公开(公告)号：US06278111B1

公开(公告)日：2001-08-21

申请号：US09191866

申请日：1998-11-12

申请人： Edward W. Sheehan ,  Ross C. Willoughby ,  Joseph A. Jarrell ,  David M. Strand

发明人： Edward W. Sheehan ,  Ross C. Willoughby ,  Joseph A. Jarrell ,  David M. Strand

IPC分类号： H01J4910

CPC分类号： H01J49/165 ,  H01J49/049

摘要： An improved electrospray (ES) apparatus has a low pressure ES chamber coupled to a desolvation chamber. The desolvation chamber desolvates the incoming analyte ions of the cone-jet with non-conductive energy. The apparatus stabilizes cone-jet formation in the ES chamber. The apparatus receives solvated ions without pressure reduction, produces desolvated ions with non-conductive energy in a low pressure region, and outputs the desolvated ions towards a mass spectrometer as a substantially solvent-free ion beam suitable for mass spectrometer analysis. The apparatus avoids the degree of pressure reduction featured in prior ES techniques.

摘要翻译： 改进的电喷雾（ES）装置具有耦合到去溶剂化室的低压ES室。 去溶剂化室以非导电能量去除锥形喷射流中的进入分析物离子。 该装置稳定了ES室中的锥形喷射形成。 该装置在没有减压的情况下接收溶剂化离子，在低压区域中产生具有非导电能的脱溶离离子，并将解溶离的离子输出到质谱仪，作为适用于质谱分析的基本上无溶剂的离子束。 该装置避免了先前ES技术中特征的减压程度。

公开(公告)号：US07375319B1

公开(公告)日：2008-05-20

申请号：US11500055

申请日：2006-08-07

申请人： Ross C. Willoughby ,  Edward W. Sheehan ,  Craig M. Whitehouse

发明人： Ross C. Willoughby ,  Edward W. Sheehan ,  Craig M. Whitehouse

IPC分类号： H01J49/04

CPC分类号： H01J49/0463 ,  H01J49/145

摘要： Atmospheric pressure, intermediate pressure and vacuum laser desorption ionization methods and ion sources are configured to increase ionization efficiency and the efficiency of transmitting ions to a mass to charge analyzer or ion mobility analyzer. An electric field is applied in the region of a sample target to accumulate ions generated from a local ion source on a solid or liquid phase sample prior to applying a laser desorption pulse. The electric field is changed just prior to or during the desorption laser pulse to promote the desorption of charged species and improve the ionization efficiency of desorbed sample species. After a delay, the electric field may be further changed to optimize focusing and transmission of ions into a mass spectrometer or ion mobility analyzer. Charged species may also be added to the region of the laser desorbed sample plume to promote ion-molecule reactions between the added ions and desorbed neutral sample species, increasing desorbed sample ionization efficiency and/or creating desired production species. The cycling of electric field changes is repeated in a timed sequence with one or more desorption laser pulse occurring per electric field change cycle. Embodiments of the invention comprise atmospheric pressure, intermediate pressure and vacuum pressure laser desorption ionization source methods and devices for increasing the analytical flexibility and improving the sensitivity of mass spectrometric analysis.

摘要翻译： 大气压力，中压和真空激光解吸电离方法和离子源被配置为增加电离效率和将离子传输到质量计量分析器或离子迁移率分析仪的效率。 在样品靶的区域内施加电场，以在施加激光解吸脉冲之前，在固相或液相样品上积聚从局部离子源产生的离子。 电场在解吸激光脉冲之前或期间改变，以促进带电物质的解吸附并提高解吸样品的离子化效率。 延迟后，可以进一步改变电场以优化离子聚焦和传输到质谱仪或离子迁移率分析仪中。 带电物质也可以添加到激光解吸的样品羽毛的区域中，以促进添加的离子和解吸的中性样品物质之间的离子 - 分子反应，增加解吸的样品离子化效率和/或产生所需的生产物质。 以定时序列重复电场变化的循环，每个电场变化周期发生一个或多个解吸激光脉冲。 本发明的实施例包括大气压力，中压和真空压力激光解吸电离源的方法和装置，用于增加分析灵活性并提高质谱分析的灵敏度。

