公开(公告)号：US5187365A

公开(公告)日：1993-02-16

申请号：US788581

申请日：1991-11-06

申请人： Paul E. Kelley

发明人： Paul E. Kelley

IPC分类号： H01J49/42

CPC分类号： H01J49/4215 ,  H01J49/428

摘要： A method for performing mass analysis with dynamic mass resolution, in which a time-varying notch filtered broadband voltage signal (sometimes denoted as a time-varying "filtered noise" signal) is applied to a quadrupole mass filter. The time-varying filtered noise signal can consist of a rapid sequence of static (time-invariant) filtered noise signals, each defining a notch having a selected width and center location. The invention facilitates performance of mass analysis over a wide range of ion mass-to-charge ratios ("mass ranges") with adequate mass resolution. By appropriately choosing the width of each notch in the applied time-varying filtered noise, mass analysis can be performed with substantially constant mass separation over a wide mass range. In order to maintain substantially constant mass separation while analyzing a selected consecutive or non-consecutive sequence of ions (by passing such sequence of ions through the mass filter), the applied filtered noise should have narrower notches at times when ions with higher mass-to-charge ratio are to be selected, and wider notches at times when ions with lower mass-to-charge ratio are to be selected.

摘要翻译： 一种用于进行动态质量分辨率的质量分析的方法，其中将时变陷波滤波宽带电压信号（有时表示为随时间变化的“滤波噪声”信号）施加到四极质量滤波器。 时变滤波噪声信号可以由静态（时间不变）滤波噪声信号的快速序列组成，每个噪声信号限定具有选定宽度和中心位置的陷波。 本发明有助于在具有足够的质量分辨率的宽范围的离子质荷比（“质量范围”）下进行质量分析的性能。 通过在施加的时变滤波噪声中适当选择每个切口的宽度，可以在宽质量范围内以基本恒定的质量分离进行质量分析。 为了在分析所选择的连续或不连续的离子序列（通过将这种离子序列通过质量过滤器）的同时保持基本恒定的质量分离，施加的滤波噪声在具有较高质量 - 要选择充电比，并且要选择具有较低质荷比的离子时的更宽的缺口。

公开(公告)号：US5134286A

公开(公告)日：1992-07-28

申请号：US662217

申请日：1991-02-28

申请人： Paul E. Kelley

发明人： Paul E. Kelley

IPC分类号： G01N27/62 ,  H01J49/42

CPC分类号： H01J49/424 ,  H01J49/0081 ,  H01J49/428

摘要： A mass spectrometry method in which notch-filtered noise is applied to an ion trap to resonate all ions except selected ions out of the region of the trapping field. Preferably, the trapping field is a quadrupole trapping field defined by a ring electrode and a pair of end electrodes positioned symmetrically along a z-axis, and the filtered noise is applied to the ring electrode to eject unwanted ions in radial directions rather than toward a detector mounted along the z-axis. Also preferably, the trapping field has a DC component selected so that the trapping field has both a high frequency and low frequency cutoff, and is incapable of trapping ions with resonant frequency below the low frequency cutoff or above the high frequency cutoff. Application of the filtered noise signal to such a trapping field is functionally equivalent to filtration of the trapped ions through a notched bandpass filter having such high and low frequency cutoffs. Application of filtered noise in accordance with the invention avoids accumulation of contaminating ions during the process of storing desired parent ions, and permits ejection of unwanted ions in directions away from an ion detector to enhance the detector's operating life and rapid ejection of unwanted ions having mass-to-charge ratio below a minimum value, above a maximum value, and outside a window determined by the filtered noise signal.

摘要翻译： 一种质谱方法，其中将陷波滤波噪声施加到离子阱以使除捕获场区域外的所选离子之外的所有离子共振。 优选地，俘获场是由环形电极和沿着z轴对称定位的一对端电极限定的四极捕获场，并且滤波的噪声被施加到环形电极以沿径向方向而不是向着 检测器沿z轴安装。 还优选地，俘获场具有选择的DC分量，使得捕获场具有高频和低频截止频率，并且不能捕获具有低于低频截止频率或高于高频截止频率的谐振频率的离子。 将滤波后的噪声信号应用于这种捕获场在功能上等同于通过具有这种高频和低频截止值的有​​缺口带通滤波器对捕获的离子的过滤。 根据本发明的过滤噪声的应用避免了在存储期望的母体离子的过程中污染离子的积累，并且允许在远离离子检测器的方向上排出不想要的离子，以增强检测器的操作寿命并快速排出具有质量的不需要的离子 - 电荷比低于最大值，高于最大值，以及由滤波噪声信号确定的窗外。

