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1. 发明授权

US08610056B2 Multipole ion guide ion trap mass spectrometry with MS/MSn analysis 失效
标题翻译：多极离子导向离子阱质谱与MS / MSn分析
公开(公告)号：US08610056B2
公开(公告)日：2013-12-17
申请号：US13164617
申请日：2011-06-20
申请人： Craig M. Whitehouse , Thomas Dresch , Bruce Andrien, Jr.
发明人： Craig M. Whitehouse , Thomas Dresch , Bruce Andrien, Jr.
IPC分类号： B01D59/44
CPC分类号： B01D59/44 , H01J49/004 , H01J49/063 , H01J49/401
摘要： An apparatus includes an atmospheric pressure ion source; a first vacuum stage and a second vacuum stage separated from the first vacuum stage by a vacuum partition; a first ion guide positioned within a first vacuum stage and arranged to receive ions from the atmospheric pressure ion source; a second ion guide positioned within a second vacuum stage downstream of the first vacuum stage from the atmospheric pressure ion source, the second ion guide being a multipole ion guide arranged to receive ions from the first ion guide; and a time-of-flight mass analyzer that includes an orthogonal pulsing region arranged to receive ions from the second ion guide.
摘要翻译：一种装置包括大气压离子源; 通过真空隔板与第一真空级分离的第一真空级和第二真空级; 位于第一真空级内并被布置成接收来自大气压离子源的离子的第一离子引导件; 位于第一真空级下游的第二真空级的第二离子导向器，其位于大气压离子源的下游，所述第二离子导向器是布置成接收来自第一离子导向器的离子的多极离子导向器; 以及飞行时间质量分析器，其包括布置成接收来自第二离子导向器的离子的正交脉冲区域。

2. 发明申请

US20120318050A1 SAMPLE COMPONENT TRAPPING, RELEASE, AND SEPARATION WITH MEMBRANE ASSEMBLIES INTERFACED TO ELECTROSPRAY MASS SPECTROMETRY 有权
标题翻译：样品组分捕获，释放和分离与膜电泳接触电泳质谱分析
公开(公告)号：US20120318050A1
公开(公告)日：2012-12-20
申请号：US13526932
申请日：2012-06-19
申请人： Craig M. Whitehouse , Thomas White
发明人： Craig M. Whitehouse , Thomas White
IPC分类号： H01J49/26 , G01N1/00
CPC分类号： B01D59/44 , G01N1/4005 , G01N30/00 , G01N30/7266 , H01J49/165 , Y10T436/212 , Y10T436/24
摘要： A method and apparatus to trap, release and/or separate sample components in solution passing through a channel with or without packing material present by passing ion current through the channel driven by an electric field. A portion of the ion current includes cation and/or anion species generated from second solution flows separated from the sample solution flow path by semipermeable membranes. Cation and/or anion ion species generated in the second solution flow regions are transferred into the sample solution flow path through ion selective semipermeable membranes. Ion current moving along the sample solution flow path is controlled by varying the composition of the second solutions and/or changing the voltage between membrane sections for a given sample solution composition. The sample composition may also be varied separately or in parallel to enhance trapping, release and/or separation efficiency and range.
摘要翻译：一种方法和装置，其通过使离子流通过由电场驱动的通道而使通过具有或不具有填充材料的通道通过通道的溶液中的样品组分被捕获，释放和/或分离。离子电流的一部分包括由通过半透膜从样品溶液流动路径分离的第二溶液流产生的阳离子和/或阴离子物质。在第二溶液流动区域中产生的阳离子和/或阴离子物质通过离子选择性半透膜转移到样品溶液流动路径中。通过改变第二溶液的组成和/或改变给定样品溶液组合物的膜部分之间的电压来控制沿样品溶液流动路径移动的离子电流。样品组合物也可以单独地或并行地改变以提高捕获，释放和/或分离效率和范围。