公开(公告)号：US07087898B2

公开(公告)日：2006-08-08

申请号：US10862304

申请日：2004-06-07

申请人： Ross C. Willoughby ,  Edward W. Sheehan ,  Craig M. Whitehouse

发明人： Ross C. Willoughby ,  Edward W. Sheehan ,  Craig M. Whitehouse

IPC分类号： H01J49/04 ,  H01J49/10 ,  H01J49/40

CPC分类号： H01J49/164 ,  H01J49/06

摘要： Atmospheric pressure, intermediate pressure and vacuum laser desorption ionization methods and ion sources are configured to increase ionization efficiency and the efficiency of transmitting ions to a mass to charge analyzer or ion mobility analyzer. An electric field is applied in the region of a sample target to accumulate ions generated from a local ion source on a solid or liquid phase sample prior to applying a laser desorption pulse. The electric field is changed just prior to or during the desorption laser pulse to promote the desorption of charged species and improve the ionization efficiency of desorbed sample species. After a delay, the electric field may be further changed to optimize focusing and transmission of ions into a mass spectrometer or ion mobility analyzer. Charged species may also be added to the region of the laser desorbed sample plume to promote ion-molecule reactions between the added ions and desorbed neutral sample species, increasing desorbed sample ionization efficiency and/or creating desired product ion species. The cycling of electric field changes is repeated in a timed sequence with one or more desorption laser pulse occurring per electric field change cycle. Embodiments of the invention comprise atmospheric pressure, intermediate pressure and vacuum pressure laser desorption ionization source methods and devices for increasing the analytical flexibility and improving the sensitivity of mass spectrometric analysis.

摘要翻译： 大气压力，中压和真空激光解吸电离方法和离子源被配置为增加电离效率和将离子传输到质量计量分析器或离子迁移率分析仪的效率。 在样品靶的区域内施加电场，以在施加激光解吸脉冲之前，在固相或液相样品上积聚从局部离子源产生的离子。 电场在解吸激光脉冲之前或期间改变，以促进带电物质的解吸附并提高解吸样品的离子化效率。 延迟后，可以进一步改变电场以优化离子聚焦和传输到质谱仪或离子迁移率分析仪中。 带电物质也可以加入到激光解吸样品羽流的区域中，以促进添加的离子和解吸的中性样品物质之间的离子 - 分子反应，增加解吸的样品电离效率和/或产生所需的产物离子种类。 以定时序列重复电场变化的循环，每个电场变化周期发生一个或多个解吸激光脉冲。 本发明的实施例包括大气压力，中压和真空压力激光解吸电离源的方法和装置，用于增加分析灵活性并提高质谱分析的灵敏度。

公开(公告)号：US07816646B1

公开(公告)日：2010-10-19

申请号：US12123669

申请日：2008-05-20

申请人： Ross C. Willoughby ,  Edward W. Sheehan ,  Craig M. Whitehouse

发明人： Ross C. Willoughby ,  Edward W. Sheehan ,  Craig M. Whitehouse

IPC分类号： H01J49/04

CPC分类号： H01J49/0463 ,  H01J49/145

摘要： Atmospheric pressure, intermediate pressure and vacuum laser desorption ionization methods and ion sources are configured to increase ionization efficiency and the efficiency of transmitting ions to a mass to charge analyzer or ion mobility analyzer. An electric field is applied in the region of a sample target to accumulate ions generated from a local ion source on a solid or liquid phase sample prior to applying a laser desorption pulse. The electric field is changed just prior to or during the desorption laser pulse to promote the desorption of charged species and improve the ionization efficiency of desorbed sample species. After a delay, the electric field may be further changed to optimize focusing and transmission of ions into a mass spectrometer or ion mobility analyzer. Charged species may also be added to the region of the laser desorbed sample plume to promote ion-molecule reactions between the added ions and desorbed neutral sample species, increasing desorbed sample ionization efficiency and/or creating desired product ion species. The cycling of electric field changes is repeated in a timed sequence with one or more desorption laser pulse occurring per electric field change cycle. Embodiments of the invention comprise atmospheric pressure, intermediate pressure and vacuum pressure laser desorption ionization source methods and devices for increasing the analytical flexibility and improving the sensitivity of mass spectrometric analysis.

