公开(公告)号：US4213557A

公开(公告)日：1980-07-22

申请号：US935132

申请日：1978-08-21

Applicant: Jochen Franzen ,  Gerhard Weiss

Inventor： Jochen Franzen ,  Gerhard Weiss

IPC: H01J49/42 ,  B23K1/02 ,  C03B23/04

CPC classification number: H01J49/4215 ,  H01J49/4255 ,  Y10S228/903

Abstract: A method for producing a highly precise and inherently stable analyzer system for a multipole mass filter, wherein a tube of material that is electrically poorly conductive and thermally softenable is put over a core which is precise in size, has a higher expansion coefficient and has parallel grooves. The tube material is joined to the grooves of the core by heating and, subsequently, after cooling for the purposes of solidifying, is removed from the core with the impressed tube indentations. Before the tube is heated, layers of electrically higher conductive metallic components, which can be easily connected to the softenable tube material, are applied between the core and the tube in the region of the grooves. The layer material is connected to the tube material when the tube is softened and joined to the grooves of the tube. When removing the tube that has been shaped in this manner, the layers connected to the impressed tube indentations are also removed from the core. An analyzer system produced according to the inventive method is also disclosed.

Abstract translation: 一种用于制造用于多极质量过滤器的高精度和固有稳定的分析仪系统的方法，其中导电性差且可热软化的材料管放置在尺寸精确的芯上，具有较高的膨胀系数并具有平行 凹槽 管材通过加热连接到芯的凹槽，并且随后在用于固化的目的的冷却之后，用压入管凹陷从芯中移除。 在管被加热之前，可以容易地连接到可软化管材料的电性较高的导电金属部件的层在槽的区域中被施加在芯和管之间。 当管软化并连接到管的凹槽时，层材料连接到管材料。 当以这种方式去除已经成型的管时，连接到印刷管凹口的层也从芯中去除。 还公开了根据本发明方法制造的分析仪系统。

公开(公告)号：US08912485B2

公开(公告)日：2014-12-16

申请号：US13103672

申请日：2011-05-09

Applicant: Thomas Maier ,  Jochen Franzen

Inventor： Thomas Maier ,  Jochen Franzen

IPC: H01J49/00 ,  H01J49/16 ,  H01J49/40

CPC classification number: H01J49/0027 ,  H01J49/164 ,  H01J49/40

Abstract: 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.

Abstract translation: 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提高重现性，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：US08704173B2

公开(公告)日：2014-04-22

申请号：US13499817

申请日：2010-09-17

Applicant: Evgenij Nikolaev ,  Ivan Boldin ,  Jochen Franzen

Inventor： Evgenij Nikolaev ,  Ivan Boldin ,  Jochen Franzen

IPC: H01J49/20 ,  H01J49/26 ,  H01J49/28

CPC classification number: H01J49/38

Abstract: Devices and methods for the acquisition of mass spectra with very high mass resolution in ion cyclotron resonance mass spectrometers include cylindrical ICR measuring cells with special electrode geometries to generate harmonic trapping potentials for orbiting ions. The sheath of the cylindrical cell is divided by longitudinal gaps into a multitude of sheath electrodes, which either have to carry layers with resistance profiles able to generate parabolic voltage profiles along the sheath electrodes, or which form sheath electrodes of varying width by parabolic gaps. Orbiting ions of a given mass m/z oscillate harmonically in an axial direction with the same frequency, independent of the radius of their orbit and their oscillation amplitude. Ideally, the cylinders are closed by endcaps with rotationally hyperbolic form, divided into partial electrodes. The ions are excited by dipolar excitation fields. The orbiting ion clouds are kept together for much longer periods than was possible hitherto.

Abstract translation: 用于在离子回旋共振质谱仪中以非常高的质量分辨率采集质谱的装置和方法包括具有特殊电极几何形状的圆柱形ICR测量单元，以产生轨道离子的谐波陷阱电位。 圆柱形电池的护套由纵向间隙分成多个护套电极，这些护套电极必须承载具有能够沿着护套电极产生抛物线电压分布的电阻分布的层，或者通过抛物线间隙形成具有不同宽度的护套电极。 给定质量m / z的轨道离子在轴向方向上以相同的频率谐振振荡，与轨道的半径和振荡幅度无关。 理想情况下，气缸由具有旋转双曲线形式的端盖封闭，分成部分电极。 离子由偶极激发场激发。 轨道离子云保持在一段比以前更长的时间。

公开(公告)号：US08648298B2

公开(公告)日：2014-02-11

申请号：US12633421

申请日：2009-12-08

Applicant: Jochen Franzen

Inventor： Jochen Franzen

IPC: H01J49/00

CPC classification number: H01J49/38

Abstract: In an ion cyclotron resonance mass spectrometer ions are excited into cyclotron orbits by an alternating current excitation signal having a nonlinear function of the excitation frequency vs. time in a “chirp.” Such an excitation signal produces transients which have no pronounced beats, even if mixtures of many ion species, all having the same mass differences, are present. The dynamic measuring range for the image currents can thus be better utilized. In particular, sum spectra of specified quality can be generated from a significantly smaller number of individual transients, and thus in a significantly shorter measuring time.

