公开(公告)号：US06365892B1

公开(公告)日：2002-04-02

申请号：US09199108

申请日：1998-11-24

Applicant: Robert J. Cotter ,  Vladimir M. Doroshenko

Inventor： Robert J. Cotter ,  Vladimir M. Doroshenko

IPC: B01D5944

CPC classification number: H01J49/405 ,  H01J49/06 ,  H01J49/40

Abstract: The present invention provides for a reflectron time-of-flight mass spectrometer in which there exists a curved field in a portion of the reflectron that takes into account acceleration and deceleration fields in upstream (from the ion source down to the reflectron) and downstream (from the reflectron down to the ion detector) regions, which are always present in any TOF-MS. The reflectron includes a decelerating section and a correcting section, with curved electric fields in the correcting and/or decelerating sections of the reflectron being considered. Moreover, analytic expressions are provided for calculating the profiles of the curved electric field in the second (correcting) section of the reflectron, which expressions are valid for arbitrary electric field distributions in the upstream and downstream regions as well as in the first (deceleration) section of the reflectron. These profiles will depend on the electric field distributions in the upstream and downstream regions and in the first (deceleration) section of the reflectron.

Abstract translation: 本发明提供了一种反射器飞行时间质谱仪，其中在反射器的一部分中存在弯曲场，其考虑上游（从离子源到反射器）和下游的加速和减速场（ 从反射器到离子检测器）区域，其总是存在于任何TOF-MS中。 反射镜包括减速部分和校正部分，在反射镜的校正和/或减速部分中考虑弯曲的电场。 此外，提供分析表达式用于计算反射器的第二（校正）部分中的弯曲电场的轮廓，该表达式对于上游和下游区域以及第一（减速）区域中的任意电场分布是有效的， 反射镜的一部分。 这些轮廓将取决于上游和下游区域以及反射镜的第一（减速）部分中的电场分布。

公开(公告)号：US5696376A

公开(公告)日：1997-12-09

申请号：US650411

申请日：1996-05-20

Applicant: Vladimir M. Doroshenko ,  Robert J. Cotter

Inventor： Vladimir M. Doroshenko ,  Robert J. Cotter

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

CPC classification number: H01J49/424 ,  H01J49/427

Abstract: A method of operation of an ion trap mass spectrometer which isolates a first group of ions having a mass-to-charge ratio range is disclosed. The method includes producing ions from a plurality of atoms or molecules; trapping the ions in an ion trap by applying a trapping voltage to a ring electrode; applying an excitation voltage to a pair of end-cap electrodes; employing as the excitation voltage a first broadband excitation waveform and a second broadband excitation waveform, with the first waveform exciting the ions excluding substantially all of the first group and also excluding substantially all of a second group of ions having a range of mass-to-charge ratios about the first group's mass-to-charge ratio range, and the second waveform exciting the second group; applying the first waveform in order to eject the ions excluding substantially all of the first and second groups; and applying the second waveform in order to successively eject the second group of ions, according to the mass-to-charge ratios thereof, excluding substantially all of the first group of ions, thereby isolating the first group of ions. In another embodiment, the excitation voltage is a broadband excitation waveform having first, second, and third excitation portions, with the first and third portions exciting the ions excluding substantially all of the first group and also excluding substantially all of the second group, and the second portion exciting the second group. Associated apparatus is also disclosed.

Abstract translation: 公开了分离具有质荷比范围的第一组离子的离子阱质谱仪的操作方法。 该方法包括从多个原子或分子产生离子; 通过向环形电极施加捕获电压将离子捕获在离子阱中; 向一对端帽电极施加激励电压; 使用第一宽带激励波形和第二宽带激励波形作为激励电压，其中第一波形激励除了基本上所有第一组之外的离子，并且还排除基本上全部具有质量 - 电荷比关于第一组的质荷比范围，第二波形激励第二组; 施加第一波形以排出除了基本上所有第一和第二组之外的离子; 以及施加所述第二波形，以便根据其质荷比，连续地排出所述第二组离子，所述第二组离子基本上不包括所述第一组离子，从而隔离所述第一组离子。 在另一个实施例中，激励电压是具有第一，第二和第三激励部分的宽带激励波形，其中第一和第三部分激励除了基本上所有第一组之外的离子，并且还排除了基本上所有的第二组， 激励第二组的第二部分。 还公开了相关装置。