摘要翻译： 大气压力，中压和真空激光解吸电离方法和离子源被配置为增加电离效率和将离子传输到质量计量分析器或离子迁移率分析仪的效率。 在样品靶的区域内施加电场，以在施加激光解吸脉冲之前，在固相或液相样品上积聚从局部离子源产生的离子。 电场在解吸激光脉冲之前或期间改变，以促进带电物质的解吸附并提高解吸样品的离子化效率。 延迟后，可以进一步改变电场以优化离子聚焦和传输到质谱仪或离子迁移率分析仪中。 带电物质也可以加入到激光解吸样品羽流的区域中，以促进添加的离子和解吸的中性样品物质之间的离子 - 分子反应，增加脱附的样品电离效率和/或产生所需的产物离子种类。 以定时序列重复电场变化的循环，每个电场变化周期发生一个或多个解吸激光脉冲。 本发明的实施例包括大气压力，中压和真空压力激光解吸电离源的方法和装置，用于增加分析灵活性并提高质谱分析的灵敏度。

公开(公告)号：US08008617B1

公开(公告)日：2011-08-30

申请号：US12344872

申请日：2008-12-29

申请人： John C. Berends, Jr. ,  Timothy P. Karpetsky ,  Ross C. Willoughby ,  Edward W. Sheehan

发明人： John C. Berends, Jr. ,  Timothy P. Karpetsky ,  Ross C. Willoughby ,  Edward W. Sheehan

IPC分类号： B01D59/44

CPC分类号： H01J49/0422

摘要： Ions carried in a flowing gas stream are transferred to another gas stream of different composition or purity through an ion selective aperture communicating between the gas streams. The ion selective aperture is formed of a central layer which has an electrically conductive layer on each of its surfaces. One or more open channels extend through the central layer and surface layers allowing physical movement of ions therethrough under the urging and influence of an electric field created by imposing a voltage differential between the conductive surface layers of the ion selective aperture. The gas flow rates of the different gas streams may be independently varied to allow adjustment of ion concentration and flow rate to meet the needs of the ion destination. This device can control sample ion introduction into gas-phase ion detectors, such as ion mobility analyzers, differential mobility analyzers, mass spectrometers, and combinations thereof.

摘要翻译： 携带在流动气流中的离子通过在气流之间连通的离子选择孔转移到不同组成或纯度的另一种气流中。 离子选择孔由中心层形成，在其每个表面上具有导电层。 在通过在离子选择孔的导电表面层之间施加电压差而产生的电场的推动和影响下，一个或多个开放通道延伸穿过中心层和表面层，允许离子物理移动。 可以独立地改变不同气流的气体流速，以允许调节离子浓度和流速以满足离子目的地的需要。 该装置可以将样品离子引入气相离子检测器，例如离子迁移率分析仪，差速移动分析仪，质谱仪及其组合。

公开(公告)号：US06914243B2

公开(公告)日：2005-07-05

申请号：US10863130

申请日：2004-06-07

申请人： Edward W. Sheehan ,  Ross C. Willoughby

发明人： Edward W. Sheehan ,  Ross C. Willoughby

IPC分类号： B01D20060101 ,  B01D59/44 ,  H01J49/00 ,  H01J49/06 ,  H01J49/10

CPC分类号： H01J49/067 ,  H01J49/0404

摘要： Improvements have been made for collecting, focusing, and directing of ions and/or charged particles generated at atmospheric or near atmospheric pressure sources, such as but not limited to, electrospray; atmospheric pressure discharge ionization, chemical ionization, photoionization, and matrix assisted laser desorption ionization; and inductively coupled plasma ionization. A multiple-aperture laminated structure is place at the interface of two pressure regions. Electric fields geometries and strengths across the laminated structure and diameters of the apertures; all of which act to optimize the transfer of the ions from the higher pressure region into the lower pressure region while reducing the gas-load on the lower pressure region. Embodiments of this invention are methods and devices for improving sensitivity of mass spectrometry when coupled to atmospheric, near atmospheric, or higher pressure ionization sources by reducing the gas-load on the vacuum system.

摘要翻译： 已经改进了在大气压或近大气压源（例如但不限于电喷雾）下产生的离子和/或带电粒子的收集，聚焦和引导; 大气压放电电离，化学电离，光电离和基体辅助激光解吸电离; 和电感耦合等离子体电离。 多孔层叠结构位于两个压力区的界面处。 横跨层叠结构和孔直径的电场几何形状和强度; 所有这些都用于优化离子从较高压力区域转移到较低压力区域，同时降低低压区域上的气体负载。 本发明的实施方案是当通过减少真空系统上的气体负载耦合到大气压，接近大气压或更高压力的电离源时，提高质谱的灵敏度的方法和装置。

公开(公告)号：US07569812B1

公开(公告)日：2009-08-04

申请号：US11544252

申请日：2006-10-07

申请人： Timothy P. Karpetsky ,  John C. Berends, Jr. ,  Edward W. Sheehan ,  Ross C. Willoughby

发明人： Timothy P. Karpetsky ,  John C. Berends, Jr. ,  Edward W. Sheehan ,  Ross C. Willoughby