Abstract translation: 在离子回旋共振质谱仪中，通过在“啁啾声”中具有激发频率对时间的非线性函数的交流激励信号将离子激发到回旋加速器轨道。 这种激发信号产生没有显着节拍的瞬变，即使存在所有具有相同质量差异的许多离子物质的混合物。 因此可以更好地利用图像电流的动态测量范围。 特别地，可以从显着较小数量的单个瞬变产生特定质量的和光谱，并且因此在显着较短的测量时间内产生。

公开(公告)号：US08624180B2

公开(公告)日：2014-01-07

申请号：US13094146

申请日：2011-04-26

Applicant: Melvin Andrew Park ,  Jochen Franzen

Inventor： Melvin Andrew Park ,  Jochen Franzen

IPC: H01J49/00

CPC classification number: G01N27/626

Abstract: In an ion mobility spectrometer in which a gas pushes ions along a spectrometer axis against and over an electrical field barrier, the electric field barrier is generated with a plateau of slightly increasing height along the axis of the spectrometer. Alternately, the electric filed barrier may have a plateau with constant height, but the gas flow decreases in velocity along the axis of the spectrometer in the vicinity of the plateau.

Abstract translation: 在离子迁移谱仪中，其中气体沿着光谱仪轴线推动离子抵抗和超过电场屏障，电场屏障是沿着光谱仪轴线的高度稍微增加的高原产生的。 或者，电场屏障可以具有恒定高度的平台，但气流在平台附近沿着光谱仪的轴线的速度减小。

公开(公告)号：US08581179B2

公开(公告)日：2013-11-12

申请号：US12708010

申请日：2010-02-18

Applicant: Jochen Franzen

Inventor： Jochen Franzen

IPC: H01J49/40 ,  H01J49/04

CPC classification number: H01J49/164 ,  G01N33/6851 ,  H01J49/0045

Abstract: In a mass spectrometer, sample ions are produced by using matrix assisted laser desorption with a matrix substance that supports spontaneous, non-ergodic ISD fragmentation and a laser light source with nanosecond light pulses and a multiple spot beam profile. A plurality of individual time-of-flight spectra are recorded from the resulting ions in such a way that amplification of ion signals in the mass spectrometer detector is initially reduced so that only ions with masses near a mass range limit are initially recorded. During the repeated acquisitions of the individual time-of-flight spectra, both the detector amplification and the mass range limit are increased. By these methods, it is possible to evaluate c and z fragment ions in lower mass ranges and to directly read N-terminal sequences from near terminus up to 80 amino acids and beyond, and C-terminal sequences up to more than 60 amino acids.

Abstract translation: 在质谱仪中，通过使用支持自发的，非遍历的ISD碎片的基质物质和具有纳秒光脉冲的激光光源和多点光束轮廓的矩阵辅助激光解吸来产生样品离子。 从所得到的离子记录多个单独的飞行时间频谱，使得质谱仪检测器中的离子信号的放大初始地减少，使得只有最初记录质量接近质量范围极限的离子。 在重复采集单个飞行时间光谱期间，检测器放大和质量范围极限都增加。 通过这些方法，可以评估较低质量范围内的c和z片段离子，并直接从近端直到80个氨基酸及其以外的N末端序列，以及直到超过60个氨基酸的C-末端序列。

公开(公告)号：US08580535B2

公开(公告)日：2013-11-12

申请号：US13523167

申请日：2012-06-14

Applicant: Vadim Markovich Govorun ,  Jochen Franzen

Inventor： Vadim Markovich Govorun ,  Jochen Franzen

IPC: C12Q1/04

CPC classification number: G01N33/6851 ,  C12Q1/18

Abstract: 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.

公开(公告)号：US08513599B2

公开(公告)日：2013-08-20

申请号：US12857161

申请日：2010-08-16

Applicant: Jochen Franzen ,  Claus Köster

Inventor： Jochen Franzen ,  Claus Köster

IPC: H01J49/26

CPC classification number: H01J49/062 ,  H01J49/0445

Abstract: Charged droplets are guided along a defined path from a droplet source to a droplet sink. A focusing pseudopotential distribution generated by audio frequencies on electrodes of a guiding device guide the charged droplets from the droplet source to the droplet sink with low loss. The droplets can be driven along the droplet guide by a gas flow, an axial electric field or a combination of both. For example, charged droplets from a spray capillary of an electrospray ion source at atmospheric pressure may be introduced into the inlet capillary leading to the vacuum system of ion analyzers, a procedure similar to that used up to now in nanoelectrospraying, but with substantially higher flow rates. In the guiding device, the droplets can be manipulated in different ways, for example evaporated down to a desired size. The introduction of small droplets into gas-aspirating capillaries is of interest because it is possible to keep the droplets on axis by Bernoulli focusing and to guide them in large quantities and with low loss through the capillary. The ability to guide the droplets makes it also possible to install a segmented inlet capillary with intermediate pumping, which allows pumping capacity to be saved. Advantageously, the sensitivity of ion analyzers such as mass spectrometers or ion mobility spectrometers by at least one order of magnitude.

