CN112362718B - A method and device for broadening the detection mass range of a mass spectrometer - Google Patents
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Abstract
本申请涉及一种拓宽质谱仪检测质量范围的方法及装置，包括以下步骤：S1，将射频信号频率和射频信号幅度调整至预设值；S2，保持所述射频信号频率不变，调整所述射频信号幅度，以使所述射频信号幅度沿特定方向扫描；S3，当所述射频信号幅度调整至极限值后，保持所述射频信号幅度不变，调整所述射频信号频率，以使所述射频信号频率沿特定方向扫描；S4，当所述射频信号频率调整至极限值时，停止扫描，输出质量范围检测的结果。本发明的有益效果是：在一个周期内分段进行射频幅度扫描和射频频率扫描，能够在相同的射频放大系统下对质量分析范围进行一定程度的扩增。
The present application relates to a method and device for broadening the mass detection range of a mass spectrometer, comprising the following steps: S1, adjusting the frequency and amplitude of a radio frequency signal to a preset value; S2, keeping the frequency of the radio frequency signal unchanged, adjusting the amplitude of the radio frequency signal so that the amplitude of the radio frequency signal scans along a specific direction; S3, when the amplitude of the radio frequency signal is adjusted to a limit value, keeping the amplitude of the radio frequency signal unchanged, adjusting the frequency of the radio frequency signal so that the frequency of the radio frequency signal scans along a specific direction; S4, when the frequency of the radio frequency signal is adjusted to a limit value, stopping scanning and outputting the result of mass range detection. The beneficial effect of the present invention is that the radio frequency amplitude scanning and the radio frequency frequency scanning are performed in segments within one cycle, and the mass analysis range can be amplified to a certain extent under the same radio frequency amplification system.
Description
技术领域Technical Field
本申请属于质谱分析技术领域，尤其是涉及一种拓宽质谱仪检测质量范围的方法。The present invention relates to the technical field of mass spectrometry analysis, and in particular to a method for broadening the mass detection range of a mass spectrometer.
背景技术Background technique
质谱技术能够分析待测物质的质荷比信息，相较于其他分析手段，具有高特异性和极快的分析速度，能够在极端的时间内完成物质的定性、定量分析，因此成为化学、生物学、临床医学等领域的重要分析手段。一些现场高精度、高准确性分析需求的出现，也推动了质谱仪的小型化，当前研究者已开发出多款采用不同质量分析器的小型化质谱仪。Mass spectrometry can analyze the mass-to-charge ratio of the substance to be tested. Compared with other analytical methods, it has high specificity and extremely fast analysis speed, and can complete qualitative and quantitative analysis of substances in an extremely short time. Therefore, it has become an important analytical method in the fields of chemistry, biology, clinical medicine, etc. The emergence of some on-site high-precision and high-accuracy analysis needs has also promoted the miniaturization of mass spectrometers. Currently, researchers have developed a number of miniaturized mass spectrometers using different mass analyzers.
然而，质谱仪体积的小型化也同时牺牲了某些仪器性能，能够应对多变环境的要求也限制了小型化质谱的功耗，进一步地限制了质量分析器上所幅高压的幅度和频率范围。当前所开发的小型化质谱仪器特别是以离子阱为质量分析器的小型化质谱仪，多专注于某一小质荷比范围物质的分析检测，例如适用于0～300Da范围内的挥发性有机物的分析，或适用于300～700Da化学物质或生物多肽等小分子物质的分析，现有技术中，质谱仪通常以固定射频信号频率和幅度进行扫描，但是小型质谱仪由于上述限制无法像大型仪器一样满足宽质量范围物质的分析。However, the miniaturization of mass spectrometers also sacrifices certain instrument performance. The requirement to cope with changing environments also limits the power consumption of miniaturized mass spectrometers, further limiting the amplitude and frequency range of the high voltage applied to the mass analyzer. Currently developed miniaturized mass spectrometers, especially miniaturized mass spectrometers with ion traps as mass analyzers, are mostly focused on the analysis and detection of substances in a small mass-to-charge ratio range, such as the analysis of volatile organic compounds in the range of 0 to 300 Da, or the analysis of small molecules such as 300 to 700 Da chemicals or biological peptides. In the prior art, mass spectrometers are usually scanned with fixed RF signal frequency and amplitude, but due to the above limitations, miniature mass spectrometers cannot meet the analysis of substances in a wide mass range like large instruments.
