公开(公告)号：US06989534B2

公开(公告)日：2006-01-24

申请号：US10849499

申请日：2004-05-19

申请人： Michael Schubert ,  Jochen Franzen

发明人： Michael Schubert ,  Jochen Franzen

IPC分类号： H01J49/42

CPC分类号： H01J49/424 ,  H01J49/067 ,  H01J49/4295

摘要： The invention relates to methods and devices for the effective capturing of externally generated ions in an RF operated quadrupole ion trap. The invention involves applying a voltage consisting of positive and negative pulses, instead of a sinusoidal RF voltage, during the capturing process, with capturing intervals between each pulse in which the voltage is low.

摘要翻译： 本发明涉及用于在RF操作的四极离子阱中有效捕获外部产生的离子的方法和装置。 本发明涉及在捕获过程期间施加由正脉冲和负脉冲组成的电压而不是正弦RF电压，其中电压低的每个脉冲之间的捕获间隔。

公开(公告)号：US5654542A

公开(公告)日：1997-08-05

申请号：US588209

申请日：1996-01-19

申请人： Michael Schubert ,  Jochen Franzen

发明人： Michael Schubert ,  Jochen Franzen

IPC分类号： H01J49/42

CPC分类号： H01J49/428

摘要： A method for the simultaneous resonant excitation of the oscillations of ions of various mass-to-charge ratios in ion traps, particularly for the ejection of undesirable ion species, by applying RF frequencies with various frequency components to electrodes of the ion trap. The method consists in generating and storing a broadband signal for as short a time as possible so that it can be fed to the ion trap a number of times in succession cyclically, without generating undesirable interference due to phase shifts. The excitation of the ions should be as temporally constant as possible throughout the waveform period. The duration of the waveform period depends on the mass resolution required. Excitation is terminated by controlling the broadband signal gradually toward zero in a constant function.

摘要翻译： 通过将具有各种频率分量的RF频率施加到离子阱的电极，同时共振激发离子阱中各种质荷比的离子的振荡，特别是用于喷射不期望的离子种类的方法。 该方法包括在尽可能短的时间内产生和存储宽带信号，使得其可以循环地连续多次馈送到离子阱，而不会由于相移而产生不期望的干扰。 在整个波形周期内，离子的激发应该尽可能地保持恒定。 波形周期的持续时间取决于所需的质量分辨率。 通过在恒定功能中将宽带信号逐渐向零控制来终止激励。

公开(公告)号：US6133568A

公开(公告)日：2000-10-17

申请号：US123337

申请日：1998-07-28

申请人： Gerhard Weiss ,  Alfred Kraffert ,  Michael Schubert ,  Jochen Franzen

发明人： Gerhard Weiss ,  Alfred Kraffert ,  Michael Schubert ,  Jochen Franzen

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

CPC分类号： H01J49/424 ,  H01J49/068 ,  H01J49/4255

摘要： The invention relates to high performance ion traps used as mass spectrometers which in spite of a variable thermal load require a high constancy of the mass scale calibrated in. Ion traps consist at least of one ring electrode, two end cap electrodes, and suitable fixing elements which determine the distance between the electrodes. When exposed to a thermal load, the parts of the ion trap are subject to thermal expansion, which leads to a change in field intensities even if the applied RF voltage is constant, and thus to an apparant shift of masses. The invention consists of selecting the thermal expansion of the ion trap parts in such a way that when a constant RF voltage is applied, the field intensity within the trap remains constant by first approximation, in spite of the altering geometric form and expansion with changing operating temperature. In this way, displacement of the mass scale is avoided. To compensate an unavoidable thermal expansion .DELTA.r.sub.0 of the ring electrode with an inscribed radius r.sub.0 by a ratio .DELTA.r.sub.0 /r.sub.0, the distance z.sub.0 of the end cap poles from the center of the trap must become smaller by the proportional ratio .DELTA.z.sub.0 /z.sub.0 =-.DELTA.r.sub.0 /r.sub.0. This compensation can be achieved by a suitable design with suitably selected expansion coefficients for the ion trap electrode material and the material of the fixing elements.

