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1.发明授权
公开(公告)号：US06011259A
公开(公告)日：2000-01-04
申请号：US694542
申请日：1996-08-09
CPC分类号： H01J49/40 , H01J49/004 , H01J49/063
摘要： A Time-Of-Flight (TOF) mass analyzer is configured with a multipole ion guide in the ion path between the ion source and pulsing region of the mass analyzer, and enables trapping or transmission of ions from an atmospheric pressure ion source. The mass-to-charge (m/z) range(s) of ions transmitted through or trapped in the ion guide can be selected. Ions with stable trajectories can undergo Collisional Induced Dissociation (CID). During ion fragmentation, the ion guide potentials can be set to transmit or trap fragment ions produced by CID. The parent and fragment ion population can be delivered from the ion guide to the pulsing region of the TOF mass analyzer for mass analysis. After the first fragmentation step, the ion guide potentials can again be set to select a narrow m/z range to clear the ion guide in trapping mode of all but a selected set of fragment ions. M/z selection and ion fragmentation can be repeated a number of times with mass analysis occurring at the end of all the MS/MS.sup.n steps or at various times during the MS/MS.sup.n stepwise process. Additionally, the normally stepwise MS/MS.sup.n analysis function can be merged into a single step, increasing the effective duty cycle. In all embodiments, the ion guide can reside in one vacuum pumping stage or can extend continuously into more than one vacuum pumping stage.
摘要翻译： 飞行时间质量分析仪（TOF）质量分析仪在质量分析仪的离子源和脉冲区域之间的离子路径中配置有多极离子导向器，并能够从大气压离子源捕获或传输离子。 可以选择通过或捕获在离子导向器中的离子的质量（m / z）范围（s）。 具有稳定轨迹的离子可以经历碰撞诱导解离（CID）。 在离子碎片化期间，离子导向电位可以设置为透过或捕获由CID产生的碎片离子。 母体和碎片离子群体可以从离子导向器输送到TOF质量分析器的脉冲区域进行质量分析。 在第一次碎裂步骤之后，离子导向电位可以再次被设置为选择窄的m / z范围，以便除所选择的一组碎片离子之外的所有离子导向器以捕获模式中的离子导向。 可以在MS / MSn步骤结束时或MS / MSn逐步处理过程中的不同时间进行质量分析，重复多次M / Z选择和离子碎片。 此外，正常逐步的MS / MSn分析功能可以合并成一个步骤，增加有效占空比。 在所有实施例中，离子导向器可以驻留在一个真空泵送阶段中，或者可以连续地延伸到多于一个的真空泵送阶段。
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2.发明授权公开(公告)号：US08598519B2
公开(公告)日：2013-12-03
申请号：US13164590
申请日：2011-06-20
IPC分类号： B01D59/44
CPC分类号： B01D59/44 , H01J49/0481 , H01J49/063
摘要： A method includes directing ions from an atmospheric pressure ion source to a first ion guide; directing ions in the first ion guide to a second ion guide, the second ion guide being a multipole ion guide extending along an axis; periodically directing ions along the axis; receiving at least some of the ions in a time-of-flight analyzer; accelerating the ions in the time-of-flight mass analyzer orthogonal to the axis; and detecting the accelerated ions.
摘要翻译： 一种方法包括将离子从大气压离子源引导到第一离子导向器; 将所述第一离子导向器中的离子引导到第二离子引导件，所述第二离子引导件是沿着轴线延伸的多极离子引导件; 沿着轴定期引导离子; 在飞行时间分析仪中接收至少一些离子; 加速与轴垂直的飞行时间质量分析仪中的离子; 并检测加速离子。
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3.发明授权公开(公告)号：US08610056B2
公开(公告)日：2013-12-17
申请号：US13164617
申请日：2011-06-20
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。
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公开(公告)号：US20110309244A1
公开(公告)日：2011-12-22
申请号：US13164617
申请日：2011-06-20
IPC分类号： H01J49/40
CPC分类号： B01D59/44 , H01J49/004 , H01J49/063 , H01J49/401
摘要： A Time-Of-Flight mass analyzer includes a multipole ion guide located in the ion flight path between the ion source and the flight tube of the Time-Of-Flight mass analyzer. In one preferred embodiment, a Time-Of-Flight (TOF) mass analyzer is configured such that a multipole ion guide is positioned in the ion path between the ion source and the ion pulsing region of the TOF mass analyzer. The multipole ion guide electronics and the ion guide entrance and exit electrostatic lenses are configured to enable the trapping or passing through of ions delivered from an atmospheric pressure ion source. The ion guide electronics can be set to select the mass to charge (m/z) range of ions which can be successfully transmitted or trapped in the ion guide. More than one set of m/z values can be selected using techniques such as notch filtering with resonant frequency ion ejection of unwanted m/z values. All or a portion of the ions with stable ion guide trajectories in transmission or trapping mode can then undergo Collisional Induced Dissociation (CID) using one of at least three techniques. During the ion fragmentation step the multipole ion guide AC and DC electric potentials are set to transmit or trap all or a portion of the fragment ions produced by the CID process. All or a portion of the parent and fragment ion population are delivered from the multipole ion guide to the pulsing region of Time-OF-Flight mass analyzer for mass analysis. After the first ion fragmentation step, the multipole ion guide AC and DC electric potentials can again be set to select a narrow m/z range to clear the ion guide in trapping mode of all but a selected set of fragment ions. The m/z selection and ion fragmentation step can be repeated a number of times with mass analysis occurring at the end of all the MS/MSn steps or at various times during the MS/MSn stepwise process. A technique is also described where the normally stepwise MS/MSn analysis function can be merged into a single step, increasing the effective duty cycle. The multipole ion guide used for ion transmission, trapping and fragmentation can reside in one vacuum pumping stage or can extend continuously into more than one vacuum pumping stage.