IPC分类号： B01D59/44 ,  H01J49/00

CPC分类号： H01J49/145 ,  H01J49/0468 ,  H01J49/067

摘要： An improved ion source and means for collecting and focusing dispersed gas-phase ions from a remote reagent chemical ionization source (R2CIS) at atmospheric or intermediate pressure is described. The R2CIS is under electronic control and can produce positive, negative, or positive and negative reagent ions simultaneously. This remote source of reagent ions is separated from a low-field sample ionization region by a stratified array of elements, each element populated with a plurality of openings, wherein DC potentials are applied to each element necessary for transferring reagent ions from the R2CIS into the low-field sample ionization region where the reagent ions react with neutral and/or ionic sample forming sample ionic species. The resulting sample ionic species are then introduced into a mass spectrometer, ion mobility spectrometer or other sensor capable of detecting the sample ions. Embodiments of this invention are methods and devices for improving sensitivity of mass spectrometry when gas and liquid chromatographic separation techniques are coupled to atmospheric and intermediate pressure photo-ionization, chemical ionization, and thermospray ionization sources; and improving the sensitivity of chemical detectors or probes.

摘要翻译： 描述了改进的离子源和用于在大气压或中压下从远程试剂化学电离源（R2CIS）收集和聚焦分散的气相离子的装置。 R2CIS处于电子控制下，可以同时产生正，负或正，负反应离子。 这种远程的试剂离子源通过分层阵列的元件与低场样品电离区域分开，每个元件填充有多个开口，其中DC电位被施加到将试剂离子从R2CIS转移到 低场样品电离区域，其中试剂离子与形成样品离子物质的中性和/或离子样品反应。 然后将所得样品离子物质引入质谱仪，离子迁移谱仪或能够检测样品离子的其他传感器。 本发明的实施例是当气体和液相色谱分离技术耦合到大气和中压光电离，化学电离和热喷射电离源时提高质谱的灵敏度的方法和装置; 并提高化学检测器或探针的灵敏度。

公开(公告)号：US5285064A

公开(公告)日：1994-02-08

申请号：US40073

申请日：1993-03-30

申请人： Ross C. Willoughby

发明人： Ross C. Willoughby

IPC分类号： G01N1/00 ,  G01N30/02 ,  G01N30/30 ,  G01N30/72 ,  H01J49/04

CPC分类号： H01J49/049 ,  H01J49/045 ,  G01N1/22 ,  G01N2030/027 ,  G01N2030/3038 ,  G01N2030/3061 ,  G01N30/7253

摘要： Methods and apparatus for liquid sample introduction into chemical detectors that require the sample to be transformed from a flowing stream into either gaseous or particulate states. The effluent from either a process stream or a liquid chromatograph is nebulized by combined thermal and pneumatic processes within an inner fused silicon capillary tube heated by conduction from a surrounding electrical resistance heated outer capillary tube composed of a pure metal having a comparatively high linear relationship between temperature and electrical resistance to provide a uniform conduction of heat energy to the inner tube to form a well-collimated, partially or completely desolvated aerosol, with the less volatile solute components of the sample stream remaining in the particulate state. The gaseous components of the aerosol are separated from the solvent-depleted solute particles using either cryotrapping or momentum separation. The enriched solute particles are vaporized, ionized, and/or detected by suitable gas-phase or particle detectors. The device is primarily an interface between the liquid chromatograph or process streams and the mass spectrometer.

摘要翻译： 将液体样品引入化学检测器的方法和设备，其需要将样品从流动物流转变为气态或微粒状态。 来自工艺流或液相色谱仪的流出物通过内部熔融硅毛细管内的组合热和气动工艺进行喷雾，所述内部熔融硅毛细管由来自周围的电阻加热的外部毛细管的传导加热，所述外部毛细管由纯金属组成，所述纯金属具有相对较高的线性关系 温度和电阻，以向内管提供均匀的热能传导，以形成准直的，部分或完全脱溶的气溶胶，其中样品流的挥发性较低的溶质组分保持颗粒状态。 气溶胶的气态组分使用低温震荡或动量分离与溶剂不足的溶质颗粒分离。 富集的溶质颗粒被合适的气相或颗粒检测器蒸发，离子化和/或检测。 该装置主要是液相色谱仪或过程流与质谱仪之间的界面。

