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公开(公告)号：US07227131B2
公开(公告)日：2007-06-05
申请号：US10929768
申请日：2004-08-31
IPC分类号： H01J49/40
CPC分类号： H01J49/408 , H01J49/406
摘要： A time of flight type mass spectrometer (TOF-MS) of the present invention includes: a flight space containing a loop orbit on which ions fly once or more than once; a flight controller for making ions of a same mass to charge ratio fly the loop orbit at several values of number of turns; a flight time measurer for measuring a length of flight time of the ions; and a processor for determining the mass to charge ratio of the ions based on a relationship between the value of number of turns and the length of flight time of the ions. The speed of ions flying a loop orbit depends on their mass to charge ratios. For ions of the same mass to charge ratio, the difference between the lengths of flight time of the ions flying the loop orbit N turns and of the ions flying the loop orbit N+1 turns depends on the speed of the ions, so that the difference depends on the mass to charge ratio of the ions. The difference in the length of flight time is unrelated to the variation in the starting time (jitter), variation in the detection timing (jitter), etc, so that the value of the mass to charge ratio can be precisely determined free from errors caused by such disturbing factors.
摘要翻译： 本发明的飞行时间型质谱仪（TOF-MS）包括：包含离子飞行一次或多次的循环轨道的飞行空间; 用于使相同质荷比的离子的飞行控制器以匝数的几个值飞行环路轨道; 用于测量离子的飞行时间长度的飞行时间测量器; 以及用于基于匝数与离子的飞行时间长度之间的关系来确定离子的质荷比的处理器。 飞行环路轨道的离子速度取决于其质荷比。 对于相同质荷比的离子，飞越环轨道N圈的离子的飞行时间长度和飞行环轨道N + 1圈的离子之间的差异取决于离子的速度，因此 差异取决于离子的质荷比。 飞行时间长度的差异与启动时间（抖动）的变化，检测定时（抖动）等的变化无关，从而可以精确地确定质荷比值，从而避免误差 受到这样的扰乱因素。
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公开(公告)号：US07211792B2
公开(公告)日：2007-05-01
申请号：US11032002
申请日：2005-01-11
CPC分类号： H01J49/408
摘要： In the mass spectrometer of the present invention, a flight space is provided before the mass analyzer, and the flight space includes a loop orbit on which ions fly repeatedly. While ions fly on the loop orbit repeatedly, ion selecting electrodes placed on the loop orbit selects object ions having a specific mass to charge ratio in such a manner that, for a limited time period when the object ions are flying through the ion selecting electrodes, an appropriate voltage is applied to the ion selecting electrodes to make them continue to fly on the loop orbit, but otherwise to make or let other ions deflect from the loop orbit. If ions having various mass to charge ratios are introduced in the loop orbit almost at the same time, the object ions having the same mass to charge ratio continue to fly on the loop orbit in a band, but ions having mass to charge ratios different from that are separated from the object ions while flying on the loop orbit repeatedly. Even if the difference in the mass to charge ratio is small, the separation becomes large when the number of turns of the flight becomes large. After such a separation is adequately achieved, the ion selecting electrodes can select the object ions with high selectivity, or at high mass resolution. By adding dissociating means, fragment ions originated only from the selected object ions can be analyzed, which enables the identification and structural analysis of the sample at high accuracy.
摘要翻译： 在本发明的质谱仪中，在质量分析器之前提供飞行空间，并且飞行空间包括离子重复飞行的环轨道。 当离子重复地在环路轨道上飞行时，放置在环路轨道上的离子选择电极以这样的方式选择具有特定质荷比的物体离子，使得在物体离子飞过离子选择电极的有限时间段内， 对离子选择电极施加适当的电压使它们继续在环轨道上飞行，而另外使其它离子从环轨道偏转。 如果几乎同时在环路轨道中引入具有各种质荷比的离子，则具有相同质荷比的物体离子在带内的环路轨道上继续飞行，但质量与电荷比的离子不同于 它们与物体离子分离，同时在环路轨道上重复飞行。 即使质荷比的差小，当飞行匝数变大时，分离也变大。 在这种分离充分实现之后，离子选择电极可以以高选择性或高质量分辨率选择目标离子。 通过添加解离手段，可以分析仅从所选择的对象离子产生的碎片离子，这使得能够高精度地鉴定和结构分析样品。
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公开(公告)号：US07148473B2
公开(公告)日：2006-12-12
申请号：US10929770
申请日：2004-08-31
IPC分类号： H01J49/40
CPC分类号： H01J49/408 , H01J49/027
摘要： In a time of flight mass spectrometer (TOF-MS) of the present invention, a flight controller makes ions fly a loop orbit a predetermined number of turns, and an ion detector detects the ions at each turn of the flight. A flight time measurer measures the length of flight time of ions of a same mass to charge ratio at every turn, and a data processor constructs a spectrum of flight time. The data processor further computes the Fourier transformation of the spectrum, and determines the mass to charge ratio of the ions based on a frequency peak appearing in the Fourier transformation.