摘要翻译： 本发明涉及用作质谱仪的高性能离子阱，尽管可变热负载需要校准的质量标准的高恒定性。离子阱由至少一个环形电极，两个端盖电极和合适的固定元件组成 其确定电极之间的距离。 当暴露于热负荷时，离子阱的部分经受热膨胀，即使所施加的RF电压恒定，导致电场强度的变化，从而导致质量偏移。 本发明包括选择离子阱部件的热膨胀，使得当施加恒定的RF电压时，尽管通过改变操作来改变几何形状和膨胀，但陷阱内的场强保持恒定。 温度。 以这种方式，避免了质量标度的位移。 为了以内切半径r0的比例DELTA r0 / r0来补偿环形电极的不可避免的热膨胀DELTA r0，端盖极距离陷阱中心的距离z0必须按照比例比DELTA z0 / z0变小 = - DELTA r0 / r0。 这种补偿可以通过合适的设计来实现，该设计具有用于离子阱电极材料和固定元件的材料的适当选择的膨胀系数。

公开(公告)号：US5903003A

公开(公告)日：1999-05-11

申请号：US32563

申请日：1998-02-27

申请人： Michael Schubert ,  John Fjeldsted ,  Jochen Franzen

发明人： Michael Schubert ,  John Fjeldsted ,  Jochen Franzen

IPC分类号： H01J49/42

CPC分类号： H01J49/0031

摘要： The invention referres to analytic methods, the accuracy of which is increased by relating signals of analyte ions to those of reference ions, or by relating ion signals from measuring methods under special conditions to those of reference methods. If such "comparative" analysis procedures are performed in ion trap mass spectrometers, problems arise with the low dynamic measuring range covered by one spectrum in such mass spectrometers and, if different spectra are compared, with the control of the space charge within the ion trap. The invention consists in acquiring analyte spectra and reference spectra in different acquisition procedures, alternating between both types of spectrum acquisitions as fast as possible, whereby control of the space charge in the ion trap proceeds separately for the spectra of both types, the control being related to previously acquired spectra of the same type. A similar procedure can be set up, if measuring results of two different sets of measurement conditions have to be compared. The control variable for the space charge control is derived from the last respective individual spectra scanned under the same conditions. Due to this fast interchanging of individual spectra, time-saving control of the space charge is achieved on the one hand, and a large dynamic measurement range is available on the other.

摘要翻译： 本发明涉及分析方法，通过将分析物离子的信号与参考离子的信号相关联，或通过将来自特定条件下的测量方法的离子信号与参考方法的离子信号相关联来提高其精度。 如果在离子阱质谱仪中进行这种“比较”分析程序，则在这种质谱仪中由一个光谱覆盖的低动态测量范围出现问题，并且如果不同的光谱被比较，则与离子阱内的空间电荷的控制 。 本发明包括在不同采集程序中获得分析物光谱和参考光谱，在两种类型的光谱采集之间尽可能快地进行交替，从而对两种类型的光谱分别对离子阱中的空间电荷进行控制，该控制是相关的 以前获得相同类型的光谱。 如果必须比较两组不同测量条件的测量结果，可以设置类似的程序。 用于空间电荷控制的控制变量来源于在相同条件下扫描的最后各个单独光谱。 由于单个频谱的快速互换，一方面实现了空间电荷的省时控制，另一方面可获得大的动态测量范围。

公开(公告)号：US5710427A

公开(公告)日：1998-01-20

申请号：US588059

申请日：1996-01-19

申请人： Michael Schubert ,  Jochen Franzen

发明人： Michael Schubert ,  Jochen Franzen

IPC分类号： H01J49/42

CPC分类号： H01J49/424 ,  H01J49/4265 ,  H01J49/4285

摘要： A method of mass selective loading of ion traps by ejection of undesirable ion species during the loading process by applying RF voltages with a mixture of frequency components to the trap electrodes. For several mass spectrometric investigations only ions with desired mass-to-charge ratios are to be loaded into the ion trap in order to achieve a more efficient utilization of the limited storage capability of the ion trap. The generation rate of the ions during the loading process in such a way that the equilibrium of the space charge inside the ion trap, balanced between ion generation rate and ion ejection rate, does not significantly deteriorate the mass resolution of the ejection process.