公开(公告)号：US4977785A

公开(公告)日：1990-12-18

申请号：US157626

申请日：1988-02-19

申请人： Ross C. Willoughby ,  James D. Buchner

发明人： Ross C. Willoughby ,  James D. Buchner

IPC分类号： G01N30/02 ,  G01N30/72 ,  H01J49/04

CPC分类号： H01J49/0468 ,  H01J49/0445 ,  G01N30/02 ,  G01N30/7246 ,  G01N30/7273 ,  G01N30/7293

摘要： Methods and apparatus for introduction of sample from a flowing stream into mass spectrometers or other analyzing apparatus for analytical and process stream analysis of the sample. The apparatus generates an aerosol during the decompression of a gas, liquid or supercritical fluid stream. The aerosol's properties are dependent upon mass flow, pressure, temperature, solubility of sample, and the physical dimensions of the aerosol generating device. Upon aerosol generation, a less volatile sample in the form of condensed particles is separated from the gaseous components by accelerating the aerosol through a nozzle restrictor and utilizing momentum differences between solute particles and carrier gas molecules to obtain high solute enrichments at various particles or gas-phase detectors. The device functions primarily as an interface between a supercritical fluid chromatograph and the mass spectrometer.

摘要翻译： 将样品从流动物引入质谱仪或其他分析装置中以用于样品的分析和工艺流分析的方法和装置。 该装置在减压气体，液体或超临界流体流期间产生气溶胶。 气溶胶的性质取决于质量流量，压力，温度，样品的溶解度和气溶胶发生装置的物理尺寸。 气溶胶产生时，通过喷嘴限制器加速气溶胶并利用溶质颗粒和载气分子之间的动量差异，在各种颗粒或气体分离器中获得高溶质富集，从而将冷凝颗粒形式的较不易挥发的样品与气体组分分离， 相位检测器。 该装置主要作为超临界流体色谱仪和质谱仪之间的界面。

公开(公告)号：US4968885A

公开(公告)日：1990-11-06

申请号：US393846

申请日：1989-08-14

申请人： Ross C. Willoughby

发明人： Ross C. Willoughby

IPC分类号： G01N1/00 ,  G01N30/02 ,  G01N30/30 ,  G01N30/72 ,  H01J49/04

CPC分类号： H01J49/049 ,  H01J49/045 ,  G01N1/22 ,  G01N2030/027 ,  G01N2030/3038 ,  G01N2030/3061 ,  G01N30/7253

摘要： Methods and apparatus for liquid sample introduction into chemical detectors that require the sample to be transformed from a flowing stream into either gaseous or particulate states. The effluent from either a process stream or a liquid chromatograph is nebulized by combined thermal and penumatic processes within an inner fused silicon capillary tube heated by conduction through a relatively conductive sheathing gas such as helium or hydrogen from a surrounding electrical resistance heated outer capillary tube composed of a pure metal having a comparatively high linear relationship between temperature and electrical resistance to provide a uniform conduction of heat energy to the inner tube to form a well-collimated, partially or completely desolvated aerosol, with the less volatile solute components of the sample stream remaining in the particulate state. An expansion chamber at atmospheric pressure or less pressure slows the sheathing gas which surrounds the solvent vapor and solute particles sufficiently to form a stream which carries the solute particles in a manner that they avoid impacting the walls of the expansion chamber. The gaseous components of the aerosol are then separated from the solvent-depleted solute particles using either cryotrapping or momentum separation. The enriched solute particles are vaporized, ionized, and/or detected by suitable gas-phase or particle detectors. The device is primarily an interface between the liquid chromatograph or process streams and the mass spectrometer.

摘要翻译： 将液体样品引入化学检测器的方法和设备，其需要将样品从流动物流转变为气态或微粒状态。 来自工艺流或液相色谱仪的流出物通过内部熔融硅毛细管中的组合的热和阴离子工艺雾化，所述内部熔融硅毛细管通过相对导电的护套气体例如氦气或氢气从由周围的电阻加热的外部毛细管组成的导热加热 具有在温度和电阻之间具有较高线性关系的纯金属，以向内管提供均匀的热能传导以形成准直的，部分或完全脱溶的气溶胶，其中样品流的挥发性较低的溶质成分 保持颗粒状态。 在大气压或更低压力下的膨胀室减慢包围溶剂蒸气的护套气体，并充分溶解颗粒以形成携带溶质颗粒的流，使其不会影响膨胀室的壁。 然后气溶胶的气态组分使用低温震动或动量分离与溶剂消耗的溶质颗粒分离。 富集的溶质颗粒被合适的气相或颗粒检测器蒸发，离子化和/或检测。 该装置主要是液相色谱仪或过程流与质谱仪之间的界面。