摘要翻译： 在本发明的飞行时间质谱仪（TOF-MS）中，飞行控制器使离子飞行预定匝数的环路轨道，并且离子检测器在飞行的每一回合处检测离子。 飞行时间测量器可以测量每一回合具有相同质荷比的离子的飞行时间长度，并且数据处理器构建飞行时间谱。 数据处理器进一步计算光谱的傅立叶变换，并且基于在傅立叶变换中出现的频率峰值来确定离子的质荷比。
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公开(公告)号：US20050151076A1
公开(公告)日：2005-07-14
申请号：US11032002
申请日：2005-01-11
CPC分类号： H01J49/408
摘要： In the mass spectrometer of the present invention, a flight space is provided before the mass analyzer, and the flight space includes a loop orbit on which ions fly repeatedly. While ions fly on the loop orbit repeatedly, ion selecting electrodes placed on the loop orbit selects object ions having a specific mass to charge ratio in such a manner that, for a limited time period when the object ions are flying through the ion selecting electrodes, an appropriate voltage is applied to the ion selecting electrodes to make them continue to fly on the loop orbit, but otherwise to make or let other ions deflect from the loop orbit. If ions having various mass to charge ratios are introduced in the loop orbit almost at the same time, the object ions having the same mass to charge ratio continue to fly on the loop orbit in a band, but ions having mass to charge ratios different from that are separated from the object ions while flying on the loop orbit repeatedly. Even if the difference in the mass to charge ratio is small, the separation becomes large when the number of turns of the flight becomes large. After such a separation is adequately achieved, the ion selecting electrodes can select the object ions with high selectivity, or at high mass resolution. By adding dissociating means, fragment ions originated only from the selected object ions can be analyzed, which enables the identification and structural analysis of the sample at high accuracy.
摘要翻译： 在本发明的质谱仪中，在质量分析器之前提供飞行空间，并且飞行空间包括离子重复飞行的环轨道。 当离子重复地在环路轨道上飞行时，放置在环路轨道上的离子选择电极以这样的方式选择具有特定质荷比的物体离子，使得在物体离子飞过离子选择电极的有限时间段内， 对离子选择电极施加适当的电压使它们继续在环轨道上飞行，而另外使其它离子从环轨道偏转。 如果几乎同时在环路轨道中引入具有各种质荷比的离子，则具有相同质荷比的物体离子在带内的环路轨道上继续飞行，但质量与电荷比的离子不同于 它们与物体离子分离，同时在环路轨道上重复飞行。 即使质荷比的差小，当飞行匝数变大时，分离也变大。 在这种分离充分实现之后，离子选择电极可以以高选择性或高质量分辨率选择目标离子。 通过添加解离手段，可以分析仅从所选择的对象离子产生的碎片离子，这使得能够高精度地鉴定和结构分析样品。
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公开(公告)号：US20050045817A1
公开(公告)日：2005-03-03
申请号：US10929770
申请日：2004-08-31
CPC分类号： H01J49/408 , H01J49/027
摘要： In a time of flight mass spectrometer (TOF-MS) of the present invention, a flight controller makes ions fly a loop orbit a predetermined number of turns, and an ion detector detects the ions at each turn of the flight. A flight time measurer measures the length of flight time of ions of a same mass to charge ratio at every turn, and a data processor constructs a spectrum of flight time. The data processor further computes the Fourier transformation of the spectrum, and determines the mass to charge ratio of the ions based on a frequency peak appearing in the Fourier transformation.
