公开(公告)号：US5910656A

公开(公告)日：1999-06-08

申请号：US911150

申请日：1997-08-14

申请人： Claus Koster ,  Armin Holle ,  Jochen Franzen

发明人： Claus Koster ,  Armin Holle ,  Jochen Franzen

IPC分类号： H01J49/40 ,  H01J49/04

CPC分类号： H01J49/0409

摘要： A time-of-flight mass spectrometers, in which the ions are generated by ionization of analyte substances on a sample support, by matrix-assisted laser desorption (MALDI). The time-of-flight mass spectrometer consists of using space-adjusting actuators to set the spacing of the sample support from the nearest acceleration electrode so that the flight time of ions of a reference substance prescribed by the calibration can be precisely adjusted. Due to this adjustment of the spacing, a once only calibration of the relationship between the flight time and mass (i.e. the mass scale) may be constantly retained.

摘要翻译： 飞行时间质谱仪通过基质辅助激光解吸（MALDI）通过电离样品载体上的分析物质产生离子。 飞行时间质谱仪包括使用空间调节执行器来设置样品支架与最近加速电极的间距，从而可以精确调整校准所规定的参比物质的离子飞行时间。 由于间隔的这种调整，可以不断地保持飞行时间和质量之间的关系（即质量标度）的一次仅校准。

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：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：US5654545A

公开(公告)日：1997-08-05

申请号：US627370

申请日：1996-04-04

申请人： Armin Holle ,  Claus Koster ,  Jochen Franzen

发明人： Armin Holle ,  Claus Koster ,  Jochen Franzen

IPC分类号： H01J49/40

CPC分类号： H01J49/405 ,  H01J49/403

摘要： A method for the high resolution analysis of analyte ions in a time-of-flight mass spectrometer. The method consists of the generation of an intermediate time-focus plane for ions of a certain mass at a location between an ion source and an ion reflector, and then using the ion reflector to temporally focus the ions of equal mass and differing velocities which pass this plane at the same time onto a detector. For time-of-flight mass spectrometers with an ion selector, the ion selector is particularly favorable location for this intermediate plane with time focus; and with a collision cell for the collision fragmentation of the ions, the collision cell is a particularly favorable location.

摘要翻译： 在飞行时间质谱仪中分析离子的高分辨率分析方法。 该方法包括在离子源和离子反射器之间的位置处产生用于一定质量的离子的中间时间聚焦平面，然后使用离子反射器来时间地聚焦通过的等质量和不同速度的离子 这个飞机同时在一个探测器上。 对于使用离子选择器的飞行时间质谱仪，离子选择器对于具有时间聚焦的中间平面是特别有利的位置; 并且与用于离子的碰撞破碎的碰撞电池一起，碰撞电池是特别有利的位置。

公开(公告)号：US5641959A

公开(公告)日：1997-06-24

申请号：US619005

申请日：1996-03-21

申请人： Armin Holle ,  Claus Koster ,  Jochen Franzen

发明人： Armin Holle ,  Claus Koster ,  Jochen Franzen

IPC分类号： H01J49/40

CPC分类号： H01J49/164 ,  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 of the ions in the space in front of the sample support plate. The invention consists of switching the potential of an intermediate electrode which is located at a short distance in front of the sample support plate, instead of switching the potential of the sample support plate itself.

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）。 详细地涉及通过已知的样品支撑板前面的空间中的离子的延迟加速方法来提高质量分辨率的方法。 本发明包括切换位于样品支撑板前方短距离的中间电极的电位，而不是切换样品支撑板本身的电位。

公开(公告)号：US5841136A

公开(公告)日：1998-11-24

申请号：US890981

申请日：1997-07-10

申请人： Armin Holle ,  Claus Koster ,  Jens Rebettge

发明人： Armin Holle ,  Claus Koster ,  Jens Rebettge

IPC分类号： H01J49/04 ,  H01J47/04

CPC分类号： H01J49/0418 ,  H01J49/0495

摘要： A system and a method for the introduction of sample supports, which hold large numbers of analysis samples, into the ion source region of a mass spectrometer. The sample supports are especially intended for the ionization method using matrix-assisted desorption through laser bombardment (MALDI). The system consists of using an evacuable, sealable and removable cassette which, instead of using a through-passage lock chamber with two lock valves, can be attached in a simple manner to the entrance opening for the ion source of the mass spectrometer. Only the entrance opening has a lock valve, and the expensive second lock valve in the lock chamber is no longer needed. The cassette can also be used for protected transport and for storage of the sample supports, and in particular for storage of the samples under protective gas or vacuum.