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5.发明申请公开(公告)号：US20110303840A1
公开(公告)日：2011-12-15
申请号：US13164590
申请日：2011-06-20
IPC分类号： H01J49/40
CPC分类号： B01D59/44 , H01J49/0481 , H01J49/063
摘要： A method includes directing ions from an atmospheric pressure ion source to a first ion guide; directing ions in the first ion guide to a second ion guide, the second ion guide being a multipole ion guide extending along an axis; periodically directing ions along the axis; receiving at least some of the ions in a time-of-flight analyzer; accelerating the ions in the time-of-flight mass analyzer orthogonal to the axis; and detecting the accelerated ions.
摘要翻译： 一种方法包括将离子从大气压离子源引导到第一离子导向器; 将所述第一离子导向器中的离子引导到第二离子引导件，所述第二离子引导件是沿着轴线延伸的多极离子引导件; 沿着轴定期引导离子; 在飞行时间分析仪中接收至少一些离子; 加速与轴垂直的飞行时间质量分析仪中的离子; 并检测加速离子。
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公开(公告)号：US06204500B1
公开(公告)日：2001-03-20
申请号：US09413443
申请日：1999-10-06
申请人： Craig M. Whitehouse , Bruce Andrien
发明人： Craig M. Whitehouse , Bruce Andrien
IPC分类号： H01J4916
CPC分类号： H01J49/40 , B82Y15/00 , B82Y30/00 , H01J49/0068
摘要： A Time-Of-Flight mass spectrometer is configured with a pulsing region and electronic controls to cause the directing of ions to a surface in the Time-Of-Flight pulsing region. The population of ions resulting from the collecting of said ions on or near said surface is subsequently accelerated into the Time-Of-Flight tube for mass to charge analysis. Ions produced away from said surface located in the pulsing region of a Time-Of-Flight mass spectrometer can be directed to the surface with high or low surface collisional energies. Higher energy ion collisions with the surface can result in Surface Induced Dissociation fragmentation and the resulting ion fragment population can be accelerated into Time-Of-Flight tube where the ions are mass to charge analyzed. Ion mass to charge selection can occur prior to directing ions to the pulsing region surface allowing MS/MS Time-Of-Flight mass analysis with SID. Ion to surface low energy collisions or soft landings resulting in little or no ion fragmentation provide a means for spatially focusing ions on or near the surface prior to accelerating the surface collected ions into the Time-Of-Flight tube. The apparatus and methods described in the invention result in refined control of ion fragmentation energy and improved Time-Of-Flight mass to charge analysis performance.
摘要翻译： 飞行时间质谱仪配置有脉冲区域和电子控制器，以将离子引导到飞行时间脉动区域中的表面。 随后在所述表面上或附近收集所述离子产生的离子群随后被加速到飞行时间管中用于质量进行电荷分析。 离开位于飞行时间质谱仪的脉冲区域的所述表面的离子可以被引导到具有高或低表面碰撞能量的表面。 与表面的高能离子碰撞可导致表面诱导解离破碎，并且所得到的离子片段群体可以加速到飞行时间管中，其中离子被质量分析。 在将离子引导到脉冲区域表面之前可以进行离子质量以进行电荷选择，从而允许使用SID的MS / MS飞行时间质量分析。 离子到表面的低能量碰撞或软着陆导致很少或没有离子碎裂提供了在将表面收集的离子加速到飞行时间管之前将离子空间聚焦在表面上或附近的手段。 本发明中描述的装置和方法导致离子断裂能量的精细控制和改进的飞行时间质量以进行电荷分析性能。
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7.发明申请公开(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
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。
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公开(公告)号：US07800057B2
公开(公告)日：2010-09-21
申请号：US12131486
申请日：2008-06-02
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。
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公开(公告)号：US07786435B2
公开(公告)日：2010-08-31
申请号：US12111484
申请日：2008-04-29
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。
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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
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。
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