摘要翻译： 在本发明的飞行时间质谱仪（TOF-MS）中，飞行控制器使离子飞行预定匝数的环路轨道，并且离子检测器在飞行的每一回合处检测离子。 飞行时间测量器可以测量每一回合具有相同质荷比的离子的飞行时间长度，并且数据处理器构建飞行时间谱。 数据处理器进一步计算光谱的傅立叶变换，并且基于在傅里叶变换中出现的频率峰值来确定离子的质荷比。
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公开(公告)号：US20050194528A1
公开(公告)日：2005-09-08
申请号：US10929768
申请日：2004-08-31
CPC分类号： H01J49/408 , H01J49/406
摘要： A time of flight type mass spectrometer (TOF-MS) of the present invention includes: a flight space containing a loop orbit on which ions fly once or more than once; a flight controller for making ions of a same mass to charge ratio fly the loop orbit at several values of number of turns; a flight time measurer for measuring a length of flight time of the ions; and a processor for determining the mass to charge ratio of the ions based on a relationship between the value of number of turns and the length of flight time of the ions. The speed of ions flying a loop orbit depends on their mass to charge ratios. For ions of the same mass to charge ratio, the difference between the lengths of flight time of the ions flying the loop orbit N turns and of the ions flying the loop orbit N+1 turns depends on the speed of the ions, so that the difference depends on the mass to charge ratio of the ions. The difference in the length of flight time is unrelated to the variation in the starting time (jitter), variation in the detection timing (jitter), etc, so that the value of the mass to charge ratio can be precisely determined free from errors caused by such disturbing factors.
摘要翻译： 本发明的飞行时间型质谱仪（TOF-MS）包括：包含离子飞行一次或多次的循环轨道的飞行空间; 用于使相同质荷比的离子的飞行控制器以匝数的几个值飞行环路轨道; 用于测量离子的飞行时间长度的飞行时间测量器; 以及用于基于匝数与离子的飞行时间长度之间的关系来确定离子的质荷比的处理器。 飞行环路轨道的离子速度取决于其质荷比。 对于相同质荷比的离子，飞越环轨道N圈的离子的飞行时间长度和飞行环轨道N + 1圈的离子之间的差异取决于离子的速度，因此 差异取决于离子的质荷比。 飞行时间长度的差异与启动时间（抖动）的变化，检测定时（抖动）等的变化无关，从而可以精确地确定质荷比值，从而避免误差 受到这样的扰乱因素。
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公开(公告)号：US09589781B2
公开(公告)日：2017-03-07
申请号：US13995042
申请日：2010-12-17
申请人： Daisuke Okumura
发明人： Daisuke Okumura
IPC分类号： H01J49/06
CPC分类号： H01J49/062 , H01J49/063
摘要： A curved ion guide includes four curved rod electrodes arranged around a curved central axis, two deflecting auxiliary electrodes which face each other across the axis, and two focusing auxiliary electrodes which are located on a curved surface orthogonal to the plane P and including the axis and which face each other across the axis. Ions are focused by the effect of an electric field created by radio-frequency voltages applied to the curved rod electrodes, and a deflecting electric field having the effect of curving ions along the axis is created by direct-current voltages applied to the deflecting auxiliary electrodes. Furthermore, a focusing direct-current electric field having the effect of pushing ions from the vicinity of the focusing auxiliary electrodes toward the axis is created by a direct-current voltage having the same polarity as that of the ions and applied to the focusing auxiliary electrodes.
摘要翻译： 弯曲的离子导向器包括围绕弯曲的中心轴布置的四个弯曲杆电极，两个相对于轴线相对的两个偏转辅助电极和位于与平面P正交并且包括轴线的曲面上的两个聚焦辅助电极， 它们跨越轴线彼此面对。 离子通过由施加到弯曲棒电极的射频电压产生的电场的影响而集中，并且通过施加到偏转辅助电极的直流电压产生具有沿轴线弯曲离子的效果的偏转电场 。 此外，通过具有与离子极性相同的极性的直流电压产生具有将聚焦辅助电极附近的离子推向轴的聚焦直流电场，并施加到聚焦辅助电极 。
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公开(公告)号：US08748811B2
公开(公告)日：2014-06-10
申请号：US13589989
申请日：2012-08-20
申请人： Daisuke Okumura
发明人： Daisuke Okumura
CPC分类号： H01J49/0009 , H01J49/004 , H01J49/4215 , H01J49/429
摘要： A mass analysis of a sample having a known mass-to-charge ratio is carried out by performing a scan at a first-stage quadrupole over a predetermined mass range, under the condition that a collision induced dissociation gas is introduced into a collision cell and a voltage applied to a third-stage quadrupole is set so that no substantial mass separation occurs in this quadrupole. Various product ions originating from a precursor ion selected by the first-stage quadrupole arrive at and are detected by a detector without being mass separated. Accordingly, based on the detection data, a data processor can obtain a relationship between the voltage applied to the first-stage quadrupole and the mass-to-charge ratio of the selected ions, with a time delay in the collision cell reflected in that relationship. This relationship is stored in a calibration data memory, to be utilized in a neutral loss scan measurement or the like.