摘要翻译： 通过将RF电压与频率分量的混合施加到陷波电极，通过在加载过程期间喷射不期望的离子种类来质量选择性地加载离子阱的方法。 对于几个质谱研究，仅将具有期望质荷比的离子装载到离子阱中，以便更有效地利用离子阱的有限存储能力。 负载过程中离子的产生速率使得离子阱内的空间电荷的平衡与离子发射速率和离子喷射速率之间的平衡不会显着降低喷射过程的质量分辨率。

公开(公告)号：US08164056B2

公开(公告)日：2012-04-24

申请号：US12854493

申请日：2010-08-11

申请人： Melvin A. Park ,  Michael Schubert ,  Jochen Franzen

发明人： Melvin A. Park ,  Michael Schubert ,  Jochen Franzen

IPC分类号： H01J49/42

CPC分类号： H01J49/4295 ,  H01J49/424

摘要： In a three-dimensional Paul RF ion trap the ring electrode and end cap electrodes are formed from pairs of pole rods. This multipole rod system is then operated as a linear ion trap with a constant field distribution along the multipole rod system. While the system is operating as a linear ion trap, analyte ions are introduced and stored within the linear ion trap. After the ions have been stored, a single-phase RF voltage is supplied to all rods of a middle segment thus forming a three-dimensional ion trap, thereby collecting the ions in a spherical cloud within this middle segment. The collected analyte ions can then be reacted in the three-dimensional ion trap and the product ions resulting from the reactions can be ejected for mass analysis.

摘要翻译： 在三维Paul RF离子阱中，环形电极和端盖电极由极棒对形成。 然后，该多极棒系统沿着多极杆系统作为具有恒定场分布的线性离子阱操作。 当系统作为线性离子阱操作时，分析物离子被引入并存储在线性离子阱内。 在离子被储存之后，单相RF电压被提供给中间段的所有棒，从而形成三维离子阱，从而在该中间段内将离子收集在球形云中。 收集的分析物离子然后可以在三维离子阱中反应，并且可以喷射由反应产生的产物离子进行质量分析。

公开(公告)号：US20110139976A1

公开(公告)日：2011-06-16

申请号：US12854493

申请日：2010-08-11

申请人： Melvin A. Park ,  Michael Schubert ,  Jochen Franzen

发明人： Melvin A. Park ,  Michael Schubert ,  Jochen Franzen

IPC分类号： B01D59/44

CPC分类号： H01J49/4295 ,  H01J49/424

摘要： In a three-dimensional Paul RF ion trap the ring electrode and end cap electrodes are formed from pairs of pole rods. This multipole rod system is then operated as a linear ion trap with a constant field distribution along the multipole rod system. While the system is operating as a linear ion trap, analyte ions are introduced and stored within the linear ion trap. After the ions have been stored, a single-phase RF voltage is supplied to all rods of a middle segment thus forming a three-dimensional ion trap, thereby collecting the ions in a spherical cloud within this middle segment. The collected analyte ions can then be reacted in the three-dimensional ion trap and the product ions resulting from the reactions can be ejected for mass analysis.

摘要翻译： 在三维Paul RF离子阱中，环形电极和端盖电极由极棒对形成。 然后，该多极棒系统沿着多极杆系统作为具有恒定场分布的线性离子阱操作。 当系统作为线性离子阱操作时，分析物离子被引入并存储在线性离子阱内。 在离子被储存之后，单相RF电压被提供给中间段的所有棒，从而形成三维离子阱，从而将该离子收集在该中间段内的球形云中。 收集的分析物离子然后可以在三维离子阱中反应，并且可以喷射由反应产生的产物离子进行质量分析。

公开(公告)号：US07872229B2

公开(公告)日：2011-01-18

申请号：US12172605

申请日：2008-07-14

申请人： Melvin A. Park ,  Michael Schubert ,  Jochen Franzen

发明人： Melvin A. Park ,  Michael Schubert ,  Jochen Franzen

IPC分类号： H01J49/42

CPC分类号： H01J49/4295 ,  H01J49/424

摘要： In a three-dimensional Paul RF ion trap at least one of the ring electrode and end cap electrodes is structured to produce a high capture efficiency for analyte ions introduced into the trap. The electrode structuring may be produced by an electrode surface profile having edges or protrusions, resulting in a scattering reflection of the introduced ions. Alternatively, at least one electrode may be formed by physically separate electrode components. In one embodiment, the trap can be switched between operating as a linear ion trap with good capture efficiency and operating as a three-dimensional ion trap with good ion reaction conditions.