摘要翻译： 将具有大量分析样品的样品载体引入质谱仪的离子源区域的系统和方法。 样品载体特别适用于通过激光轰击（MALDI）使用基质辅助解吸的电离方法。 该系统包括使用可抽空，可密封和可拆卸的盒，其可以以简单的方式附接到质谱仪的离子源的入口，而不是使用具有两个锁定阀的通道锁定室。 只有入口具有锁定阀，并且不再需要锁定室中昂贵的第二锁定阀。 盒还可以用于保护运输和储存样品支架，特别是用于在保护气体或真空下储存样品。

公开(公告)号：US5869830A

公开(公告)日：1999-02-09

申请号：US914695

申请日：1997-08-19

申请人： Jochen Franzen ,  Claus Koster

发明人： Jochen Franzen ,  Claus Koster

IPC分类号： H01J49/16 ,  H01J49/40

CPC分类号： H01J49/403

摘要： A method relates to exact mass determination of analyte ions in time-of-flight mass spectrometers using an ionization of analyte substances on sample supports by matrix-assisted laser desorption (MALDI), and an improvement in mass resolution by time-delayed ion acceleration in the field between the sample support and an intermediate acceleration electrode. It particularly relates to methods for the stabilization of a once calibrated mass scale when there are unwanted changes in the distance of the sample support from the intermediate acceleration electrode.An unknown change of this distance can be compensated for by a coupled change of both total accelerating voltage and partial acceleration voltage between sample support and intermediate electrode in a simple manner by adjusting the time of flight of ions from a reference substance to the value given by the calibrated mass scale. Oligomeric ions from the matrix of the MALDI method serve very well as reference ions. Furthermore, if the range of optimum focus is shifted by a change in the time delay, the calibrated mass scale can be kept valid for all masses through a simultaneous change of the accelerating voltage.

摘要翻译： 一种方法涉及使用通过基质辅助激光解吸（MALDI）的样品载体上的分析物质离子化的飞行时间质谱仪中的分析物离子的精确质量测定，以及通过时间延迟离子加速的质量分辨率的改善 样品载体和中间加速电极之间的场。 它特别涉及当样品载体与中间加速电极的距离有不希望的变化时稳定一次校准的质量标度的方法。该距离的未知变化可以通过总加速度的耦合变化来补偿 通过调整离子从参考物质的飞行时间到由校正的质量标度给出的值，以简单的方式，在样品载体和中间电极之间的电压和部分加速电压。 来自MALDI方法的基质的低聚离子作为参考离子起很好的作用。 此外，如果通过时间延迟的变化来移动最佳焦点的范围，则通过同时改变加速电压，校准的质量标度可以保持对所有质量有效。

公开(公告)号：US20100301204A1

公开(公告)日：2010-12-02

申请号：US12767273

申请日：2010-04-26

申请人： Claus Koster ,  Jochen Franzen

发明人： Claus Koster ,  Jochen Franzen

IPC分类号： B01D59/44 ,  H01J49/00

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：US06465778B1

公开(公告)日：2002-10-15

申请号：US09364244

申请日：1999-07-29

申请人： Claus Koster ,  Jochen Franzen

发明人： Claus Koster ,  Jochen Franzen

IPC分类号： H01J4404

CPC分类号： H01J49/164 ,  G01N1/22

摘要： The invention relates to ionization with low fragmentation and adduct formation, of high-molecular analyte molecules, particularly of large biopolymers, by matrix-assisted laser desorption (MALDI) from liquid matrices for mass-spectrometric analysis of the resulting ions, particularly for determination of their molecular weight. The invention uses liquids as matrix substances with very low vapor pressures from the group of minimally trihydroxylic alcohols with at least one ether bond (ether polyols or polyether polyols). These can be used advantageously for energy absorption and ionization by infrared lasers (IR-MALDI), however other lasers, such as conventional. UV lasers, can be used for other wavebands by the addition of light-absorbing compounds.

摘要翻译： 本发明涉及通过基质辅助激光解吸（MALDI）从液体基质中获得高分子分析物分子，特别是大生物聚合物的低分裂和加合物形成的离子，用于所得离子的质谱分析，特别是用于确定 它们的分子量。 本发明使用液体作为具有非常低蒸气压的基质物质，其具有至少一个醚键的最小三羟基醇（醚多元醇或聚醚多元醇）。 这些可以有利地用于通过红外激光器（IR-MALDI）的能量吸收和电离，然而其他激光器，例如常规的。 UV激光器可以通过添加光吸收化合物用于其他波段。

公开(公告)号：US5828063A

公开(公告)日：1998-10-27

申请号：US832469

申请日：1997-04-02

申请人： Claus Koster ,  Jochen Franzen

发明人： Claus Koster ,  Jochen Franzen

IPC分类号： H01J49/16 ,  H01J49/10

CPC分类号： H01J49/164

摘要： A method for matrix-assisted ionizing laser desorption of large analyte molecules (MALDI) in a vacuum for the generation of ions for mass spectrometric investigation of the analyte substance is provided. The matrix substance for matrix-assisted ionizing laser desorption is formed from at least two different components. One of the components is very adsorptive, as well as being decomposable thermolytically into small fractions. Additional matrix components are selected for protonation of the analyte molecules. In particular, a thin layer of nitrocellulose (also called cellulose nitrate) with a protonating substance embedded within it is particularly suitable. This layer, which is insoluble in water, adsorbs large analyte molecules from an aqueous solution at its surface.

摘要翻译： 提供了一种在真空中的大分析物分子（MALDI）的基质辅助电离激光解吸的方法，用于产生离子用于分析物质的质谱研究。 用于基质辅助电离激光解吸的基质物质由至少两种不同的组分形成。 其中一个组分是非常吸附的，以及可热分解成小部分。 选择附加的基质组分用于分析物分子的质子化。 特别地，嵌入其中的质子化物质的硝酸纤维素（也称为硝酸纤维素）的薄层是特别合适的。 这种不溶于水的层在其表面从水溶液中吸收大的分析物分子。