Abstract translation: 带电液滴沿着从液滴源到液滴槽的限定路径被引导。 由引导装置的电极上的音频产生的聚焦伪势分布将带电液滴从液滴源引导到具有低损耗的液滴槽。 液滴可以通过气流，轴向电场或两者的组合沿液滴引导件驱动。 例如，在大气压下来自电喷雾离子源的喷雾毛细管的带电液滴可以引入入口毛细管中，导入离子分析仪的真空系统，该方法与迄今为止在纳电电喷雾中使用的方法类似，但具有显着更高的流动 价格。 在引导装置中，液滴可以以不同的方式进行操作，例如蒸发到所需尺寸。 将小液滴引入吸气毛细管是令人感兴趣的，因为可以通过伯努利聚焦将液滴保持在轴上，并且通过毛细管大量引导并以低损耗引导。 引导液滴的能力使得还可以安装具有中间泵送的分段入口毛细管，这允许节省泵送能力。 有利地，诸如质谱仪或离子迁移谱仪的离子分析仪的灵敏度至少有一个数量级。

公开(公告)号：US08481928B2

公开(公告)日：2013-07-09

申请号：US12862299

申请日：2010-08-24

Applicant: Jochen Franzen

Inventor： Jochen Franzen

IPC: H01J49/26

CPC classification number: H01J49/0422

Abstract: Ions entrained in a gas are transported into the vacuum system of an ion user, such as a mass spectrometer, from an ion source located outside the vacuum. The gas and ions pass through a nozzle that connects the ion source to the vacuum system and is shaped to form a supersonic gas jet in a first vacuum chamber of the vacuum system. In the first vacuum chamber, ions entrained in the supersonic gas jet are extracted electrically or magnetically and are collected, for example, by an RF ion funnel and transmitted to the ion user. The supersonic gas jet travels on and, after passing through the first vacuum chamber, the supersonic gas jet is directed into a separate pump chamber out of which the gas is pumped.

Abstract translation: 携带在气体中的离子从位于真空外部的离子源转移到离子用户（例如质谱仪）的真空系统中。 气体和离子通过将离子源连接到真空系统的喷嘴，并被成形为在真空系统的第一真空室中形成超音速气体射流。 在第一真空室中，夹带在超声波气体射流中的离子被电或磁性地提取，并且例如通过RF离子漏斗收集并传输给离子用户。 超音速气体射流在通过第一真空室之后行进，超音速气体射流被引导到单独的泵室中，气体被泵送。

公开(公告)号：US08481927B2

公开(公告)日：2013-07-09

申请号：US12853637

申请日：2010-08-10

Applicant: Jochen Franzen ,  Thorsten Benter ,  Hendrik Kersten ,  Matthias Lorenz ,  Klaus J. Brockmann

Inventor： Jochen Franzen ,  Thorsten Benter ,  Hendrik Kersten ,  Matthias Lorenz ,  Klaus J. Brockmann

IPC: G21K5/04 ,  H01J49/26

CPC classification number: H01J49/0431 ,  Y10T436/25

Abstract: Gaseous analyte molecules are ionized at atmospheric pressure and provided to an inlet capillary of an ion spectrometer vacuum system by passing the ions through a reaction tube that ends in a conical intermediate piece for a gastight and smooth transition into the inlet capillary. The reaction tube is shaped so that the atmospheric pressure gas stream passing therethrough form the entrance of the tune to the intermediate piece is stably laminar. Analyte molecules from gas chromatographs, spray devices or vaporization devices can be introduced into the entrance of the reaction tube and ionized within the tube by single- or multi-photon ionization, by chemical ionization, by reactant ions or by physical ionization. For single- or multi-photon ionization, a beam from a laser can be passed axially down the reaction tube. Reactant ions can be produced by any means outside of the reaction tube and mixed with the analyte molecules within the tube.

Abstract translation: 气态分析物分子在大气压下离子化，并通过使离子通过端接在锥形中间件中的反应管提供给离子光谱仪真空系统的入口毛细管，以便气密和平滑过渡到入口毛细管。 反应管成形为使得通过其的大气压力气流形成曲调到中间件的入口是稳定的层流的。 来自气相色谱仪，喷雾装置或蒸发装置的分析物分子可以通过单光子或多光子电离，通过化学电离，反应物离子或物理电离引入反应管的入口并离子化。 对于单光子或多光子电离，来自激光束的光束可以沿着反射管轴向通过。 反应物离子可以通过反应管外的任何方式产生并与管内的分析物分子混合。