公开(公告)号：US5399857A

公开(公告)日：1995-03-21

申请号：US68697

申请日：1993-05-28

Applicant: Vladimir M. Doroshenko ,  Robert J. Cotter

Inventor： Vladimir M. Doroshenko ,  Robert J. Cotter

IPC: H01J49/42

CPC classification number: H01J49/4295 ,  H01J49/164 ,  H01J49/424

Abstract: A method and apparatus for trapping ions in an ion trap having a ring electrode and a plurality of end-cap electrodes. Ions are introduced into a ion trap cavity of the ion trap from an external source or by desorption of a substance in the ion trap cavity. In a first embodiment, as the ions are introduced in the ion trap cavity, the amplitude of an RF voltage being applied to the ring electrode is gradually increased to trap the ions in the ion trap cavity. In a second embodiment, as the ions are introduced in the ion trap cavity, a retarding voltage is applied to the end-caps to reduce the initial kinetic energy of the ions. In a third embodiment, as the ions are introduced in the ion trap cavity from a probe tip inserted in the cavity, a retarding voltage is applied to the probe tip.

Abstract translation: 一种用于在具有环形电极和多个端帽电极的离子阱中捕获离子的方法和装置。 离子从外部源引入离子阱的离子阱空穴中或者通过物质在离子阱腔中的解吸引入。 在第一实施例中，当离子被引入离子阱腔中时，施加到环形电极的RF电压的幅度逐渐增加以捕获离子陷阱腔中的离子。 在第二实施例中，当离子被引入离子阱腔中时，延迟电压被施加到端帽以减小离子的初始动能。 在第三实施例中，当离子从插入空腔中的探针尖端引入到离子阱腔中时，延迟电压被施加到探针尖端。

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：US07397029B2

公开(公告)日：2008-07-08

申请号：US11620504

申请日：2007-01-05

Applicant: Vadym D. Berkout ,  Vladimir M. Doroshenko

Inventor： Vadym D. Berkout ,  Vladimir M. Doroshenko

IPC: B01D59/44

CPC classification number: H01J49/0045

Abstract: An apparatus for mass analyzing molecules includes a mass spectrometer configured to select precursor ions having a mass to charge ratio range, a metastable species generator configured to generate a metastable species for introduction into the mass spectrometer, and a mass detector configured to detect a mass of the product ions. The apparatus also includes interaction region in the mass spectrometer where the precursor ions are converted into product ions via interaction of the precursor ions with the metastable species. The mass spectrometer includes at least one of a three-dimensional ion trap, a linear ion trap, or an ion guide. The interaction region is located inside the three-dimensional ion trap, the linear trap, or the ion guide; and at least one of the precursor ions or at least one of the product ions are excited by an alternating electric field or collisionally activated to produce additional product ions.

Abstract translation: 用于质量分析分子的装置包括：质谱仪，其被配置为选择具有质荷比范围的前体离子;构造成产生用于引入质谱仪的亚稳态物质的亚稳态物质发生器;以及质量检测器， 产品离子。 该装置还包括质谱仪中的相互作用区域，其中前体离子通过前体离子与亚稳态物质的相互作用转化成产物离子。 质谱仪包括三维离子阱，线性离子阱或离子导体中的至少一种。 相互作用区域位于三维离子阱，线性阱或离子导向器内; 并且至少一种前体离子或至少一种产物离子被交变电场激发或者被碰撞激活以产生另外的产物离子。

公开(公告)号：US06791080B2

公开(公告)日：2004-09-14

申请号：US10367917

申请日：2003-02-19

Applicant: Vladimir M. Doroshenko ,  Victor V. Laiko ,  Phillip V. Tan

Inventor： Vladimir M. Doroshenko ,  Victor V. Laiko ,  Phillip V. Tan

IPC: H01J4904

CPC classification number: H01J49/403

Abstract: An apparatus and a method which produce a pulse of ions, generate a transient electric field correlated in time with a duration of the pulse of ions, receive the pulse of ions into the transient electric field, and collect the ions from an ion drift region of the transient electric field into a gas dynamic flow region of the mass analyzer. As such, an apparatus for transferring ions into a mass analyzer includes an ion source configured to generate the pulse of ions, a transient electric field device configured to receive the pulse of ions and generate the transient electric field, and an ion collector configured to collect the ions from the ion drift region and transfer the ions into the mass analyzer.

