公开(公告)号：US5886345A

公开(公告)日：1999-03-23

申请号：US918087

申请日：1997-08-25

申请人： Claus Koster ,  Jochen Franzen ,  Armin Holle

发明人： Claus Koster ,  Jochen Franzen ,  Armin Holle

IPC分类号： H01J49/16 ,  H01J49/40

CPC分类号： H01J49/40 ,  H01J49/0009

摘要： The invention relates to the exact mass determination of analyte ions in time-of-flight mass spectrometers with ionization of analyte substances on sample supports by matrix-assisted laser desorption (MALDI), and with an improvement in mass resolution by delayed ion acceleration in the field between the sample support and an intermediate electrode. It particularly relates to methods for subsequent correction of the flight time values if, during the scan, an incorrect adjustment of the distance from the sample support to the nearest acceleration electrode has occurred.The invention obtains a correction parameter for the flight times of all ions in the spectrum from an internal reference substance and corrects all flight times using a quadratic correction equation, before using the calibrated mass scale for the calculation of the exact masses. The quadratic correction equation contains a control parameter which multiplicatively affects both the linear and quadratic correction term. If no better suitable reference ions are available, oligomeric ions from the matrix of the MALDI method may be used as reference ions. The method can be applied regardless of adjustment in the optimum focus range before measurement of the spectrum, if the adjustments were made in a particular manner.

摘要翻译： 本发明涉及通过基质辅助激光解吸（MALDI）离子化样品载体上分析物质离子化飞行时间质谱仪中的分析物离子的精确质量测定，并且通过延迟离子加速在质量分辨率方面得到改善 样品支撑体和中间电极之间。 特别涉及用于随后校正飞行时间值的方法，如果在扫描期间，已经发生从样品支架到最近的加速电极的距离的不正确调整。 本发明从内部参考物质获得光谱中所有离子的飞行时间的校正参数，并在使用校准的质量标度计算精确质量之前，使用二次校正方程校正所有飞行时间。 二次校正方程包含一个对线性和二次校正项有乘法影响的控制参数。 如果没有更好的合适的参考离子可用，则可以使用来自MALDI方法的基质的低聚离子作为参考离子。 如果以特定的方式进行调整，则可以应用该方法而不考虑在光谱测量之前的最佳对焦范围内的调整。

公开(公告)号：US5818055A

公开(公告)日：1998-10-06

申请号：US891116

申请日：1997-07-10

申请人： Jochen Franzen

发明人： Jochen Franzen

IPC分类号： H01J49/04 ,  H01J49/42

CPC分类号： H01J49/065 ,  H01J49/424

摘要： An ion trap consists of separating the ions into ion packages within an electrical travelling wave field operated at the frequency of the drive voltage for the ion trap, or at an integral fraction of the same, transporting the ion packages by the travelling wave field to the ion trap, and injecting the ion packages into the ion trap with a favorably selected velocity and at the correct point in time. A slowing-down path at the end of the travelling field allows ions of a greater mass to be injected somewhat earlier than light ions, whereby the simultaneous capture of ions of different masses becomes more favorable.

摘要翻译： 离子阱包括将离子分离成在以离子阱的驱动电压的频率操作的电行波中，或者以其整数分数运行的离子包，将离子包通过行波场输送到 离子阱，并且以适当选择的速度和在正确的时间点将离子包注入离子阱。 在行进末端的减速路径允许比轻离子稍早地注入更大质量的离子，由此同时捕获不同质量的离子变得更有利。

公开(公告)号：US5742049A

公开(公告)日：1998-04-21

申请号：US618843

申请日：1996-03-20

申请人： Armin Holle ,  Claus Koster ,  Jochen Franzen

发明人： Armin Holle ,  Claus Koster ,  Jochen Franzen

IPC分类号： H01J49/40 ,  B01D59/44 ,  H01J49/00

CPC分类号： H01J49/164 ,  H01J49/067 ,  H01J49/403

摘要： The invention relates to the use of a time-of-flight mass spectrometer to analyze substance molecules which are ionized by laser desorption, particularly by matrix-assisted laser desorption (MALDI). In detail it relates to the process for improving mass resolution by the known method of delayed acceleration (sometimes called delayed extraction) of the ions, and devices for the performance of this method. The invention consists of using an optical device with gridless apertures for the acceleration of the ions and refocusing the ion beam divergence due to the lens effect of the apertures, by means of a lens arrangement in the drift region of the time-of-flight spectrometer. For laser light pulses, illumination, and observation, there are further lateral holes in the electrodes of the optical device.