3. 发明授权

US07800057B2 Atmospheric pressure ion source performance enhancement 有权
标题翻译：大气压离子源性能提升
公开(公告)号：US07800057B2
公开(公告)日：2010-09-21
申请号：US12131486
申请日：2008-06-02
申请人： Craig M. Whitehouse , Thomas P. White
发明人： Craig M. Whitehouse , Thomas P. White
IPC分类号： B01D59/44 , H01J49/04 , H01J49/10
CPC分类号： H01J49/165
摘要： Electrospray ionization sources interfaced to mass spectrometers have become widely used tools in analytical applications. Processes occurring in Electrospray (ES) ionization generally include the addition or removal of a charged species such as H+ or other cation to effect ionization of a sample species. Electrospray includes ionization processes that occur in the liquid and gas phase and in both phases ionization processes require a source or sink for such charged species. Electrolyte species, that aid in oxidation or reduction reactions occurring in Electrospray ionization, are added to sample solutions in many analytical applications to increase the ES ion signal amplitude detected by a mass spectrometer (MS). Electrolyte species that may be required to enhance an upstream sample preparation or separation process may be less compatible with the downstream ES processes and cause reduction in MS signal. A new set of Electrolytes has been found that increases positive and negative polarity analyte ion signal measured in ESMS analysis when compared with analyte ESMS signal achieved using more conventional electrolytes. The new electrolyte species increase ES MS signal when added directly to a sample solution or when added to a second solution flow in an Electrospray membrane probe. The new electrolytes can also be added to a reagent ion source configured in a combination Atmospheric pressure ion source to improve ionization efficiency.
摘要翻译：与质谱仪接口的电喷雾离子源已成为分析应用中广泛使用的工具。在电喷雾（ES）电离中发生的过程通常包括加入或除去诸如H +或其它阳离子的带电物质以实现样品物质的离子化。电喷雾包括在液相和气相中发生的电离过程，并且在两相中，电离过程需要这种带电物质的源或汇。在许多分析应用中，在电喷雾电离中发生氧化或还原反应的电解质物质被添加到样品溶液中以增加由质谱仪（MS）检测到的ES离子信号幅度。可能需要增强上游样品制备或分离过程的电解质物质可能与下游ES过程较不相容，并导致MS信号的降低。已经发现一组新的电解质在ESMS分析中测量的正极和负极性分析物离子信号与使用更常规电解质获得的分析物ESMS信号相比较。新的电解质物质直接添加到样品溶液中或当添加到电喷雾膜探针中的第二溶液流中时，增加ES MS信号。新的电解质也可以添加到组合大气压离子源的试剂离子源中，以提高电离效率。

4. 发明授权

US07786435B2 RF surfaces and RF ion guides 有权
标题翻译： RF表面和RF离子导向
公开(公告)号：US07786435B2
公开(公告)日：2010-08-31
申请号：US12111484
申请日：2008-04-29
申请人： Craig M. Whitehouse , David G. Welkie , Lisa Cousins
发明人： Craig M. Whitehouse , David G. Welkie , Lisa Cousins
IPC分类号： H01J49/42
CPC分类号： H01J49/42 , H01J49/062
摘要： Apparatus and methods are provided for trapping, manipulation and transferring ions along RF and DC potential surfaces and through RF ion guides potential wells are formed near RF-field generating surfaces due to the overlap of the radio-frequency (RF) fields and electrostatic fields created by static potentials applied to surrounding electrodes. Ions can be constrained and accumulated over time in such wells During confinement, ions may be subjected to various processes, such as accumulation, fragmentation, collisional cooling, focusing, mass-to-charge filtering, spatial separation ion mobility and chemical interactions, leading to improved performance in subsequent processing and analysis steps, such as mass analysis. Alternatively, the motion of ions may be better manipulated during confinement to improve the efficiency of their transport to specific locations, such as an entrance aperture into vacuum from atmospheric pressure or into a subsequent vacuum stage.
摘要翻译：提供了设备和方法，用于捕获，操纵和转移沿着RF和DC电势表面的离子，并通过RF离子引导，由于射频（RF）场和产生的静电场的重叠，在RF场产生表面附近形成势阱通过施加到周围电极的静电势。离子可以在这样的井中被约束和积累随着时间的推移在限制期间，离子可以经历各种过程，例如积累，碎裂，碰撞冷却，聚焦，质量 - 电荷过滤，空间分离离子迁移和化学相互作用，导致在后续处理和分析步骤中提高性能，如质量分析。或者，可以在限制期间更好地操作离子的运动，以提高其运送到特定位置的效率，例如从大气压进入真空的入口孔或进入随后的真空级。

