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：US08384019B2

公开(公告)日：2013-02-26

申请号：US12767273

申请日：2010-04-26

申请人： Claus Köster ,  Jochen Franzen

发明人： Claus Köster ,  Jochen Franzen

IPC分类号： B01D59/44

CPC分类号： H01J49/02 ,  H01J49/26 ,  H01J49/425

摘要： In a Kingdon ion trap in which harmonic ion oscillation in a potential well in a longitudinal direction is completely decoupled from ion oscillation in a direction transverse to the longitudinal direction, ions enter the trap via an entrance tube extending through, but electrically insulated from, one of the Kingdon trap housing electrodes and located outside the minimum of the potential well in the longitudinal direction. The geometry of the Kingdon trap is arranged so that the oscillating ions introduced through the entrance tube cannot return to the entrance tube until they have performed several longitudinal oscillations during which time heavy ions can be introduced into the trap.

摘要翻译： 在Kingdon离子阱中，纵向方向的势阱中的谐波离子振荡在垂直于纵向的方向上与离子振荡完全解耦，离子通过入口管进入陷阱，该入口管延伸通过一个 的Kingdon陷阱壳体电极并且位于纵向方向上的势阱的最小值之外。 Kingdon陷阱的几何形状被布置成使得通过入口管引入的振荡离子不能返回到入口管，直到它们执行几个纵向振荡，在该时间期间可以将重离子引入陷阱。

公开(公告)号：US08319180B2

公开(公告)日：2012-11-27

申请号：US13208803

申请日：2011-08-12

申请人： Evgenij Nikolaev ,  Jochen Franzen

发明人： Evgenij Nikolaev ,  Jochen Franzen

IPC分类号： H01J49/28 ,  H01J49/26 ,  H01J49/42

CPC分类号： H01J49/4245

摘要： The invention relates to measuring devices of an electrostatic Fourier transform mass spectrometer and measurement methods for the acquisition of mass spectra with high mass resolution. The measuring device includes electrostatic measuring cells according to the Kingdon principle, in which ions can, when appropriate voltages are applied, orbit on circular trajectories around the cylinder axis between two concentric cylindrical surfaces, which are composed of specially shaped sheath electrodes, insulated from each other by parabolic gaps, and can harmonically oscillate in the axial direction, independently of their orbiting motion. In the longitudinal direction, the two cylindrical surfaces of the measuring cell are divided by the parabolic separating gaps into different types of double-angled and tetragonal sheath electrode segments. Appropriate voltages at the sheath electrode segments generate a potential distribution between the two concentric cylindrical surfaces which forms a parabolic potential well in the axial direction for orbiting ions. The ion clouds oscillating harmonically in the axial direction in this potential well induce image currents in suitable electrodes, from which the oscillation frequencies can be determined by Fourier analyses.

摘要翻译： 本发明涉及静电傅立叶变换质谱仪的测量装置和用于以高质量分辨率采集质谱的测量方法。 测量装置包括根据Kingdon原理的静电测量单元，其中当适当的电压施加时，离子可以在围绕圆柱体轴线的圆周轨迹上轨道在两个同心圆柱表面之间，这两个同心圆柱表面由特殊形状的护套电极组成 另一个是抛物线间隙，并且可以在轴向方向上谐振振荡，而不受其轨道运动的影响。 在纵向方向上，测量单元的两个圆柱形表面被抛物线分离间隔分成不同类型的双角和四角形电极段。 护套电极段处的适当电压在两个同心圆柱形表面之间产生电位分布，这两个同心圆柱形表面在轴向方向上很好地形成抛物线势垒，用于轨道离子。 在该势阱中在轴向上谐波振荡的离子云在合适的电极中引起图像电流，通过傅立叶分析可以确定振荡频率。

公开(公告)号：US20120264162A1

公开(公告)日：2012-10-18

申请号：US13523167

申请日：2012-06-14

申请人： Vadim Markovich Govorun ,  Jochen Franzen

发明人： Vadim Markovich Govorun ,  Jochen Franzen

IPC分类号： G01N27/62

CPC分类号： G01N33/6851 ,  C12Q1/18

摘要： Microorganisms, particularly bacteria, are identified and characterized on the basis of a mass spectrometric measurement of their protein profiles with ionization by matrix-assisted laser desorption. In order to measure the microbial resistance to antibiotics, the protein profiles of microorganisms are measured after cultivation for a short time duration in nutrient media containing the antibiotics.