公开(公告)号：US5703358A

公开(公告)日：1997-12-30

申请号：US526599

申请日：1995-09-11

申请人： Doneil J. Hoekman ,  Paul E. Kelley

发明人： Doneil J. Hoekman ,  Paul E. Kelley

IPC分类号： H01J49/42 ,  B01D59/44 ,  H01J49/40

CPC分类号： H01J49/428

摘要： A method for generating a filtered noise signal, which includes the steps of generating a broadband signal having optimized (reduced or minimized) dynamic range, and filtering the broadband signal in a notch filter to generate a broadband signal whose frequency-amplitude spectrum has one or more notches (the "filtered noise" signal). In preferred embodiments, the filtered noise signal is a voltage signal suitable for application to an ion trap during a mass spectrometry operation. The invention enables rapid generation of different filtered noise signals (for use in different mass spectrometry experiments) by filtering a single, optimized broadband signal using a set of different notch filters, each having a simple, easily implementable design. The invention enables rapid generation of filtered noise signals (for example, in real time during mass spectrometry experiments) without prior knowledge of the mass spectrum of unwanted ions to be ejected from a trap during application of the filtered noise signal to the trap. The invention also enables rapid generation of a filtered noise signal having no missing frequency components outside the notches of the notch filter employed to generate the filtered noise signal. Digital values indicative of the amplitude, frequency, and phase of each sinusoidal (or other periodic) component of an optimized broadband signal can be iteratively generated by a digital computer in accordance with the invention, and the digital values can then be processed to generate an analog version of the optimized broadband signal.

摘要翻译： 一种用于产生滤波噪声信号的方法，其包括以下步骤：产生具有优化（减小或最小化）动态范围的宽带信号，以及对陷波滤波器中的宽带信号进行滤波以产生其频率幅度谱具有一个或者多个 更多的凹口（“滤波噪声”信号）。 在优选实施例中，滤波噪声信号是在质谱分析操作期间适用于离子阱的电压信号。 通过使用一组不同的陷波滤波器过滤单个优化的宽带信号，本发明能够快速生成不同的滤波噪声信号（用于不同的质谱实验），每一个具有简单易于实现的设计。 本发明能够在将已滤波的噪声信号施加到捕获器的过程中快速产生滤波噪声信号（例如，在质谱分析实验期间实时地），而无需从捕获阱中排出不需要的离子的质谱。 本发明还能够快速生成在用于产生滤波噪声信号的陷波滤波器的缺口外部没有丢失频率分量的滤波噪声信号。 可以由根据本发明的数字计算机迭代地产生指示优化的宽带信号的每个正弦（或其他周期性）分量的幅度，频率和相位的数字值，然后可以处理数字值以产生 模拟版本的优化宽带信号。

公开(公告)号：US5381007A

公开(公告)日：1995-01-10

申请号：US067575

申请日：1993-05-25

申请人： Paul E. Kelley

发明人： Paul E. Kelley

IPC分类号： H01J49/42

CPC分类号： H01J49/424 ,  H01J49/427 ,  H01J49/429

摘要： 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 example for detection. The improved field can also include a supplemental field of different spatial form. The changing improved field can sequentially eject selected ones of the trapped ions from the improved field for detection (or other purposes). 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. Alternatively, a trapping field capable of storing ions having mass to charge ratio within a selected range is established, a supplemental field is superimposed with the trapping field to eject unwanted ions having mass-to-charge ratio within a second selected range from the improved field, the supplemental field having frequency components in one frequency range from a first frequency up to a notch frequency band and in another frequency range from the notch frequency band up to second frequency, and an improved field is then established by superimposing the trapping field with a second trapping field of substantially identical spatial form. Preferably, the relative phase of two or more component fields of the improved field is controlled to achieve an optimal combination of mass resolution, sensitivity, and mass peak stability.

摘要翻译： 建立了一种质谱方法，其中建立了包含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，例如用于检测。 改进的领域还可以包括不同空间形式的补充领域。 改变的改变场可以从改进的场中顺序地排出被捕获的离子，以进行检测（或其他目的）。 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。 或者，建立能够将具有质荷比的离子存储在选定范围内的俘获场，补充场与俘获场叠加，以从改进的场中喷射具有质荷比的不需要的离子，该物质与电荷的比例在第二选定范围内 所述补充场具有从第一频率到陷波频带的一个频率范围内的频率分量，以及从陷波频带直到第二频率的另一个频率范围，然后通过将捕获场与 基本相同的空间形式的第二捕集场。 优选地，控制改善场的两个或更多个分量场的相对相位以实现质量分辨率，灵敏度和质量峰值稳定性的最佳组合。