摘要翻译： 具有已知质荷比的样品的质量分析通过在预定质量范围内的第一级四极杆进行扫描，在碰撞诱导的解离气体被引入到碰撞池中的条件下进行， 设置施加到第三级四极的电压，使得在该四极中不发生实质的质量分离。 源自由第一级四极杆选择的前体离子的各种产物离子到达并被检测器检测而不被质量分离。 因此，基于检测数据，数据处理器可以获得施加到第一级四极杆的电压与所选择的离子的质荷比之间的关系，以该关系反映的碰撞单元中的时间延迟 。 该关系存储在校准数据存储器中，以用于中性损失扫描测量等。
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公开(公告)号：US20130334415A1
公开(公告)日：2013-12-19
申请号：US13982489
申请日：2011-09-30
申请人： Hiroshi Sugawara , Daisuke Okumura
发明人： Hiroshi Sugawara , Daisuke Okumura
IPC分类号： H01J49/42
CPC分类号： H01J49/42 , H01J49/0009 , H01J49/005 , H01J49/4215
摘要： A high-quality mass spectrum is provided with alleviated mass/charge axis deviation in a triple quadrupole mass spectrometer even when executing a high-speed mass scan with MS/MS analysis. Mass calibration tables which denote relations between m/z and a mass deviation value which scan speed is a parameter are prepared separately for use in MS analyses without involving dissociation operations and MS/MS analyses with involving dissociation operations. According to a measuring mode, such as a product ion scan measurement or a neutral loss scan measurement, when performing MS/MS analysis, a mass deviation value for the minimum scan speed in a table is used for a quadrupole where the selected m/z is fixed, and a mass deviation value for a designated scan speed in a table is used for a quadrupole where the mass scan is performed, thus controlling the operations of each of a pre-stage and a post-stage quadrupoles.
摘要翻译： 即使在使用MS / MS分析执行高速质谱扫描时，三重四极杆质谱仪也可以提供质量/充电轴偏差的优质质谱。 分别准备表示m / z和扫描速度参数的质量偏差值之间的关系的质量校准表，用于MS分析，不涉及解离操作和涉及解离操作的MS / MS分析。 根据诸如产品离子扫描测量或中性损耗扫描测量的测量模式，当执行MS / MS分析时，将表中的最小扫描速度的质量偏差值用于四极，其中所选择的m / z 并且将用于表中的指定扫描速度的质量偏差值用于执行质量扫描的四极杆，从而控制前级和后级四极杆中的每一个的操作。
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公开(公告)号：US20130284918A1
公开(公告)日：2013-10-31
申请号：US13995042
申请日：2010-12-17
申请人： Daisuke Okumura
发明人： Daisuke Okumura
IPC分类号： H01J49/06
CPC分类号： H01J49/062 , H01J49/063
摘要： A curved ion guide (2) includes four curved rod electrodes (201-204) arranged around a curved central axis (O), two deflecting auxiliary electrodes (205, 206) which are located on a plane P on which the curved central axis (O) lies and which face each other across the axis (O), and two focusing auxiliary electrodes (207, 208) which are located on a curved surface orthogonal to the plane P and including the axis (O) and which face each other across the axis (O). Ions are focused by the effect of an electric field created by radio-frequency voltages applied to the curved rod electrodes, and a deflecting electric field having the effect of curving ions along the axis (O) is created by direct-current voltages applied to the deflecting auxiliary electrodes. Furthermore, a focusing direct-current electric field having the effect of pushing ions from the vicinity of the focusing auxiliary electrodes toward the axis (O) is created by a direct-current voltage having the same polarity as that of the ions and applied to the focusing auxiliary electrodes. The spatial spread of ions having large amounts of energy is suppressed by the effect of this focusing direct-current electric field, and the ions efficiently arrive at the exit end of the ion guide.
摘要翻译： 弯曲离子引导件（2）包括围绕弯曲中心轴线（O）布置的四个弯曲杆状电极（201-204），位于平面P上的两个偏转辅助电极（205,206），弯曲中心轴线 O）位于并且彼此面对轴线（O），并且两个聚焦辅助电极（207,208）位于与平面P正交且包括轴线（O）并且彼此面对的弯曲表面上 轴（O）。 离子通过由施加到弯曲棒电极的射频电压产生的电场的影响而集中，并且具有沿着轴（O）弯曲离子的效果的偏转电场由施加到 偏转辅助电极。 此外，通过具有与离子的极性相同的极性的直流电压产生具有将离子从聚焦辅助电极附近向轴线（O）推压的效果的聚焦直流电场， 聚焦辅助电极。 通过该聚焦直流电场的影响来抑制具有大量能量的离子的空间扩散，并且离子有效地到达离子导向器的出口端。
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