5. 发明授权

US07619216B1 Charged droplet sprayers 有权
标题翻译：带电液滴喷雾器
公开(公告)号：US07619216B1
公开(公告)日：2009-11-17
申请号：US11803984
申请日：2007-05-15
申请人： Craig M. Whitehouse , Thomas White
发明人： Craig M. Whitehouse , Thomas White
IPC分类号： B01D59/44 , G01N24/00
CPC分类号： H01J49/165 , B01D61/00 , B01D61/425 , B01D2313/345 , G01N30/7266 , H01J49/0018 , H01J49/167 , Y10T436/212 , Y10T436/24
摘要： Charged droplet spray is formed from a solution with all or a portion of the charged droplet spray current generated from reduction or oxidation (redox) reactions occurring on surfaces removed from the first or sample solution flow path. In one embodiment of the invention, two solution flow channels are separated by a semipermeable membrane. A first or sample solution flowing through the first solution flow channel exchanges cation or anion charged species through the semipermeable membrane with a second solution or gas flowing through the second flow channel. Charge exchange is driven by the electric field applied at the charged droplet sprayer sample solution outlet. Redox reactions occur at an electrode surface in contact with the second solution. The second solution or gas phase composition can be changed as a step function or as a gradient to run pH or conductivity scans in the first solution to optimize or modify Electrospray performance in Electrospray mass spectrometry applications. The first or sample solution forms a charged droplet spray by Electrospray or pneumatic nebulization in the presence of an electric field from the first solution flow channel exit. Evaporating charged liquid droplets form ions from species in solution that are transferred into vacuum and mass to charge analyzed. The second solution or composition can be modified to selectively change pH, conductivity and/or composition of the sample solution during Electrospray ionization to enhance or extend analytical performance for given ES/MS analytical applications. The invention increases the control and range of the Electrospray ionization process during ES/MS operation. Alternative embodiments of the invention provide for conducting redox reactions on conductive surfaces removed from the first or sample solution flow path but not separated by semipermeable membranes.
摘要翻译：由溶液形成带电的液滴喷雾，其中从在第一或样品溶液流动路径上去除的表面上发生的还原或氧化（氧化还原）反应产生的全部或一部分带电液滴喷雾电流。在本发明的一个实施方案中，两个溶液流动通道被半透膜隔开。流过第一溶液流动通道的第一或样品溶液通过半透膜与穿过第二流动通道的第二溶液或气体交换阳离子或阴离子带电物质。电荷交换由在带电液滴喷雾器样品溶液出口处施加的电场驱动。在与第二溶液接触的电极表面处发生氧化还原反应。可以将第二溶液或气相组合物作为步骤功能或梯度来改变以在第一溶液中进行pH或电导率扫描，以优化或改变电喷雾质谱法应用中的电喷雾性能。第一或样品溶液在来自第一溶液流动通道出口的电场的存在下通过电喷雾或气动雾化形成带电的液滴喷雾。蒸发的带电液滴从溶液中的物质形成离子，转移到真空中并进行质量分析。可以修改第二种溶液或组合物以在电喷雾离子化期间选择性地改变样品溶液的pH，电导率和/或组成，以增强或扩大给定的ES / MS分析应用的分析性能。本发明增加了ES / MS操作期间电喷雾电离过程的控制和范围。本发明的替代实施例提供了在从第一或样品溶液流动路径移除但不被半透膜隔离的导电表面上进行氧化还原反应。