摘要翻译： 基于通过基质辅助激光解吸电离的蛋白质谱的质谱测定，鉴定和表征微生物，特别是细菌。 为了测量微生物对抗生素的抗性，微生物的蛋白质分布在含有抗生素的营养培养基中培养短时间后测量。

公开(公告)号：US20120228492A1

公开(公告)日：2012-09-13

申请号：US13503202

申请日：2010-11-15

申请人： Jochen Franzen

发明人： Jochen Franzen

IPC分类号： H01J49/26

CPC分类号： H01J49/421 ,  H01J49/401

摘要： The invention relates to ions guided by gas flows in mass spectrometers, particularly in RF multipole systems, and to RF quadrupole mass filters and their operation with gas flows in tandem mass spectrometers. The invention provides a tandem mass spectrometer in which the RF quadrupole mass filter is operated at vacuum pressures in the medium vacuum pressure regime, utilizing a gas flow to drive the ions are through the mass filter. Vacuum pressures between 0.5 to 10 pascal are maintained in the mass filter. The mass filter may be enclosed by a narrow enclosure to guide the gas flow. The quadrupole mass filter may be followed by an RF multipole system, operated at the same vacuum pressure, serving as fragmentation cell to fragment the selected parent ions. The fragmentation cell may be enclosed by the same enclosure which already encloses the mass filter, so the ions may be driven by the same gas flow at the same vacuum pressure, greatly simplifying the required vacuum pumping system in tandem mass spectrometers. There are many other applications utilizing gas flows including supersonic gas jets in mass spectrometry.

摘要翻译： 本发明涉及在质谱仪，特别是RF多极系统中的气流引导的离子，以及RF串联质谱仪和其在串联质谱仪中的气流的操作。 本发明提供一种串联质谱仪，其中RF四极杆质量过滤器在中等真空压力状态下在真空压力下操作，利用气流驱动离子通过质量过滤器。 在质量过滤器中保持0.5至10帕斯卡之间的真空压力。 质量过滤器可以被狭窄的外壳包围以引导气流。 四极质量过滤器之后可以是在相同的真空压力下操作的RF多极体系统，用作碎裂细胞以分离所选择的母体离子。 分裂单元可以被已经包围质量过滤器的相同外壳封闭，因此离子可以在相同的真空压力下由相同的气流驱动，大大简化了串联质谱仪中所需的真空泵送系统。 在质谱法中还有许多其他的应用，包括使用超声波气体射流的气流。

公开(公告)号：US20120043461A1

公开(公告)日：2012-02-23

申请号：US13208803

申请日：2011-08-12

申请人： Evgenij Nikolaev ,  Jochen Franzen

发明人： Evgenij Nikolaev ,  Jochen Franzen

IPC分类号： H01J49/28

CPC分类号： H01J49/4245

摘要： The invention relates to measuring devices of an electrostatic Fourier transform mass spectrometer and measurement methods for the acquisition of mass spectra with high mass resolution. The measuring device includes electrostatic measuring cells according to the Kingdon principle, in which ions can, when appropriate voltages are applied, orbit on circular trajectories around the cylinder axis between two concentric cylindrical surfaces, which are composed of specially shaped sheath electrodes, insulated from each other by parabolic gaps, and can harmonically oscillate in the axial direction, independently of their orbiting motion. In the longitudinal direction, the two cylindrical surfaces of the measuring cell are divided by the parabolic separating gaps into different types of double-angled and tetragonal sheath electrode segments. Appropriate voltages at the sheath electrode segments generate a potential distribution between the two concentric cylindrical surfaces which forms a parabolic potential well in the axial direction for orbiting ions. The ion clouds oscillating harmonically in the axial direction in this potential well induce image currents in suitable electrodes, from which the oscillation frequencies can be determined by Fourier analyses.

摘要翻译： 本发明涉及静电傅立叶变换质谱仪的测量装置和用于以高质量分辨率采集质谱的测量方法。 测量装置包括根据Kingdon原理的静电测量单元，其中当适当的电压施加时，离子可以在围绕圆柱体轴线的圆周轨迹上轨道在两个同心圆柱形表面之间，这两个同心圆柱表面由特殊形状的护套电极组成 另一个是抛物线间隙，并且可以在轴向方向上谐振振荡，而不受其轨道运动的影响。 在纵向方向上，测量单元的两个圆柱形表面被抛物线分离间隔分成不同类型的双角和四角形电极段。 护套电极段处的适当电压在两个同心圆柱形表面之间产生电位分布，这两个同心圆柱形表面在轴向方向上很好地形成抛物线势垒，用于轨道离子。 在该势阱中在轴向上谐波振荡的离子云在合适的电极中引起图像电流，通过傅立叶分析可以确定振荡频率。

