公开(公告)号：US20060063145A1

公开(公告)日：2006-03-23

申请号：US11195365

申请日：2005-08-02

申请人： Detlev Suckau ,  Martin Schurenberg ,  Jochen Franzen

发明人： Detlev Suckau ,  Martin Schurenberg ,  Jochen Franzen

IPC分类号： C12Q1/00 ,  G06F19/00

CPC分类号： G01N33/483 ,  H01J49/0004 ,  Y10T436/24

摘要： The invention relates to the determination and visualization of the spatial distribution of tissue states in histologic tissue sections on the basis of mass spectrometric signals acquired so as to be spatially resolved. The invention provides a method which determines the tissue state for the tissue spots as a state characteristic, which is calculated as a mathematical or logical expression from at least two mass signals of this tissue spot, and which indicates the tissue state as a gray-level or false-color image in one or two dimensions.

摘要翻译： 本发明涉及基于获得的空间分辨的质谱信号来确定和可视化组织组织切片中组织状态的空间分布。 本发明提供了一种方法，其将组织斑点的组织状态确定为状态特征，其从该组织斑点的至少两个质量信号计算为数学或逻辑表达，并且将组织状态指示为灰度级 或一维或二维的假彩色图像。

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：US06949739B2

公开(公告)日：2005-09-27

申请号：US10624913

申请日：2003-07-22

申请人： Jochen Franzen

发明人： Jochen Franzen

IPC分类号： H01J49/00 ,  H01J49/04 ,  H01J49/10 ,  H01J49/16

CPC分类号： H01J49/16

摘要： The invention relates to the feeding of analyte ions, generated at atmospheric pressure, efficiently into the mass spectrometer. The invention provides a lengthy ion mobility drift tube with a focusing electric field inside to guide the ions from an ionization cloud generated at atmospheric pressure towards the entrance opening of the mass spectrometer, and to dry droplets which might occur in the ionization cloud by a hot drying gas flowing through the ion mobility drift tube towards the ionization cloud.

摘要翻译： 本发明涉及在大气压下产生的分析物离子进料到质谱仪中。 本发明提供了一种长时间的离子迁移率漂移管，其内部具有聚焦电场，以引导离子从在大气压下产生的电离云朝向质谱仪的入口开口，并且可以通过热量在电离云中发生干燥的液滴 干燥气体流过离子迁移率漂移管朝向电离云。

公开(公告)号：US06861645B2

公开(公告)日：2005-03-01

申请号：US10685332

申请日：2003-10-14

申请人： Jochen Franzen

发明人： Jochen Franzen

IPC分类号： H01J49/02 ,  H01J49/40

CPC分类号： H01J49/401 ,  H01J49/0031

摘要： The invention relates to a time-of-flight mass spectrometer in which a fine beam of ions is injected orthogonally into a fast pulser that pulses the ions from the fine ion beam into the spectrometer's drift region for precise determination of mass. The invention consists in increasing the duty cycle of the ions through the use of a high pulser frequency, recording the data cyclically at the same frequency, and assigning slow ions that are only measured in one of the subsequent cycles to the correct initiating pulse through the form of their lines or line patterns.

摘要翻译： 本发明涉及一种飞行时间质谱仪，其中将精细的离子束正交地注入快速脉冲发生器中，该快速脉冲发生器将离子从精细离子束脉冲进入光谱仪的漂移区域以精确确定质量。 本发明包括通过使用高脉冲发生器频率来增加离子的占空比，以相同的频率周期性地记录数据，以及将仅在随后的周期之一测量的慢离子分配给正确的起始脉冲 他们的线条或线条图案的形式。

公开(公告)号：US06559444B2

公开(公告)日：2003-05-06

申请号：US09801204

申请日：2001-03-07

申请人： Jochen Franzen

发明人： Jochen Franzen

IPC分类号： H01J4926

CPC分类号： H01J49/062 ,  H01J49/004 ,  H01J49/421

摘要： The invention relates to a tandem mass spectrometer and a method for scanning daughter ion spectra which uses a quadrupole mass spectrometer for selection of parent ions and another one for the measurement of the daughter ions. The invention consists of not using a conventional third quadrupole filter as a collision cell for fragmentation of the parent ions but an ion guide system with helically coiled wires, especially in the form of a double helix, in which the ions can be completely decelerated and can be actively fed to the outlet aperture.

摘要翻译： 本发明涉及串联质谱仪和用于扫描子离子光谱的方法，其使用四极质谱仪来选择母离子，另一种用于测量子离子。本发明包括不使用常规的第四四极滤波器 用于分离母体离子的碰撞电池，但是具有螺旋线圈导线的离子导向系统，特别是双螺旋形式，其中离子可以被完全减速并且可以被主动地馈送到出口孔。

公开(公告)号：US06414306B1

公开(公告)日：2002-07-02

申请号：US09632448

申请日：2000-08-04

申请人： Franz-Josef Mayer-Posner ,  Jochen Franzen

发明人： Franz-Josef Mayer-Posner ,  Jochen Franzen

IPC分类号： B01D5944

CPC分类号： H01J49/0418 ,  G01N30/95

摘要： The invention relates to the coupling of thin-layer chromatography with mass spectrometry with ionization of the separated analyte substances by matrix-assisted laser desorption (MALDI). The invention performs thin-layer chromatography (TLC) directly on a contactable, electrically conductive carrier plate which, after generation of small matrix crystals at the surface by suitable application of a matrix solution and drying, can be directly inserted into a mass spectrometer so that the chromatographically separated analyte substances contained in the matrix crystals, can be ionized and analyzed by MALDI mass spectrometry. The invention covers type and shape of the carrier plates and the application procedure of the matrix solution to the carrier plates for MALDI analysis.