6. 发明授权

US07232992B2 Charged droplet sprayers 有权
标题翻译：带电液滴喷雾器
公开(公告)号：US07232992B2
公开(公告)日：2007-06-19
申请号：US11132953
申请日：2005-05-19
申请人： Craig M. Whitehouse , Thomas White
发明人： Craig M. Whitehouse , Thomas White
IPC分类号： B01D59/44 , G01N24/00
CPC分类号： H01J49/165 , B01D61/00 , B01D61/425 , B01D2313/345 , G01N30/7266 , H01J49/0018 , H01J49/167 , Y10T436/212 , Y10T436/24
摘要： Charged droplet spray is formed from a solution with all or a portion of the charged droplet spray current generated from reduction or oxidation (redox) reactions occurring on surfaces removed from the first or sample solution flow path. In one embodiment of the invention, two solution flow channels are separated by a semipermeable membrane. A first or sample solution flowing through the first solution flow channel exchanges cation or anion charged species through the semipermeable membrane with a second solution or gas flowing through the second flow channel. Charge exchange is driven by the electric field applied at the charged droplet sprayer sample solution outlet. Redox reactions occur at an electrode surface in contact with the second solution. The invention increases the control and range of the Electrospray ionization process during ES/MS operation. Alternative embodiments of the invention provide for conducting redox reactions on conductive surfaces removed from the first or sample solution flow path but not separated by semipermeable membranes.
摘要翻译：由溶液形成带电的液滴喷雾，其中从在第一或样品溶液流动路径上去除的表面上发生的还原或氧化（氧化还原）反应产生的全部或一部分带电液滴喷雾电流。在本发明的一个实施方案中，两个溶液流动通道被半透膜隔开。流过第一溶液流动通道的第一或样品溶液通过半透膜与穿过第二流动通道的第二溶液或气体交换阳离子或阴离子带电物质。电荷交换由在带电液滴喷雾器样品溶液出口处施加的电场驱动。在与第二溶液接触的电极表面处发生氧化还原反应。本发明增加了ES / MS操作期间电喷雾电离过程的控制和范围。本发明的替代实施例提供了在从第一或样品溶液流动路径移除但不被半透膜隔离的导电表面上进行氧化还原反应。

7. 发明授权

US07189967B1 Mass spectrometry with multipole ion guides 有权
标题翻译：多极离子导向质谱仪
公开(公告)号：US07189967B1
公开(公告)日：2007-03-13
申请号：US11333086
申请日：2006-01-17
申请人： Craig M. Whitehouse , Bruce A. Andrien, Jr. , Erol E. Gulcicek
发明人： Craig M. Whitehouse , Bruce A. Andrien, Jr. , Erol E. Gulcicek
IPC分类号： H01J49/42
CPC分类号： H01J49/063 , H01J49/004
摘要： Multipole ion guides configured with one or more segments and positioned in a higher pressure vacuum region, are operated in mass to charge selection and ion fragmentation modes. Individual multipole ion guides are mounted in a linear assembly with no electrodes configured in between each multipole ion guide. At least a portion of each multipole ion guide mounted in a linear assembly resides in a vacuum region with higher background pressure. At least one ion guide can be configured to extend continuously from one vacuum stage into another. Individual sets of RF, +/−DC and secular frequency voltage supplies provide potentials to the rods of each multipole ion guide allowing the operation of ion transmission, ion trapping, mass to charge selection and ion fragmentation functions independently in each ion guide. The presence of higher background pressure along a portion of the multiple ion guide linear assembly allows the Collisional Induced Dissociation (CID) fragmentation of ions by axially accelerating ions from one multipole ion guide to an adjacent ion guide, analogous to a triple quadrupole function. A variety of MS and MS/MSn analysis functions can be achieved with a mass analyzer configured with multiple ion guide linear assembly operated in a higher background pressure.
摘要翻译：配置有一个或多个段并位于较高压力真空区域的多极离子引导件被质量运行以进行选择和离子碎片模式的充电。单个多极离子导向器安装在线性组件中，没有电极配置在每个多极离子导向器之间。安装在线性组件中的每个多极离子导体的至少一部分位于具有较高背景压力的真空区域中。至少一个离子导向器可被配置为从一个真空级连续地延伸到另一个。各组RF，+/- DC和长期频率电压电源为每个多极离子导向器的棒提供电位，从而允许在每个离子导向器中独立地进行离子传输，离子捕获，质量到电荷选择和离子碎片功能的操作。沿多重离子导向线性组件的一部分存在更高的背景压力允许离子的碰撞诱导离解（CID）通过将离子从一个多极离子导向轴向加速到相邻的离子导向器，类似于三重四极杆功能。通过质量分析器可以实现各种MS和MS / MS分析功能，质量分析器配置有在较高背景压力下操作的多个离子导向线性组件。