公开(公告)号：US5256875A

公开(公告)日：1993-10-26

申请号：US928262

申请日：1992-08-11

申请人： Doneil J. Hoekman ,  Paul E. Kelley

发明人： Doneil J. Hoekman ,  Paul E. Kelley

IPC分类号： G01N27/62 ,  H01J49/42 ,  B01D59/44 ,  H01J49/40

CPC分类号： H01J49/428

摘要： A method for generating a filtered noise signal, which includes the steps of generating a broadband signal having optimized (reduced or minimized) dynamic range, and filtering the broadband signal in a notch filter to generate a broadband signal whose frequency-amplitude spectrum has one or more notches (the "filtered noise" signal). In preferred embodiments, the filtered noise signal is a voltage signal suitable for application to an ion trap during a mass spectrometry operation. The invention enables rapid generation of different filtered noise signals (for use in different mass spectrometry experiments) by filtering a single, optimized broadband signal using a set of different notch filters, each having a simple, easily implementable design. The invention enables rapid generation of filtered noise signals (for example, in real time during mass spectrometry experiments) without prior knowledge of the mass spectrum of unwanted ions to be ejected from a trap during application of the filtered noise signal to the trap. The invention also enables rapid generation of a filtered noise signal having no missing frequency components outside the notches of the notch filter employed to generate the filtered noise signal. Digital values indicative of the amplitude, frequency, and phase of each sinusoidal (or other periodic) component of an optimized broadband signal can be iteratively generated by a digital computer in accordance with the invention, and the digital values can then be processed to generate an analog version of the optimized broadband signal.

摘要翻译： 一种用于产生滤波噪声信号的方法，其包括以下步骤：产生具有优化（减小或最小化）动态范围的宽带信号，以及对陷波滤波器中的宽带信号进行滤波以产生其频率幅度谱具有一个或者多个 更多的凹口（“滤波噪声”信号）。 在优选实施例中，滤波噪声信号是在质谱分析操作期间适用于离子阱的电压信号。 通过使用一组不同的陷波滤波器过滤单个优化的宽带信号，本发明能够快速生成不同的滤波噪声信号（用于不同的质谱实验），每一个具有简单易于实现的设计。 本发明能够在将已滤波的噪声信号施加到捕获器的过程中快速产生滤波噪声信号（例如，在质谱分析实验期间实时地），而无需从捕获阱中排出不需要的离子的质谱。 本发明还能够快速生成在用于产生滤波噪声信号的陷波滤波器的缺口外部没有丢失频率分量的滤波噪声信号。 可以由根据本发明的数字计算机迭代地产生指示优化的宽带信号的每个正弦（或其他周期性）分量的幅度，频率和相位的数字值，然后可以处理数字值以产生 模拟版本的优化宽带信号。

公开(公告)号：US5206507A

公开(公告)日：1993-04-27

申请号：US809767

申请日：1991-12-18

申请人： Paul E. Kelley

发明人： Paul E. Kelley

IPC分类号： H01J49/38 ,  H01J49/42

CPC分类号： H01J49/424 ,  H01J49/428 ,  H01J49/429

摘要： A mass spectrometry method in which a trapping field signal (such as a three-dimensional quadrupole trapping field signal or other multipole trapping field signal) set to store ions of interest is superimposed with a notch-filtered broadband ("filtered noise") signal, and ions are formed or injected in the resulting combined field. The filtered noise signal resonates all ions (except selected ones of the ions) from the combined field, so that only selected ones of the ions remain trapped in the combined field. The combined filtered noise and trapping field signal (the "combined signal") is then changed to excite the trapped ions sequentially, so that the excited ions can be detected sequentially. The invention can be applied to perform an (MS).sup.n or CI, or combined CI/(MS).sup.n, mass spectrometry operation.

摘要翻译： 设置用于存储感兴趣的离子的捕获场信号（例如三维四极捕获场信号或其他多极捕获场信号）与陷波滤波宽带（“滤波噪声”）信号叠加的质谱法， 并在所得到的组合场中形成或注入离子。 经滤波的噪声信号使所有离子（除了选定的离子之外）从组合场共振，使得只有选定的离子保留在组合场中。 然后，组合的滤波噪声和捕获场信号（“组合信号”）被改变以顺序地激发捕获的离子，使得可以顺序地检测受激离子。 本发明可以应用于执行（MS）n或CI或组合的CI /（MS）n质谱操作。