摘要翻译： 本发明涉及使用飞行时间质谱仪来分析通过激光解吸电离的物质分子，特别是通过基质辅助激光解吸（MALDI）。 具体而言，涉及通过已知的离子加速（有时称为延迟提取）方法提高质量分辨率的方法以及用于执行该方法的装置。 本发明包括使用具有无栅隙的光学装置用于加速离子，并通过在飞行时间谱仪的漂移区域中的透镜布置来重新聚焦由于孔的透镜效应引起的离子束发散 。 对于激光脉冲，照明和观察，光学装置的电极中存在另外的侧孔。

公开(公告)号：US5708268A

公开(公告)日：1998-01-13

申请号：US644044

申请日：1996-05-09

申请人： Jochen Franzen

发明人： Jochen Franzen

IPC分类号： H01J49/04 ,  H01J49/42 ,  B01D59/44 ,  H01J37/10 ,  H01J49/00

CPC分类号： H01J49/063

摘要： The invention relates to methods and devices for the efficient and loss-free transfer of ions in moderate vacuum from a first location (a source) to a second location (a user). The invention consists of an arrangement, reaching from the first location to the second, of five pole rods (a pentapole) to which a five-phase radio frequency (RF) voltage is applied.

摘要翻译： 本发明涉及用于在中等真空中从第一位置（源）到第二位置（用户）有效和无损地转移离子的方法和装置。 本发明包括从第一位置到第二位置施加五相射频（RF）电压的五极杆（五极）的布置。

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：US5521379A

公开(公告)日：1996-05-28

申请号：US277666

申请日：1994-07-20

申请人： Jochen Franzen ,  Reemt-Holger Gabling

发明人： Jochen Franzen ,  Reemt-Holger Gabling

IPC分类号： B01J19/08 ,  H01J49/42

CPC分类号： H01J49/428 ,  B01J19/087 ,  H01J49/145 ,  H01J49/4295

摘要： A method is disclosed for chemical ionization of the molecules of an analysis gas or analysis gas mixture or for studying ion-molecule reactions in ion traps. Specifically, by superposing a quadrupole field with a dipolar introduced frequency mixture in which there are accurately selected frequency gaps in the ionization phase of the analysis, the only ions which are stored are those which are on the selected reaction path of the reactant gas ions for making the proper reactant ions for the desired ion-molecule reaction. All the other ions are eliminated from storage by excitation of their secular oscillations. In a second phase, by switching off the dipolar introduced frequency mixture, all the ions can be stored in a wide range of mass-to-charge ratios, and therefore also the product ions of the desired ion-molecule reactions of the analysis gas. In a third phase the spectrum of the product ions is scanned.

摘要翻译： 公开了用于分析气体或分析气体混合物的分子的化学电离或用于研究离子阱中的离子 - 分子反应的方法。 具体地说，通过将具有偶极引入频率混合的四极场叠加在分析的电离阶段中存在准确选择的频率间隙的情况下，存储的唯一离子是在反应物气体离子的选定反应路径上 使合适的反应物离子进行所需的离子 - 分子反应。 所有其他离子通过其长期振荡的激发从储存中消除。 在第二阶段，通过关闭偶极引入的频率混合物，所有离子可以以宽范围的质荷比存储，因此也可以分析气体所需的离子 - 分子反应的产物离子。 在第三阶段，扫描产物离子的光谱。

公开(公告)号：US5298746A

公开(公告)日：1994-03-29

申请号：US997284

申请日：1992-12-23

申请人： Jochen Franzen ,  Reemt-Holger Gabling

发明人： Jochen Franzen ,  Reemt-Holger Gabling

IPC分类号： H01J49/42

CPC分类号： H01J49/424 ,  H01J49/429

摘要： An improved scanning method used in an ion trap mass spectrometer comprises controlling the amplitude of the excitation RF during the mass scan to produce a smooth, nonlinear, highly suitable function. A smooth function is a function with a steady derivative. According to one embodiment of the invention, the excitation amplitude is set proportionally to the square root of the storage amplitude, thus making the excitation amplitude proportional to the root of the mass number.