摘要翻译： 在三维Paul RF离子阱中，环形电极和端盖电极中的至少一个被构造成为引入陷阱的分析物离子产生高捕获效率。 电极结构可以通过具有边缘或突起的电极表面轮廓来产生，导致引入离子的散射反射。 或者，可以通过物理分离的电极组件形成至少一个电极。 在一个实施例中，可以在具有良好捕获效率的线性离子阱之间切换陷阱，并且作为具有良好离子反应条件的三维离子阱操作。

公开(公告)号：US5811800A

公开(公告)日：1998-09-22

申请号：US713812

申请日：1996-09-13

申请人： Jochen Franzen ,  Michael Schubert

发明人： Jochen Franzen ,  Michael Schubert

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

CPC分类号： H01J49/062 ,  H01J49/422

摘要： The invention relates to methods and devices for the temporary storage of ions which are to be subjected to mass spectrometric analysis. Such temporary storage of ions in an RF multipole rod system for their analysis in an RF quadrupole ion trap is known from U.S. Pat. No. 5,179,278. The invention uses this known temporary storage for such ions which are produced in an ion source from substance peaks from chromatographic or electrophoretich separation devices, or from other devices which feed substances in form of short-lasting peaks. The temporary store thereby accepts sufficient ions of a substance peak for several successive mass spectrometric analyses, so that a mass spectrometric characterization of the substances, which may also require varying measurement methods, is made possible to the desired degree. Particularly ions from electrophoretically or chromatographically separated substance peaks should be able to be temporarily stored long enough until the mass spectrometric analyses have been concluded to the desired extent. Several temporary stores can collect the ions from several rapidly successive substance peaks. However, short-lasting substance peaks from laser desorptive or pyrolitic processes can also be thoroughly analyzed by means of temporary storage.

摘要翻译： 本发明涉及临时储存待进行质谱分析的离子的方法和装置。 在RF多极杆系统中这样的临时存储离子在RF四极杆离子阱中进行分析是已知的。 第5,179,278号。 本发明使用这种已知的临时储存用于离子源中产生的这些离子，所述离子源来自色谱或电泳分离装置的物质峰，或者从其它以短持久峰形式供给物质的装置。 临时存储器由此接受足够的物质峰离子以进行几次连续的质谱分析，使得可能需要改变测量方法的物质的质谱表征成为可能达到期望的程度。 特别是来自电泳或色谱分离的物质峰的离子应该能够被暂时保存足够长的时间，直到质谱分析已经达到预期的程度。 几个临时商店可以从几个快速连续的物质峰中收集离子。 然而，也可以通过临时储存来彻底地分析来自激光解吸或热解过程的短暂物质峰。

公开(公告)号：US20050023461A1

公开(公告)日：2005-02-03

申请号：US10849499

申请日：2004-05-19

申请人： Michael Schubert ,  Jochen Franzen

发明人： Michael Schubert ,  Jochen Franzen

IPC分类号： G01N23/00 ,  H01J49/42

CPC分类号： H01J49/424 ,  H01J49/067 ,  H01J49/4295

摘要： The invention relates to methods and devices for the effective capturing of externally generated ions in an RF operated quadrupole ion trap. The invention involves applying a voltage consisting of positive and negative pulses, instead of a sinusoidal RF voltage, during the capturing process, with capturing intervals between each pulse in which the voltage is low.

摘要翻译： 本发明涉及用于在RF操作的四极离子阱中有效捕获外部产生的离子的方法和装置。 本发明涉及在捕获过程期间施加由正脉冲和负脉冲组成的电压而不是正弦RF电压，其中电压低的每个脉冲之间的捕获间隔。