Abstract translation: 产生离子脉冲的装置和方法产生时间上与离子脉冲持续时间相关的瞬时电场，将离子脉冲接收到瞬态电场中，并从离子漂移区域 瞬态电场进入质量分析仪的气体动态流动区域。 因此，用于将离子转移到质量分析器中的装置包括被配置为产生离子脉冲的离子源，被配置为接收离子脉冲并产生瞬态电场的瞬态电场装置，以及被配置为收集离子的离子收集器 来自离子漂移区域的离子并将离子转移到质谱仪中。

公开(公告)号：US08825413B2

公开(公告)日：2014-09-02

申请号：US12755977

申请日：2010-04-07

Applicant: Alexander Misharin ,  Konstantin Novoselov ,  Vladimir M. Doroshenko

Inventor： Alexander Misharin ,  Konstantin Novoselov ,  Vladimir M. Doroshenko

IPC: G01N31/00 ,  H01J49/38 ,  H01J49/00 ,  H03F1/26

CPC classification number: H01J49/0036 ,  H01J49/38

Abstract: A method and system for deconvolution of a frequency spectrum obtained in an ICR mass spectrometer based on a detection of ion oscillation overtones of the M-th order (where the integer M>1). A plurality of frequency peaks is collected within the frequency spectrum corresponding respectively to oscillations of different groups of ions, and associates at least one of the frequency peaks having a frequency f and a measured amplitude A with a particular group of the ions. The method and system identify whether the frequency peak is related to one of an overtone frequency, a subharmonic frequency, a higher harmonic frequency, or a side-shifted frequency of the oscillations of the different group of ions. The method and system derive calculated amplitudes of the overtone frequency peaks associated with the groups of ions by incorporating measured amplitudes of the frequency peaks related to the subharmonic frequency, the higher harmonic frequency, or the side-shifted frequency associated with the groups of ions into the calculated amplitudes of the overtone frequency peaks. The method and system generate a deconvoluted frequency spectrum including the overtone frequency peaks associated with the different groups of ions.

Abstract translation: 基于对M阶离子振荡泛音（其中整数M> 1）的检测，在ICR质谱仪中获得的频谱的去卷积方法和系统。 在分别对应于不同离子组的振荡的频谱内收集多个频率峰值，并且将具有频率f和测量幅度A的频率峰值中的至少一个与特定的一组离子相关联。 该方法和系统识别频率峰值是否与不同离子组的振荡的泛音频率，次谐波频率，高次谐波频率或侧移频率之一相关。 该方法和系统通过将与次谐波频率，高次谐波频率或与离子组相关联的侧移频率相关的频率峰值的测量幅度并入到离子组相关的泛音频率峰值中来计算振幅 计算的泛音频率峰值的幅度。 该方法和系统产生包括与不同离子组相关的泛音频率峰值的解卷积频谱。

公开(公告)号：US20120326026A1

公开(公告)日：2012-12-27

申请号：US13168690

申请日：2011-06-24

Applicant: Alexander MISHARIN ,  Vladimir M. Doroshenko

Inventor： Alexander MISHARIN ,  Vladimir M. Doroshenko

IPC: H01J49/34 ,  H01J49/26

CPC classification number: H01J49/424 ,  H01J49/0013 ,  H01J49/0081 ,  H01J49/0481 ,  H01J49/422

Abstract: A mass spectrometry (MS) method which includes generating in a vicinity of the quadrupole ion trap hydrogen molecules, directing at least part of the hydrogen molecules into the quadrupole ion trap cell, applying AC and DC voltages to quadrupole ion trap cell electrodes to create a combined AC/DC trapping field, placing sample ions inside the quadrupole ion trap cell, cooling at least part of said ions using said hydrogen molecules as a buffer gas, changing the combined AC/DC trapping field to eject the ions from the quadrupole ion trap cell, and detecting the ejected ions