要拓宽小型化质谱仪的应用范围，提高应用的普适性，需要在便携性要求的功耗和体积范围内，拓宽质量分析器的质量分析范围。To broaden the application scope of miniaturized mass spectrometers and improve the universality of their applications, it is necessary to broaden the mass analysis range of the mass analyzer within the power consumption and volume range required for portability.
发明内容Summary of the invention
本发明要解决的技术问题是：为了拓宽小型化质谱仪器的质量分析范围，本发明提出了一种拓宽质谱仪检测质量范围的方法及装置。The technical problem to be solved by the present invention is: in order to broaden the mass analysis range of a miniaturized mass spectrometer, the present invention proposes a method and a device for broadening the mass detection range of a mass spectrometer.
本发明解决其技术问题所采用的技术方案是：The technical solution adopted by the present invention to solve the technical problem is:
一种拓宽质谱仪检测质量范围的方法，包括以下步骤：A method for broadening the mass detection range of a mass spectrometer comprises the following steps:
S1，将射频信号频率和射频信号幅度调整至预设值；S1, adjusting the RF signal frequency and RF signal amplitude to preset values;
S2，保持所述射频信号频率不变，调整所述射频信号幅度，以使所述射频信号幅度沿特定方向扫描；S2, keeping the frequency of the radio frequency signal unchanged, and adjusting the amplitude of the radio frequency signal so that the amplitude of the radio frequency signal scans along a specific direction;
S3，当所述射频信号幅度调整至极限值后，保持所述射频信号幅度不变，调整所述射频信号频率，以使所述射频信号频率沿特定方向扫描；S3, when the RF signal amplitude is adjusted to the limit value, the RF signal amplitude is kept unchanged, and the RF signal frequency is adjusted so that the RF signal frequency scans along a specific direction;
S4，当所述射频信号频率调整至极限值时，停止扫描，输出质量范围检测的结果。S4, when the frequency of the radio frequency signal is adjusted to a limit value, the scanning is stopped and the result of the mass range detection is output.
优选地，本发明的拓宽质谱仪检测质量范围的方法，所述射频信号频率的预设值为最大值。Preferably, in the method for broadening the mass detection range of a mass spectrometer of the present invention, the preset value of the radio frequency signal frequency is a maximum value.
优选地，本发明的拓宽质谱仪检测质量范围的方法，所述射频信号幅度的预设值为最小值。Preferably, in the method for broadening the mass detection range of a mass spectrometer of the present invention, the preset value of the RF signal amplitude is a minimum value.
优选地，本发明的拓宽质谱仪检测质量范围的方法，在步骤S2中，所述射频信号幅度从所述最小值开始呈线性变化逐步增大至最大值。Preferably, in the method for broadening the mass detection range of a mass spectrometer of the present invention, in step S2, the amplitude of the radio frequency signal changes linearly from the minimum value and gradually increases to a maximum value.
优选地，本发明的拓宽质谱仪检测质量范围的方法，在步骤S3中，所述射频信号频率从所述最大值开始呈线性变化逐步减小至最小值。Preferably, in the method for broadening the mass detection range of a mass spectrometer of the present invention, in step S3, the frequency of the radio frequency signal changes linearly from the maximum value and gradually decreases to the minimum value.
优选地，本发明的拓宽质谱仪检测质量范围的方法，所述极限值为质谱仪能够输出的射频信号频率或射频信号幅度的最大值或最小值。Preferably, in the method for broadening the mass detection range of a mass spectrometer of the present invention, the limit value is the maximum value or the minimum value of the radio frequency signal frequency or the radio frequency signal amplitude that the mass spectrometer can output.
