公开(公告)号：US5449905A

公开(公告)日：1995-09-12

申请号：US281505

申请日：1994-07-27

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：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：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：US5679951A

公开(公告)日：1997-10-21

申请号：US691841

申请日：1996-08-01

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。

公开(公告)号：US4540884A

公开(公告)日：1985-09-10

申请号：US454351

申请日：1982-12-29

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

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

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

CPC分类号： H01J49/424 ,  H01J49/429

摘要： 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.

摘要翻译： 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：US5466931A

公开(公告)日：1995-11-14

申请号：US298388

申请日：1994-08-30

申请人： Paul E. Kelley

发明人： Paul E. Kelley

IPC分类号： G01N27/62 ,  H01J49/42

CPC分类号： H01J49/424 ,  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 parent 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(rather than to the end electrodes) to eject unwanted ions in radial directions (toward the ring electrode) rather than toward a detector mounted along the z-axis. Application of the filtered noise to the trap in this manner can significantly increase the operating lifetime of such an ion detector. 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 of the invention 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 has several significant advantages over the conventional techniques it replaces, including avoidance of accumulation of contaminating ions during the process of storing desired parent ions, ejection of unwanted ions in directions away from an ion detector to enhance the detector's operating life, rapid ejection of unwanted ions having mass-to-charge ratio below a minimum value, above a maximum value, and outside a window (between the minimum and maximum values) determined by the filtered noise signal.

摘要翻译： 一种质谱方法，其中将陷波滤波的噪声施加到离子阱以使除所选母体离子之外的所有离子在捕获场的区域外谐振。 优选地，捕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，并且将滤波的噪声施加到环形电极（而不是端部电极）以排出不需要的 离子沿径向（朝向环形电极）而不是沿着沿z轴安装的检测器。 以这种方式将滤波噪声施加到陷阱可以显着增加这种离子检测器的工作寿命。 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。 将本发明的滤波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。 根据本发明的滤波噪声的应用与其替代的常规技术相比具有几个显着的优点，包括避免在存储期望的母体离子的过程中污染离子的积累，不期望的离子沿远离离子检测器的方向喷射以增强 检测器的使用寿命，快速排出具有低于最小值的质荷比低于最大值的不想要的离子，以及由滤波的噪声信号确定的窗口之外（在最小值和最大值之间）。

公开(公告)号：US5610397A

公开(公告)日：1997-03-11

申请号：US434476

申请日：1995-05-04

申请人： Paul E. Kelley

发明人： Paul E. Kelley

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

CPC分类号： H01J49/0081 ,  H01J49/0063 ,  H01J49/424 ,  H01J49/427 ,  H01J49/429

摘要： A mass spectrometry method in which one or more high power supplemental AC voltage signals and one or more low power supplemental AC voltage signals are applied to an ion trap. The frequency of each supplemental AC voltage is selected to match a resonance frequency of an ion having a desired mass-to-charge ratio. The low power supplemental voltage signals are applied for the purpose of dissociating specific ions (i.e., parent ions) within the trap, and the high power supplemental voltage signals are applied to resonate products of the dissociation process (i.e., daughter ions) so that they can be detected. In one class of embodiments, the high power voltage signals resonate daughter ions out from the trap for detection by an external detector. In another class of embodiments, each high power voltage signal resonates the daughter ions only to a degree sufficient for detection by an in-trap detector (which may comprise one or more of the electrodes which define the trapping field, or may be mounted integrally with such electrodes).

摘要翻译： 一种质谱方法，其中将一个或多个高功率补充AC电压信号和一个或多个低功率补充AC电压信号施加到离子阱。 选择每个补充AC电压的频率以匹配具有期望质荷比的离子的共振频率。 施加低功率补充电压信号用于解离陷阱内的特定离子（即母体离子），并且施加高功率补充电压信号以共振解离过程（即，子离子）的产物，使得它们 可以检测。 在一类实施例中，高功率电压信号使子离子从陷阱中共振，由外部检测器检测。 在另一类实施例中，每个高功率电压信号仅使子离子谐振到足以由陷阱检测器（其可以包括定义捕获场的一个或多个电极，或可以与 这样的电极）。

公开(公告)号：US5196699A

公开(公告)日：1993-03-23

申请号：US662427

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： H01J49/145 ,  H01J49/424 ,  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 reagent 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 reagent 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 (between the minimum and maximum values) determined by the filtered noise signal.

摘要翻译： 一种质谱方法，其中将陷波滤波的噪声施加到离子阱以使除所选择的试剂离子之外的所有离子在捕获场的区域外谐振。 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。 根据本发明的滤波噪声的应用避免了在存储期望的试剂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，超过最大值，并且由滤波的噪声信号确定的窗口之外（最小值和最大值之间）。

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。