Abstract translation: 一种质谱（MS）方法，其包括在四极离子阱附近产生氢分子，将至少部分氢分子引入四极离子阱电池中，向四极离子阱电池电极施加AC和DC电压，以产生 组合的AC / DC捕获场，将样品离子放置在四极离子阱单元内，使用所述氢分子作为缓冲气体冷却至少部分所述离子，改变组合的AC / DC捕获场以从四极离子阱中排出离子 电池，并检测被排出的离子

公开(公告)号：US08188423B2

公开(公告)日：2012-05-29

申请号：US12784532

申请日：2010-05-21

Applicant: Vladimir M. Doroshenko ,  Vadym D. Berkout ,  Andrey Vilkov

Inventor： Vladimir M. Doroshenko ,  Vadym D. Berkout ,  Andrey Vilkov

IPC: H01J49/00 ,  B01D59/44

CPC classification number: H01J49/0045

Abstract: A method for fragmentation of analyte ions for mass spectroscopy and a system for mass spectroscopy. The method produces gas-phase analyte ions, produces gas-phase odd-electron containing species separately from the analyte ions, and mixes the gas-phase analyte ions and the odd-electron containing species at substantially atmospheric pressure conditions to produce fragment ions prior to introduction into a mass spectrometer. The system includes a gas-phase analyte ion source, a gas-phase odd-electron containing species source separate from the gas-phase analyte ion source, a mixing region where the gas-phase analyte ions and the odd-electron containing species are mixed at substantially atmospheric pressure to produce fragment ions of the analyte ions, a mass spectrometer having an entrance where at least a portion of the fragment ions are introduced into a vacuum of the mass spectrometer, and a detector in the mass spectrometer which determines a mass to charge ratio analysis of the fragment ions.

Abstract translation: 用于质谱分析的分析物离子的碎裂方法和用于质谱的系统。 该方法产生气相分析物离子，与分析物离子分开产生含气相奇异电子物质，并在基本大气压条件下将气相分析离子和含奇异电子的物质混合，以在 引入质谱仪。 该系统包括气相分析物离子源，与气相分析物离子源分离的气相奇电子物质源，气相分析物离子和含奇异电子的物质混合的混合区域 在基本上大气压下产生分析物离子的碎片离子，质谱仪具有入口，其中至少一部分碎片离子被引入质谱仪的真空中，以及质谱仪中的检测器， 电荷比分析碎片离子。

公开(公告)号：US20100288920A1

公开(公告)日：2010-11-18

申请号：US12784532

申请日：2010-05-21

Applicant: Vladimir M. Doroshenko ,  Vadym D. Berkout ,  Andrey Vilkov

Inventor： Vladimir M. Doroshenko ,  Vadym D. Berkout ,  Andrey Vilkov

IPC: H01J49/00 ,  B01D59/44

CPC classification number: H01J49/0045

Abstract: A method for fragmentation of analyte ions for mass spectroscopy and a system for mass spectroscopy. The method produces gas-phase analyte ions, produces gas-phase odd-electron containing species separately from the analyte ions, and mixes the gas-phase analyte ions and the odd-electron containing species at substantially atmospheric pressure conditions to produce fragment ions prior to introduction into a mass spectrometer. The system includes a gas-phase analyte ion source, a gas-phase odd-electron containing species source separate from the gas-phase analyte ion source, a mixing region where the gas-phase analyte ions and the odd-electron containing species are mixed at substantially atmospheric pressure to produce fragment ions of the analyte ions, a mass spectrometer having an entrance where at least a portion of the fragment ions are introduced into a vacuum of the mass spectrometer, and a detector in the mass spectrometer which determines a mass to charge ratio analysis of the fragment ions.

Abstract translation: 用于质谱分析的分析物离子的碎裂方法和用于质谱的系统。 该方法产生气相分析物离子，与分析物离子分开产生含气相奇异电子物质，并在基本大气压条件下将气相分析离子和含奇异电子的物质混合，以在 引入质谱仪。 该系统包括气相分析物离子源，与气相分析物离子源分离的气相奇电子物质源，气相分析物离子和含奇异电子的物质混合的混合区域 在基本上大气压下产生分析物离子的碎片离子，质谱仪具有入口，其中至少一部分碎片离子被引入质谱仪的真空中，以及质谱仪中的检测器， 电荷比分析碎片离子。