一种拓宽质谱仪检测质量范围的装置，包括：A device for broadening the mass detection range of a mass spectrometer, comprising:
数值设定模块，用于将射频信号频率和射频信号幅度调整至预设值；A value setting module, used for adjusting the frequency and amplitude of the radio frequency signal to preset values;
射频信号调节模块，用于保持所述射频信号频率不变，调整所述射频信号幅度，以使所述射频信号幅度沿特定方向扫描；或当所述射频信号幅度调整至极限值后，保持所述射频信号幅度不变，调整所述射频信号频率，以使所述射频信号频率沿特定方向扫描；A radio frequency signal adjustment module, used to keep the frequency of the radio frequency signal unchanged and adjust the amplitude of the radio frequency signal so that the amplitude of the radio frequency signal scans along a specific direction; or when the amplitude of the radio frequency signal is adjusted to a limit value, keep the amplitude of the radio frequency signal unchanged and adjust the frequency of the radio frequency signal so that the frequency of the radio frequency signal scans along a specific direction;
结果输出模块，用于当所述射频信号频率调整至极限值时，停止扫描，输出质量范围检测的结果。The result output module is used to stop scanning and output the result of mass range detection when the frequency of the radio frequency signal is adjusted to a limit value.
本发明的有益效果是：在一个周期内分段进行射频幅度扫描和射频频率扫描，能够在相同的射频放大系统下一定程度上扩增分析范围。The beneficial effect of the present invention is that the radio frequency amplitude scanning and the radio frequency frequency scanning are performed in segments within one cycle, so that the analysis range can be expanded to a certain extent under the same radio frequency amplification system.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
下面结合附图和实施例对本申请的技术方案进一步说明。The technical solution of the present application is further described below in conjunction with the accompanying drawings and embodiments.
图1是本申请实施例1的拓宽质谱仪检测质量范围的方法步骤流程图；FIG1 is a flow chart of the method steps for broadening the mass detection range of a mass spectrometer according to Example 1 of the present application;
图2是本申请实施例1的质谱仪检测质量范围时射频信号幅度和频率的对应关系图；2 is a diagram showing the corresponding relationship between the amplitude and frequency of the radio frequency signal when the mass spectrometer of Example 1 of the present application detects the mass range;
图3是本申请实施例2的质谱仪检测质量范围时射频信号幅度和频率的对应关系图；3 is a diagram showing the corresponding relationship between the amplitude and frequency of the radio frequency signal when the mass spectrometer of Example 2 of the present application detects the mass range;
图4是本申请实施例3的质谱仪检测质量范围时射频信号幅度和频率的对应关系图。FIG4 is a diagram showing the corresponding relationship between the amplitude and frequency of the radio frequency signal when the mass spectrometer of Example 3 of the present application detects the mass range.
具体实施方式Detailed ways
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application may be combined with each other.
在本申请的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请保护范围的限制。此外，术语“第一”、“第二”等仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”等的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明创造的描述中，除非另有说明，“多个”的含义是两个或两个以上。In the description of the present application, it should be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the scope of protection of the present application. In addition, the terms "first", "second", etc. are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", etc. may explicitly or implicitly include one or more of the features. In the description of the invention, unless otherwise specified, "multiple" means two or more.
在本申请的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以通过具体情况理解上述术语在本申请中的具体含义。In the description of this application, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood by specific circumstances.
下面将参考附图并结合实施例来详细说明本申请的技术方案。The technical solution of the present application will be described in detail below with reference to the accompanying drawings and in combination with embodiments.
实施例1Example 1
为了拓宽小型化质谱仪器的质量分析范围，本发明提出了一种双模式结合射频扫描方法，能够在不改变仪器功耗的条件下，拓宽对应质量分析器的质量分析范围，提高对应小型化质谱的应用普适性，使其同时满足宽质量范围被分析物的检出。In order to broaden the mass analysis range of miniaturized mass spectrometers, the present invention proposes a dual-mode combined with radio frequency scanning method, which can broaden the mass analysis range of the corresponding mass analyzer without changing the power consumption of the instrument, improve the application universality of the corresponding miniaturized mass spectrometer, and enable it to simultaneously meet the detection of analytes in a wide mass range.