公开(公告)号：US20110272573A1

公开(公告)日：2011-11-10

申请号：US13103672

申请日：2011-05-09

申请人： Markus Kostrzewa ,  Jochen Franzen

发明人： Markus Kostrzewa ,  Jochen Franzen

IPC分类号： H01J49/40

CPC分类号： H01J49/0027 ,  H01J49/164 ,  H01J49/40

摘要： The invention relates to acquisition techniques for time-of-flight mass spectra with ionization of the analyte substances by matrix assisted laser desorption. Generally speaking, these acquisition techniques involve adding together a large number of individual time-of-flight spectra, each with restricted dynamic measuring range, to form a sum spectrum. The invention provides a method that improves, in particular, the reproducibility, the concentration accuracy and therefore the ability to quantify the mass spectra. Particular embodiments also increase the dynamic range of measurement. For this purpose, multiple series of mass spectra are acquired, whereby the energy density in the laser spot is increased in discrete steps. As a result, many ion signals saturate the detector and can therefore no longer be evaluated. However, it is possible to employ a technique in which the ion beam is increasingly defocused, or, secondly, to replace parts of the spectrum that are subject to saturation by intensity extrapolations from mass spectra acquired with lower energy density. In the first case, hundreds or thousands of individual mass spectra must be added together in order to increase the dynamic measuring range. In the second case, the finally acquired mass spectrum, with its replacements, forms a mass spectrum with a high dynamic measuring range, improved reproducibility and better concentration accuracy. The gradient of the increasing intensities of the ion signals, as a function of the energy density, supplies additional information about the proton affinity of the analyte ions. The concentration accuracy is enhanced because the increase in the number of proton donors in the ionization plasma leads to an increase in the ionization of those analyte substances that have a lower proton affinity.

摘要翻译： 本发明涉及通过基质辅助激光解吸附物质分析物质离子化的飞行时间质谱采集技术。 一般来说，这些采集技术包括将大量具有限制动态测量范围的单个飞行时间频谱相加在一起以形成和频谱。 本发明提供了一种特别改进重现性，浓度精度以及因此量化质谱的能力的方法。 具体实施例还增加了测量的动态范围。 为此，获得了多个质谱系列，从而在离散步骤中激光斑点的能量密度增加。 因此，许多离子信号使检测器饱和，因此不再能被评估。 然而，可以采用这样一种技术，其中离子束越来越散焦，或者其次，通过由具有较低能量密度获得的质谱的强度外推替代经受饱和的部分光谱。 在第一种情况下，为了增加动态测量范围，必须将数百或数千个单个质谱加在一起。 在第二种情况下，最终获得的质谱与其替代物形成具有高动态测量范围，改进的再现性和更好的浓度精度的质谱。 作为能量密度的函数的离子信号的增加强度的梯度提供关于分析物离子的质子亲和力的附加信息。 由于离子化等离子体中的质子供体的数量的增加导致具有较低质子亲和力的分析物质的电离增加，所以浓度精度得到提高。

公开(公告)号：US07893402B2

公开(公告)日：2011-02-22

申请号：US12052267

申请日：2008-03-20

申请人： Ian Sanders ,  Gökhan Baykut ,  Jochen Franzen

发明人： Ian Sanders ,  Gökhan Baykut ,  Jochen Franzen

IPC分类号： B01D59/44

CPC分类号： H01J49/004 ,  G01N27/622

摘要： The mobility of mass-selected ions in gases is measured at pressures of a few hectopascal by selecting the ions under investigation in a quadrupole filter according to their mass-to-charge ratio m/z, measuring their mobility in a drift region at a pressure of a few hundred Pascal under the influence of a DC electric field and then filtering the measured ions by means of a quadrupole field in order to eliminate, or detect changes in, the mass-to-charge ratio. Several embodiments for the drift region are disclosed, in which the ions are kept in the axis of the drift region by RF fields. As these drift regions can also be utilized for a collision-induced decomposition of the ions, the device can additionally be used as a so-called triple quadrupole mass spectrometer.

摘要翻译： 质量选择的离子在气体中的迁移率通过在四极滤波器中根据其质荷比m / z选择正在研究的离子来测量几何百帕斯卡的压力，测量它们在压力下的漂移区域中的迁移率 在直流电场的影响下，几百帕斯卡，然后通过四极场过滤测量的离子，以消除或检测质荷比的变化。 公开了漂移区的几个实施例，其中通过RF场将离子保持在漂移区的轴上。 由于这些漂移区域也可以用于离子的碰撞诱导分解，因此该装置可另外用作所谓的三重四极杆质谱仪。