摘要翻译： 本发明涉及通过基质辅助激光解吸（MALDI）将薄层色谱与质谱联用分离的分析物质的离子化。本发明直接在可接触的导电载体板上进行薄层色谱（TLC） 其通过适当应用基质溶液和干燥后在表面生成小基体晶体后，可以直接插入质谱仪中，使基质晶体中所含的色谱分离的分析物质能够通过MALDI质量离子化和分析 光谱测定。 本发明涵盖载体板的类型和形状以及基质溶液对载体板的MALDI分析的应用程序。

公开(公告)号：US06300627B1

公开(公告)日：2001-10-09

申请号：US09452641

申请日：1999-12-01

申请人： Claus Köster ,  Armin Holle ,  Jochen Franzen

发明人： Claus Köster ,  Armin Holle ,  Jochen Franzen

IPC分类号： B01D5944

CPC分类号： H01J49/004 ,  H01J49/40

摘要： The invention relates to time-of-flight mass spectrometers for the measurement of daughter ion spectra (also called fragment ion spectra or MS/MS spectra) and corresponding measurement methods. According to the invention, the ions of an ion source are initially accelerated only to an intermediate level of energy, allowing them to decompose at that energy level by metastable decomposition or by collisionally induced fragmentation (CID). The ions are then accelerated in a second step to a high energy level. Light fragment ions gain a higher velocity than heavier fragment ions or non-decomposed parent ions. The spectrum of fragment ions can be detected separated by mass in either linear or reflector mode. An ion selector at the low energy level selects a single type of parent ion in order to avoid superpositions with fragment ions of other parent ions. A particularly preferred embodiment raises the potential of ions, for there second acceleration, during their flight through a small electrically isolated flight path chamber.

摘要翻译： 本发明涉及用于测量子离子谱（也称为碎片离子谱或MS / MS谱）的飞行时间质谱仪和相应的测量方法。根据本发明，离子源的离子最初仅被加速 达到中等水平的能量，允许它们通过亚稳分解或碰撞诱导的分裂（CID）在该能级分解。 然后将离子在第二步骤中加速至高能级。 轻碎片离子比较重的碎片离子或未分解的亲本离子获得更高的速度。 碎片离子的光谱可以通过质量以线性或反射模式进行检测。 低能级的离子选择器选择单一类型的母体离子，以避免与其他母体离子的碎片离子叠加。 特别优选的实施例在通过小的电隔离的飞行路径室飞行时提高了离子的潜力，因为第二加速度。

公开(公告)号：US06288389B1

公开(公告)日：2001-09-11

申请号：US09248131

申请日：1999-02-10

申请人： Jochen Franzen

发明人： Jochen Franzen

IPC分类号： B01D5944

CPC分类号： H01J49/0036

摘要： The invention relates to a method of fast real time evaluation of mass spectra for analytical methods where in tens of thousands of spectra a day the only result to be established is whether previously known mass signals are present or not present. The invention consists of calculating the positions of those signals within the measured raw data of a spectrum (e.g. the time coordinates of a time-of-flight spectrum) from the known masses by an inverted mass calibration curve, and investigating the raw data for the presence of ion current peaks only at these positions. By weighted summation with special weight functions the signal-to-noise ratio can be improved so that even very small signals can be detected reliably. Data evaluation can therefore be reduced to about one microsecond per expected mass on modern computers so even if there is a large number of expected masses the establishing procedure only takes a few milliseconds. Measurement can even be repeated where necessary if, contrary to expectation, no signal is found. This procedure is completely different from the conventional technique: up to now, at the data evaluation stage the ion currents recorded at fixed time intervals are normally first investigated with regard to the presence of ion current peaks, the associated peak times are then converted to masses with the aid of a calibration function, and the data of the mass spectrum are investigated according to the problem involved.

摘要翻译： 本发明涉及用于分析方法的质谱的快速实时评估方法，其中每天数万个光谱中唯一的结果是确定先前已知的质量信号是否存在。 本发明包括通过反向质量校准曲线计算来自已知质量的所测量的原始数据中的那些信号的位置（例如飞行时间频谱的时间坐标），并且调查原始数据 仅在这些位置存在离子电流峰值。 通过具有特殊权重函数的加权求和，可以提高信噪比，从而可以可靠地检测到非常小的信号。 因此，即使有大量的预期质量，建立程序只需要几毫秒，因此数据评估可以在现代计算机上减少到每个预期质量大约一微秒。 如果与预期相反，没有发现信号，甚至可以在必要时重复测量。 该过程与传统技术完全不同：迄今为止，在数据评估阶段，以固定时间间隔记录的离子电流通常首先针对离子电流峰值的存在进行研究，然后将相关峰值时间转换为质量 借助于校准功能，根据所涉及的问题调查质谱数据。

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。