以四极杆质量分析器为例，四极杆的两组电极上分别施加数值相等极性相反的直流电压U和射频信号幅度V，射频信号频率为ω，所包围空间产生的双曲线型电场。离子在四极杆中的运动轨迹满足马修方程Taking the quadrupole mass analyzer as an example, the two sets of electrodes of the quadrupole are respectively applied with a DC voltage U and an RF signal amplitude V of equal value and opposite polarity. The RF signal frequency is ω, and the hyperbolic electric field generated in the enclosed space. The motion trajectory of ions in the quadrupole satisfies the Matthew equation
可以用a代表直流强度的参数，q代表射频交流参数的强度，其中A can be used to represent the parameter of DC intensity, and q can be used to represent the intensity of RF AC parameters.
r0为电极表面与四极杆中心的距离，求解马修方程，可得到四极杆中离子运动的稳定性图(a，q)。选择第一稳定区进行离子操作，以稳定区顶点为操作点，在固定的直流电压条件下通过改变射频电压的参数，实现四极滤质功能，使满足条件的离子通过四极杆进入检测器，非目标离子湮没在四极杆中。 r0 is the distance between the electrode surface and the center of the quadrupole. Solving the Matthew equation, we can get the stability diagram (a, q) of ion movement in the quadrupole. Select the first stable region for ion operation, take the vertex of the stable region as the operation point, and change the parameters of the RF voltage under the condition of fixed DC voltage to realize the quadrupole mass filtering function, so that the ions that meet the conditions pass through the quadrupole into the detector, and the non-target ions are annihilated in the quadrupole.
本实施例提供一种拓宽质谱仪检测质量范围的方法，包括以下步骤：This embodiment provides a method for broadening the mass detection range of a mass spectrometer, comprising the following steps:
S1，将射频信号频率和射频信号幅度调整至预设值；S1, adjusting the RF signal frequency and RF signal amplitude to preset values;
S2，保持所述射频信号频率不变，调整所述射频信号幅度，以使所述射频信号幅度沿特定方向扫描(也即射频信号幅度的变化由大到小或者由小到达)；S2, keeping the frequency of the RF signal unchanged, adjusting the amplitude of the RF signal so that the amplitude of the RF signal scans along a specific direction (that is, the amplitude of the RF signal changes from large to small or from small to large);
S3，当所述射频信号幅度调整至极限值后，保持所述射频信号幅度不变，调整所述射频信号频率，以使所述射频信号频率沿特定方向扫描(也即射频信号频率的变化由大到小或者由小到达)；S3, when the RF signal amplitude is adjusted to the limit value, the RF signal amplitude is kept unchanged, and the RF signal frequency is adjusted so that the RF signal frequency scans along a specific direction (that is, the RF signal frequency changes from large to small or from small to reach);
S4，当所述射频信号频率调整至极限值时，停止扫描，输出质量范围检测的结果。S4, when the frequency of the radio frequency signal is adjusted to a limit value, the scanning is stopped and the result of the mass range detection is output.
优选地，本实施例的拓宽质谱仪检测质量范围的方法，所述射频信号频率的预设值为最大值。Preferably, in the method for broadening the mass detection range of a mass spectrometer of this embodiment, the preset value of the radio frequency signal frequency is a maximum value.
优选地，本实施例的拓宽质谱仪检测质量范围的方法，所述射频信号幅度的预设值为最小值。Preferably, in the method for broadening the mass detection range of a mass spectrometer of this embodiment, the preset value of the RF signal amplitude is a minimum value.
优选地，本实施例的拓宽质谱仪检测质量范围的方法，在步骤S2中，所述射频信号幅度从所述最小值开始呈线性变化逐步增大至最大值。Preferably, in the method for broadening the mass detection range of a mass spectrometer of this embodiment, in step S2, the amplitude of the radio frequency signal changes linearly from the minimum value and gradually increases to a maximum value.
优选地，本实施例的拓宽质谱仪检测质量范围的方法，在步骤S3中，所述射频信号频率从所述最大值开始呈线性变化逐步减小至最小值。Preferably, in the method for broadening the mass detection range of a mass spectrometer of this embodiment, in step S3, the frequency of the radio frequency signal changes linearly from the maximum value and gradually decreases to the minimum value.
优选地，本实施例的拓宽质谱仪检测质量范围的方法，所述极限值为质谱仪能够输出的射频信号频率或射频信号幅度的最大值或最小值。Preferably, in the method for broadening the mass detection range of a mass spectrometer of this embodiment, the limit value is a maximum value or a minimum value of the radio frequency signal frequency or the radio frequency signal amplitude that the mass spectrometer can output.