摘要翻译： 在离子阱质谱仪中使用的改进的扫描方法包括在质量扫描期间控制激发RF的振幅以产生平滑，非线性，高度适合的功能。 平滑函数是具有稳定导数的函数。 根据本发明的一个实施例，激励振幅与存储幅度的平方根成比例地设定，从而使激励振幅与质量数的根成正比。

公开(公告)号：US4259572A

公开(公告)日：1981-03-31

申请号：US39478

申请日：1979-05-16

申请人： Curt Brunnee ,  Jochen Franzen ,  Stefan Meier

发明人： Curt Brunnee ,  Jochen Franzen ,  Stefan Meier

IPC分类号： G01N27/68 ,  G01N30/02 ,  G01N30/84 ,  H01J49/04 ,  H01J49/14 ,  H05H3/02 ,  H01J27/00 ,  B01D59/44

CPC分类号： H01J49/0431 ,  G01N27/68 ,  H01J49/049 ,  H01J49/142 ,  H05H3/02 ,  G01N2030/027 ,  G01N2030/8417 ,  G01N35/00009

摘要： Organic samples from a liquid chromatograph are deposited on a conveyor belt which transports them into a vacuum chamber at the entry end of a mass spectrometer. The samples are ionized directly on the belt by particle bombardment or by means of a laser beam. Ionization is enhanced by applying an oxide layer to the belt, by neutralizing the image force, and by vaporizing alkali atoms on the belt to reduce the ionization potential.

摘要翻译： 来自液相色谱仪的有机样品沉积在传送带上，将其输送到质谱仪入口端的真空室中。 通过粒子轰击或通过激光束将样品直接电离在带上。 通过将氧化层施加到带上，通过中和图像力以及通过汽化带上的碱原子来降低电离电位来提高电离。

公开(公告)号：US08410429B2

公开(公告)日：2013-04-02

申请号：US13017803

申请日：2011-01-31

申请人： Jochen Franzen ,  Gökhan Baykut ,  Oliver Räther ,  Carsten Stoermer ,  Evgenij Nikolaev

发明人： Jochen Franzen ,  Gökhan Baykut ,  Oliver Räther ,  Carsten Stoermer ,  Evgenij Nikolaev

IPC分类号： H01J49/06 ,  H01J49/36

CPC分类号： H01J49/4205 ,  H01J49/062

摘要： An ion cell having an axis includes a sheath of individual electrodes that extends along the axis and defines an internal volume. Adjacent individual electrodes are electrically insulated from each other. The individual electrodes each receive a DC potential and RF voltage. At least some of the individual electrodes have a width that varies in the axial direction such that an electrical effect on an axis potential varies along the axis of the ion cell.

摘要翻译： 具有轴的离子电池包括沿着轴线延伸并且限定内部体积的各个电极的护套。 相邻的单个电极彼此电绝缘。 各个电极各自接收DC电位和RF电压。 单个电极中的至少一些具有在轴向上变化的宽度，使得轴电位上的电效应沿离子电池的轴线变化。

公开(公告)号：US08368012B2

公开(公告)日：2013-02-05

申请号：US12699550

申请日：2010-02-03

申请人： Evgenij Nikolaev ,  Jochen Franzen

发明人： Evgenij Nikolaev ,  Jochen Franzen

IPC分类号： H01J49/10 ,  H01J27/02 ,  H01J3/14

CPC分类号： H01J37/248 ,  H01J49/062 ,  H01J49/165 ,  H01J2237/03

摘要： Charged spray droplets are guided in a pseudopotential distribution generated by audio frequency voltages at electrodes of a guiding device, focusing the spray droplets toward the axis. An axial electric field profile and an axial flow profile of a drying gas in the guiding device allow the drift of different-sized droplets to be controlled in the longitudinal direction of the guiding device, so that the droplets are roughly equal in size when they leave the guiding device and finally dry up shortly after leaving. As a result, the ions are formed in a relatively small spatial region. Electrostatic potentials guide the analyte ions from this small spatial region to the entrance aperture of the inlet capillary; during this process, very light ions, especially protons and water-proton complexes, can be filtered out by a mobility filter.

摘要翻译： 带电喷雾液滴由引导装置的电极处的音频电压产生的赝势分布引导，将喷雾液滴聚焦到轴上。 引导装置中的干燥气体的轴向电场分布和轴向流动分布允许不同尺寸的液滴在引导装置的纵向方向上的漂移被控制，使得当它们离开时液滴大小相当大小 引导装置，最后在离开后立即干燥。 结果，离子形成在较小的空间区域。 静电势将分析离子从该小空间区域引导到入口毛细管的入口孔; 在此过程中，非常轻的离子，特别是质子和水 - 质子复合物可以通过迁移率过滤器过滤掉。