公开(公告)号：US5200613A

公开(公告)日：1993-04-06

申请号：US753325

申请日：1991-08-30

申请人： Paul E. Kelley

发明人： Paul E. Kelley

IPC分类号： G01N27/62 ,  H01J49/42

CPC分类号： H01J49/0063 ,  H01J49/424 ,  H01J49/4285

摘要： A mass spectrometry method in which a supplemental AC voltage signal having at least one high power frequency component, and at least one low power frequency component, is applied to an ion trap. Each high power component has an amplitude sufficiently large to eject one or more selected ions from the trap, by resonantly exciting the ions. Each low power component has an amplitude sufficient to induce dissociation (or reaction) of one or more selected ions, but insufficient to resonate the ions for detection. The frequency (or band of frequencies) of each high and low power frequency component is selected to match a resonance frequency of ions having a desired mass-to-charge ratio. Each low power component is applied for the purpose of inducing dissociation or reaction of specific trapped ions, which may be parent, daughter, reagent, or product ions, and each high power component is applied to eject undesired products of each such dissociation or reaction process from the trap. In accordance with the invention, a supplemental voltage signal having appropriately selected high and low power frequency components is applied to a trap during an (MS).sup.n or CI, or combined CI/(MS).sup.n, mass spectrometry operation.

摘要翻译： 一种质谱法，其中具有至少一个高功率频率分量和至少一个低功率频率分量的补充AC电压信号被施加到离子阱。 每个高功率分量具有足够大的振幅，通过共振地激发离子从捕获器中排出一个或多个选定的离子。 每个低功率分量具有足以引起一个或多个选定离子的解离（或反应）的振幅，但不足以共振用于检测的离子。 选择每个高和低功率频率分量的频率（或频带）以匹配具有期望质荷比的离子的谐振频率。 施加每个低功率组分以诱导特定捕获离子的解离或反应的目的，所述离子可以是亲本，子代，试剂或产物离子，并且每个高功率组分被施加以排出每个这样的解离或反应过程的不需要的产物 从陷阱。 根据本发明，在（MS）n或CI或组合的CI /（MS）n质谱操作期间，将具有适当选择的高功率和低功率频率分量的补充电压信号施加到陷阱。

公开(公告)号：US5105081A

公开(公告)日：1992-04-14

申请号：US662271

申请日：1991-02-28

申请人： Paul E. Kelley

发明人： Paul E. Kelley

IPC分类号： G01N27/62 ,  H01J49/02 ,  H01J49/26 ,  H01J49/42

CPC分类号： H01J49/025 ,  H01J49/424

摘要： A mass spectrometry method and apparatus in which trapped ions of interest are detected as they strike a detector comprising at least one of the electrodes which establish the ion trapping field. The invention eliminates the need to eject ions from the trap, and thus eliminates the need to perforate one or more of the trap electrodes. In one class of preferred embodiments, the trapping field is a three-dimensional quadrupole trapping field within a region bounded by a ring electrode and a pair of end electrodes. In one embodiment, the inventive in-trap detector is a trap electrode composed (or partially composed) of phosphorescent material which emits photons in response to incidence of ions at its inward-facing surface (the surface of the electrode which faces the trap region). In another embodiment, the in-trap ion detector is a Faraday effect detector which includes an electrically isolated conductive pin mounted with its tip flush with the inward-facing surface of one of the trap electrodes.

摘要翻译： 一种质谱方法和设备，其中当感兴趣的被捕获的离子撞击到包括建立离子捕获场的电极中的至少一个的检测器时被检测。 本发明消除了从陷阱中排出离子的需要，因此不需要穿孔一个或多个捕获电极。 在一类优选实施例中，捕获场是由环形电极和一对末端电极限定的区域内的三维四极捕获场。 在一个实施方案中，本发明的捕集阱检测器是由磷光材料组成（或部分组成）的捕获电极，其响应于其向内的表面（电极的面向陷阱区域的表面）的入射而发射光子， 。 在另一个实施例中，陷阱离子检测器是法拉第效应检测器，其包括电绝缘导电销，其安装成其尖端与一个捕获电极的向内表面齐平。

公开(公告)号：US4686367A

公开(公告)日：1987-08-11

申请号：US773339

申请日：1985-09-06

申请人： John N. Louris ,  John E. P. Syka ,  Paul E. Kelley

发明人： John N. Louris ,  John E. P. Syka ,  Paul E. Kelley

IPC分类号： G01N27/62 ,  H01J49/10 ,  H01J49/14 ,  H01J49/26 ,  H01J49/42

CPC分类号： H01J49/424 ,  H01J49/0081 ,  H01J49/145 ,  H01J49/429

摘要： The method of performing chemical ionization and mass analysis with a quadrupole ion trap.

摘要翻译： 用四极离子阱进行化学电离和质量分析的方法。

公开(公告)号：US5864136A

公开(公告)日：1999-01-26

申请号：US879731

申请日：1997-06-20

申请人： Paul E. Kelley ,  John N. Louris

发明人： Paul E. Kelley ,  John N. Louris

IPC分类号： H01J49/42

CPC分类号： H01J49/424 ,  H01J49/4265 ,  H01J49/429

摘要： 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.

摘要翻译： 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。