8. 发明授权

US6121607A Ion transfer from multipole ion guides into multipole ion guides and ion traps 失效
公开(公告)号：US6121607A
公开(公告)日：2000-09-19
申请号：US857191
申请日：1997-05-15
申请人： Craig M. Whitehouse , Erol Gulcicek
发明人： Craig M. Whitehouse , Erol Gulcicek
IPC分类号： B01D59/44 , H01J49/00 , H01J49/04 , H01J49/42
CPC分类号： H01J49/063 , H01J49/067 , H01J49/424
摘要： A multipole ion guide is configured to improve the transmission efficiency of ions which traverse the length of one ion guide and enter either another multipole ion guide such as a quadrupole mass analyzer or a three dimensional ion trap. The ion transfer multipole ion guide radial dimensions are reduced such that the pole assembly and an appropriately shaped exit lens can be positioned within a portion of the internal space defined by the larger radius second multipole ion guide poles. Ions exiting the first ion guide of reduced size find themselves inside the second ion guide close to the centerline. In this manner ions can be efficiently transferred from one ion guide to another, even for those ions with low kinetic energies. In a second embodiment of the invention, the exit region of a multipole ion guide is configured such that the multipole ion guide poles can be extended into a counterbore of a three dimensional ion trap end cap electrode. With this configuration, ions (including those with low kinetic energies) can be transferred into a three dimensional ion trap with increased trapping efficiency.

9. 发明授权

US5844237A Electrospray and atmospheric pressure chemical ionization sources 失效
公开(公告)号：US5844237A
公开(公告)日：1998-12-01
申请号：US791346
申请日：1997-01-31
申请人： Craig M. Whitehouse , J. Fred Banks, Jr. , Clement Catalano
发明人： Craig M. Whitehouse , J. Fred Banks, Jr. , Clement Catalano
IPC分类号： G01N27/62 , G01N30/72 , H01J49/04 , H01J49/10 , H01J49/26 , B01D59/44 , H01J49/00
CPC分类号： G01N30/7266 , H01J49/067 , H01J49/165 , G01N30/7293
摘要： Improvements have been made to the Electrospray and Atmospheric Pressure Chemical Ionization source chambers interfaced to mass spectrometers to simplify source performance optimization and source operation and to improve system sensitivity. The atmospheric pressure ion source procedure for optimizing performance has been simplified by adding windows along the sides of the atmospheric pressure ionization chamber allowing direct viewing of the Electrospray and Atmospheric pressure ion sources during operation. A cylindrical lens which extends along the side walls of the atmospheric pressure chamber has been configured to be semitransparent for viewing into the chamber. This cylindrical shaped side lens is electrically isolated from the Electrospray liquid introduction needle and Electrospray chamber endplate. Improved Electrospray mass spectrometer system sensitivity can be achieved when operating the cylindrical lens with a higher potential difference between it and the Electrospray liquid introduction needle than is set between the needle and the endplate.

10. 发明授权

US5306412A Method and apparatus for improving electrospray ionization of solute species 失效
标题翻译：改善溶质物质电喷雾离子化的方法和装置
公开(公告)号：US5306412A
公开(公告)日：1994-04-26
申请号：US46379
申请日：1993-04-08
申请人： Craig M. Whitehouse , John B. Fenn , Shida Shen , Cawthon Smith
发明人： Craig M. Whitehouse , John B. Fenn , Shida Shen , Cawthon Smith
IPC分类号： B05B17/06 , G01N30/60 , G01N30/72 , H01J49/04 , G01N27/26 , G01N27/447 , H01J49/10
CPC分类号： H01J49/167 , B05B17/0623 , B05B17/063 , G01N30/7246 , G01N30/7266 , H01J49/0454 , G01N2030/6013 , G01N30/7273 , G01N30/7293
摘要： The subject invention teaches the use of mechanical vibration to enhance the electrostatic dispersion of sample solutions into the small, highly charged droplets that can produce ions of solute species for mass spectrometric analysis. Such vibration turns out to be surprisingly effective at ultrasonic frequencies for solutions with flow rates, conductivities and surface tensions too high for stable dispersion by electrostatic forces alone as in conventional electrospray ionization. Several embodiments of the invention are described for purposes of illustration. Other possible embodiments will become apparent to those skilled in the art.
摘要翻译：本发明教导了使用机械振动来增强样品溶液到可以产生用于质谱分析的溶质物质离子的小的高电荷液滴中的静电分散。这种振动在超声波频率下对于流速，电导率和表面张力过高，对于通过静电力的稳定分散（如在常规电喷雾离子化）中的解决方案而言，是惊人的有效的。为了说明的目的描述了本发明的若干实施例。其他可能的实施例对于本领域技术人员将变得显而易见。

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