公开(公告)号：US09818595B2

公开(公告)日：2017-11-14

申请号：US14709329

申请日：2015-05-11

Applicant: Thermo Finnigan LLC

Inventor： Philip M. Remes ,  Michael W. Senko ,  Jae C. Schwartz

IPC: H01J49/42

CPC classification number: H01J49/422 ,  H01J49/428

Abstract: A mass spectrometer includes a radio frequency ion trap; and a controller. The controller is configured to cause an ion population to be injected into the radio frequency ion trap; supply a first isolation waveform to the radio frequency ion trap for a first duration, and supply a second isolation waveform to the radio frequency ion trap for a second duration. The first isolation waveform has at least a first wide notch at a first mass-to-charge ratio, and the second isolation waveform has at least a first narrow notch at the first mass-to-charge ratio. The first and second isolation waveforms are effective to isolate one or more precursor ions from the ion population.

公开(公告)号：US20160336163A1

公开(公告)日：2016-11-17

申请号：US14709329

申请日：2015-05-11

Applicant: Thermo Finnigan LLC

Inventor： Philip M. REMES ,  Michael W. SENKO ,  Jae C. SCHWARTZ

IPC: H01J49/42

CPC classification number: H01J49/422 ,  H01J49/428

Abstract: A mass spectrometer includes a radio frequency ion trap; and a controller. The controller is configured to cause an ion population to be injected into the radio frequency ion trap; supply a first isolation waveform to the radio frequency ion trap for a first duration, and supply a second isolation waveform to the radio frequency ion trap for a second duration. The first isolation waveform has at least a first wide notch at a first mass-to-charge ratio, and the second isolation waveform has at least a first narrow notch at the first mass-to-charge ratio. The first and second isolation waveforms are effective to isolate one or more precursor ions from the ion population.

Abstract translation: 质谱仪包括射频离子阱; 和控制器。 控制器配置成使离子群体注入射频离子阱; 在第一持续时间内向射频离子阱提供第一隔离波形，并在第二持续时间内向射频离子阱提供第二隔离波形。 第一隔离波形具有至少第一宽电容比的第一宽陷波，第二隔离波形至少具有第一质荷比的第一窄陷波。 第一和第二隔离波形对从离子群体分离一个或多个前体离子是有效的。

公开(公告)号：US09048074B2

公开(公告)日：2015-06-02

申请号：US14374035

申请日：2013-01-24

Applicant: Thermo Finnigan LLC

Inventor： Michael W. Senko

IPC: H01J49/00 ,  H01J49/42 ,  G01N33/68

CPC classification number: H01J49/0045 ,  G01N33/6848 ,  G06F19/18 ,  H01J49/0031 ,  H01J49/0081 ,  H01J49/428

Abstract: A mass spectrometry method for analyzing isobarically-labeled analyte compounds comprising (a) ionizing compounds including the isobarically-labeled analyte compounds to generate a plurality of precursor ion species comprising different respective m/z ratios, (b) isolating a precursor ion species, (c) fragmenting the precursor ion species to generate a plurality of first-generation fragment ion species comprising different respective m/z ratios, and (d) selecting and co-isolating two or more of the first-generation product-ion species, the method characterized by: (e) fragmenting all of the selected and isolated first-generation product ion species so as to generate a plurality of second-generation fragment ion species including released label ions; (f) generating a mass spectrum of the second-generation fragment ion species; and (g) generating quantitative information relating to at least one analyte compound based on peaks of the mass spectrum attributable to the released label ions.

Abstract translation: 一种用于分析等压标记的分析物质的质谱法，其包括（a）电离化合物，包括等量标记的分析物质，以产生包含不同相应m / z比的多种前体离子物质，（b）分离前体离子物质， c）使前体离子物质碎裂以产生包含不同相应m / z比率的多个第一代碎片离子物质，和（d）选择和共分离两种或更多种第一代产物离子种类，该方法 其特征在于：（e）将所有选择和分离的第一代产物离子物质分段，以产生多个第二代碎片离子物质，包括释放的标记离子; （f）产生第二代碎片离子物质的质谱; 和（g）基于归因于释放的标记离子的质谱的峰产生与至少一种分析物化合物相关的定量信息。

公开(公告)号：US20050067565A1

公开(公告)日：2005-03-31

申请号：US10873107

申请日：2004-06-23

Applicant: Yasuaki Takada ,  Hisashi Nagano

Inventor： Yasuaki Takada ,  Hisashi Nagano

IPC: G01N27/62 ,  H01J49/42

CPC classification number: H01J49/424 ,  H01J49/0063 ,  H01J49/428

Abstract: A mass spectrometer capable of analysis at high speed and high accuracy comprising a device for applying a high frequency signal not containing resonance frequencies for plural precursor ions but containing resonance frequencies of other ions, and having different amplitudes on every frequencies to an electrode constituting the mass spectrometer thereby controlling the selection for the plural precursor ions, and a device for applying a high frequency signal having amplitudes set individually on every resonance frequencies of the plural precursor ions and superimposed with the resonance frequencies for the plural precursor ions to the electrode constituting the mass spectrometer thereby controlling the dissociation of the plural precursor ions, and judging the presence or absence of the aimed chemical substance based on the mass spectra of the obtained by dissociating the plural fragment ions.