本实施例提供一种拓宽质谱仪检测质量范围的装置，包括：This embodiment provides a device for broadening the mass detection range of a mass spectrometer, comprising:
数值设定模块，用于将射频信号频率和射频信号幅度调整至预设值；A value setting module, used for adjusting the frequency and amplitude of the RF signal to preset values;
射频信号调节模块，用于保持所述射频信号频率不变，调整所述射频信号幅度，以使所述射频信号幅度沿特定方向扫描；或当所述射频信号幅度调整至极限值后，保持所述射频信号幅度不变，调整所述射频信号频率，以使所述射频信号频率沿特定方向扫描；A radio frequency signal adjustment module, used to keep the frequency of the radio frequency signal unchanged and adjust the amplitude of the radio frequency signal so that the amplitude of the radio frequency signal scans along a specific direction; or when the amplitude of the radio frequency signal is adjusted to a limit value, keep the amplitude of the radio frequency signal unchanged and adjust the frequency of the radio frequency signal so that the frequency of the radio frequency signal scans along a specific direction;
结果输出模块，用于当所述射频信号频率调整至极限值时，停止扫描，输出质量范围检测的结果。The result output module is used to stop scanning and output the result of mass range detection when the frequency of the radio frequency signal is adjusted to a limit value.
具体的，本实例以四极杆质量分析器为例，设置四极杆长L，电极表面与四极杆中心的距离为r0，如图2所示，射频电路可升压范围100～500V，频率变化范围200～1000kHz，单次扫描总时间为t2。一个扫描周期分为两个阶段，0～t1时间段内，射频信号频率保持1000kHz不变，射频信号幅度线性扫描，从100V线性扫描至500V，电压在t1时刻达到500V，t1～t2时间段内射频信号幅度保持500V，射频信号频率扫描，从1000kHz降至200kHz。整个扫描周期离子按照质荷比从小到大的顺序依次用过四极杆，到达检测器，完成分析过程。原理上，在操作过程中保持四极杆电极上所加直流信号U相同，且离子选择在同一个q点条件下。在一个扫描周期内，首先固定射频信号频率ω相同，对射频信号幅度V由低到高扫描，由于操作q点及射频信号频率一定，四极杆中的离子会按照质荷比由低到高的顺序逐一通过四极杆，被检测器捕获。当射频电压扫描到射频电路输出最高值Vmax时，更换操作模式，保证射频信号电压保持最大值Vmax，逐步改变射频信号频率ω，使射频信号频率由高向低扫描，此时由于q点和射频电压Vmax固定，随着射频信号频率ω的不断减小，四极杆内满足条件的离子会按照质荷比由低到高的顺序依次通过，被检测器捕获。此种扫描方式无论是与射频幅度扫描还是射频频率扫描相比，均增大了相同射频条件下的离子质荷比覆盖范围。Specifically, this example takes a quadrupole mass analyzer as an example, sets the quadrupole length L, and the distance between the electrode surface and the center of the quadrupole is r 0 , as shown in FIG2 , the RF circuit can boost the voltage range of 100 to 500 V, the frequency range of 200 to 1000 kHz, and the total time of a single scan is t 2 . A scanning cycle is divided into two stages. During the time period of 0 to t 1 , the frequency of the RF signal remains unchanged at 1000 kHz, and the amplitude of the RF signal is linearly scanned from 100 V to 500 V. The voltage reaches 500 V at time t 1 , and during the time period of t 1 to t 2 , the amplitude of the RF signal remains 500 V, and the frequency of the RF signal is scanned from 1000 kHz to 200 kHz. During the entire scanning cycle, the ions pass through the quadrupole in order from small to large mass-to-charge ratio, arrive at the detector, and complete the analysis process. In principle, the DC signal U applied to the quadrupole electrode is kept the same during the operation, and the ions are selected under the same q point condition. In a scanning cycle, the RF signal frequency ω is first fixed to be the same, and the RF signal amplitude V is scanned from low to high. Since the operation q point and the RF signal frequency are fixed, the ions in the quadrupole will pass through the quadrupole one by one in the order of mass-to-charge ratio from low to high and be captured by the detector. When the RF voltage scans to the maximum value V max output by the RF circuit, the operation mode is changed to ensure that the RF signal voltage maintains the maximum value V max , and the RF signal frequency ω is gradually changed to scan the RF signal frequency from high to low. At this time, since the q point and the RF voltage V max are fixed, as the RF signal frequency ω continues to decrease, the ions that meet the conditions in the quadrupole will pass through in the order of mass-to-charge ratio from low to high and be captured by the detector. This scanning method increases the coverage range of ion mass-to-charge ratio under the same RF conditions, whether compared with RF amplitude scanning or RF frequency scanning.
