Inventor： Jochen Franzen ,  Reemt-Holger Gabling

IPC: H01J49/42

CPC classification number: H01J49/424 ,  H01J49/429

Abstract: An improved scanning method used in an ion trap mass spectrometer comprises controlling the amplitude of the excitation RF during the mass scan to produce a smooth, nonlinear, highly suitable function. A smooth function is a function with a steady derivative. According to one embodiment of the invention, the excitation amplitude is set proportionally to the square root of the storage amplitude, thus making the excitation amplitude proportional to the root of the mass number.

Abstract translation: 在离子阱质谱仪中使用的改进的扫描方法包括在质量扫描期间控制激发RF的振幅以产生平滑，非线性，高度适合的功能。 平滑函数是具有稳定导数的函数。 根据本发明的一个实施例，激励振幅与存储幅度的平方根成比例地设定，从而使激励振幅与质量数的根成正比。

公开(公告)号：US4540884A

公开(公告)日：1985-09-10

申请号：US454351

申请日：1982-12-29

Applicant: George C. Stafford ,  Paul E. Kelley ,  David R. Stephens

Inventor： George C. Stafford ,  Paul E. Kelley ,  David R. Stephens

IPC: H01J49/38 ,  G01N27/62 ,  H01J49/42 ,  B01D59/44

CPC classification number: H01J49/424 ,  H01J49/429

Abstract: In a quadrupole ion store or ion trap type mass spectometer, significantly improved mass selection is achieved by simultaneously trapping ions within the mass range of interest and then scanning the applied RF and DC voltages or the frequency .omega. to sequentially render unstable trapped ions of consecutive specific masses. These are passed out through apertures in an end cap to a high gain electron multiplier to provide a signal indicative of the ion mass. Sensitivity and mass resolution is also enhanced by operating the ion trap at a relatively high pressure in the range 1.times.10.sup.-1 to 1.times.10.sup.-5 torr. The presence of collision gas molecules, such as helium, improves sensitivity and mass resolution. In addition, the structure itself is built of stacked units, sealed by O-rings, which are easily disassembled for cleaning.

Abstract translation: 在四极离子存储或离子阱型质谱仪中，通过在感兴趣的质量范围内同时捕获离子然后扫描所施加的RF和DC电压或频率ω，来实现显着改进的质量选择，以顺序地呈现连续特定的不稳定捕获的离子 群众 它们通过端盖中的孔传递到高增益电子倍增器，以提供指示离子质量的信号。 通过在1x10-1至1×10-5乇范围内的较高压力下操作离子阱也可以提高灵敏度和质量分辨率。 碰撞气体分子（如氦气）的存在提高了灵敏度和质量分辨率。 此外，结构本身由堆叠单元构成，由O型圈密封，易于拆卸清洁。

公开(公告)号：US3784814A

公开(公告)日：1974-01-08

申请号：US3784814D

申请日：1971-03-12

Applicant: NIPPON ELECTRIC VARIAN LTD

Inventor： SAKAI T ,  SAKIMURA M ,  INO Y

IPC: H01J49/42 ,  H01J39/34

CPC classification number: H01J49/4215 ,  H01J49/429

Abstract: A quadrupole mass spectrometer includes an ionization chamber, an ion detector, and a quadrupole structure having four electrodes extending therebetween. A d.c. voltage U and a high frequency voltage of amplitude V are linearly superimposed and are applied to the electrodes while maintaining the relationship U Alpha MV - K, where Alpha M denotes a critical U/V ratio. This constrains the mass peaks of a spectrum to be of substantially uniform shape. Variation of the parameter K permits the spectrometer resolution to be varied. In accordance with one aspect of the present invention, the d.c. voltage is maintained constant at values lower than the peak value of the stability curve for atomic hydrogen in a range of smaller values of the voltage amplitude V. The spectrum for atomic hydrogen can thereby be isolated.

Abstract translation: 四极质谱仪包括电离室，离子检测器和四极结构，四极结构具有在其间延伸的四个电极。 一个d.c. 电压U和振幅V的高频电压线性叠加并施加到电极，同时保持关系U =αMV-K，其中αM表示临界U / V比。 这限制了光谱的质谱峰值基本均匀的形状。 参数K的变化允许光谱分辨率变化。