Abstract translation: 能够以高速，高精度进行分析的质谱仪，其特征在于，包括用于施加不包含多个前体离子的共振频率但含有其他离子的共振频率的高频信号的装置，并且在构成所述质量的电极的每个频率上具有不同的振幅 光谱仪，从而控制多个前体离子的选择，以及用于施加具有单独设置在多个前体离子的每个共振频率上的振幅的高频信号并与多个前体离子的共振频率叠加到构成质量的电极的装置 从而控制多个前体离子的解离，并且基于通过解离多个片段离子获得的质谱来判断目标化学物质的存在或不存在。

公开(公告)号：US06815673B2

公开(公告)日：2004-11-09

申请号：US10322464

申请日：2002-12-19

Applicant: Jeffry B. Plomley ,  Frank A. Londry

Inventor： Jeffry B. Plomley ,  Frank A. Londry

IPC: H01J4942

CPC classification number: H01J49/005 ,  H01J49/004 ,  H01J49/4225 ,  H01J49/428

Abstract: A method and apparatus for the analysis of a narrow range of fragment ions by application of a notched broadband waveform during ion accumulation within a quadrupole collision cell operated as a linear ion trap. The fragment ions are formed via the axial acceleration and collision activated dissociation of mass resolved precursor ions. A narrow band of frequencies is purposefully omitted from the spectrum, so that the secular frequency of a particular fragment ion will fall within this notch of absent frequencies and as a result will not experience resonant excitation and are retained in the linear ion trap. Simultaneously, all other ions are lost either through neutralization when they strike electrodes or through (additional) collision activated dissociation. Accordingly, a particular mass or range of masses, whose secular frequencies fall within the notch of absent frequencies in the notched broadband waveform, may be selectively accumulated during the collision activated dissociation event.

Abstract translation: 一种用于通过在作为线性离子阱操作的四极碰撞池中的离子累积期间施加缺口宽带波形来分析窄范围的碎片离子的方法和装置。 碎片离子通过质量分辨前体离子的轴向加速度和碰撞激活解离形成。 从频谱中有目的地省略了一个窄带频率，使得特定片段离子的长期频率将落在缺失频率的该陷波范围内，结果将不会经历共振激发并保留在线性离子阱中。 同时，当所有其他离子发射电极或通过（附加）碰撞激活解离时，通过中和而丢失。 因此，可以在碰撞激活的解离事件期间选择性地累积特定的质量或质量范围，其质量或范围的长期频率落在缺口宽带波形中的缺失频率的陷波中。

公开(公告)号：US5517025A

公开(公告)日：1996-05-14

申请号：US436993

申请日：1995-05-08

Applicant: Gregory J. Wells ,  Charles K. Huston

Inventor： Gregory J. Wells ,  Charles K. Huston

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

CPC classification number: H01J49/427 ,  H01J49/428

Abstract: A method of isolating selected ion species in a quadrupole ion trap mass spectrometer is disclosed. One or more ranges of masses to be eliminated from the ion trap are ejected by applying a supplemental dipole excitation waveform, sparsely populated with frequency components, while the trapping field is modulated. The spacing of the frequency components in the supplemental excitation waveform varies across the range of frequencies in the waveform. Preferably, the frequency range is divided into a plurality of subranges, and the spacing of the frequency components in each of the subranges is constant. A method of creating a master set of frequencies used for generating a supplemental excitation waveform is also shown. Likewise, a method of calculating edge frequencies defining a gap in the mass spectrum that is excited by the supplemental waveform is also shown. Modulation of the trapping field may be varied while the supplemental excitation waveform is applied to change the width of the gap in the mass spectrum.

公开(公告)号：US5324939A

公开(公告)日：1994-06-28

申请号：US68915

申请日：1993-05-28

Applicant: John N. Louris ,  Dennis M. Taylor

Inventor： John N. Louris ,  Dennis M. Taylor

IPC: G01N27/62 ,  H01J49/42

CPC classification number: H01J49/424 ,  H01J49/428

Abstract: A method and apparatus is described which determines a plurality of spaced discrete frequencies covering the range of frequencies of the characteristic motion of unwanted ions and processes said discrete frequencies to generate a plurality of time dependent voltage amplitude values which vary throughout the time domain such that the frequency content of said plurality of time dependent voltage amplitude values is relatively uniform over the entire time domain, and such that the magnitude associated with the discrete frequencies is relatively uniform over the frequency domain.

Abstract translation: 描述了一种方法和装置，其确定覆盖不想要的离子的特征运动的频率范围的多个间隔的离散频率，并处理所述离散频率以产生在整个时域中变化的多个随时间变化的电压振幅值，使得 所述多个时间相关电压振幅值的频率内容在整个时域上相对均匀，并且使得与离散频率相关联的幅度在频域上相对均匀。

公开(公告)号：US5196699A

公开(公告)日：1993-03-23

申请号：US662427

申请日：1991-02-28

Applicant: Paul E. Kelley

Inventor： Paul E. Kelley

IPC: G01N27/62 ,  H01J49/42

CPC classification number: H01J49/145 ,  H01J49/424 ,  H01J49/428

Abstract: 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.

Abstract translation: 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

Applicant: Paul E. Kelley

Inventor： Paul E. Kelley

IPC: H01J49/42

CPC classification number: H01J49/4215 ,  H01J49/428

Abstract: 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.

Abstract translation: 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

Applicant: Paul E. Kelley

Inventor： Paul E. Kelley

IPC: G01N27/62 ,  H01J49/42

CPC classification number: H01J49/424 ,  H01J49/0081 ,  H01J49/428

Abstract: 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.

Abstract translation: 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。