实施例2Example 2
本实施例提供一种拓宽质谱仪检测质量范围的方法，包括以下步骤：This embodiment provides a method for broadening the mass detection range of a mass spectrometer, comprising the following steps:
S1，将射频信号频率和射频信号幅度调整至第一预设值；S1, adjusting the frequency and amplitude of the radio frequency signal to a first preset value;
S2，保持所述射频信号频率不变，调整所述射频信号幅度，以使所述射频信号幅度沿特定方向扫描；S2, keeping the frequency of the radio frequency signal unchanged, and adjusting the amplitude of the radio frequency signal so that the amplitude of the radio frequency signal scans along a specific direction;
S3，当所述射频信号幅度调整至第二预设值后，保持所述射频信号幅度不变，调整所述射频信号频率，以使所述射频信号频率沿特定方向扫描；S3, when the RF signal amplitude is adjusted to a second preset value, the RF signal amplitude is kept unchanged, and the RF signal frequency is adjusted so that the RF signal frequency scans along a specific direction;
S4，将所述射频信号频率重新调整至第一预设值，射频信号幅度从第二预设值调整至极限值；停止扫描，输出质量范围检测的结果。S4, readjusting the frequency of the radio frequency signal to the first preset value, and adjusting the amplitude of the radio frequency signal from the second preset value to the limit value; stopping scanning, and outputting the result of the quality range detection.
以四极杆质量分析器为例，设置四极杆长L，电极表面与四极杆中心的距离为r0，如图3所示，射频电路可升压范围100～500V，但是射频信号幅度的第二预设值为升压范围内的一个中间值，比如为300V，频率变化范围200～1000kHz，单次扫描总时间为t3。此时，可以将扫描周期分为三个阶段，0～t1时间段内，射频信号频率保持1000kHz不变，射频信号幅度线性扫描，从100V线性扫描至300V，射频信号幅度(电压)在t1时刻达到300V，t1～t2时间段内射频信号幅度保持300V，射频信号频率扫描，从1000kHz降至200kHz，t2～t3时间段内射频信号频率保持1000kHz不变，射频信号幅度线性扫描，从300V线性扫描至500V。整个扫描周期离子按照质荷比从小到大的顺序依次用过四极杆，到达检测器，完成分析过程。此种扫描方式无论是与射频幅度扫描还是射频频率扫描相比，均增大了相同射频条件下的离子质荷比覆盖范围。.Taking a quadrupole mass analyzer as an example, the length of the quadrupole is set to L, and the distance between the electrode surface and the center of the quadrupole is r 0 . As shown in FIG3 , the RF circuit can boost the voltage range of 100 to 500 V, but the second preset value of the RF signal amplitude is an intermediate value within the boost range, such as 300 V, and the frequency variation range is 200 to 1000 kHz. The total time of a single scan is t 3 . At this time, the scanning cycle can be divided into three stages. In the time period 0 to t 1 , the RF signal frequency remains unchanged at 1000 kHz, and the RF signal amplitude is linearly scanned from 100 V to 300 V. The RF signal amplitude (voltage) reaches 300 V at t 1 . In the time period t 1 to t 2 , the RF signal amplitude remains 300 V, and the RF signal frequency is scanned from 1000 kHz to 200 kHz. In the time period t 2 to t 3 , the RF signal frequency remains unchanged at 1000 kHz, and the RF signal amplitude is linearly scanned from 300 V to 500 V. During the entire scanning cycle, the ions pass through the quadrupole in order from small to large mass-to-charge ratio, reach the detector, and complete the analysis process. This scanning method increases the coverage of ion mass-to-charge ratio under the same RF conditions, whether compared with RF amplitude scanning or RF frequency scanning.
实施例3Example 3
本实施例提供一种拓宽质谱仪检测质量范围的方法，包括以下步骤：This embodiment provides a method for broadening the mass detection range of a mass spectrometer, comprising the following steps:
S1，将射频信号频率和射频信号幅度调整至第一预设值；S1, adjusting the frequency and amplitude of the radio frequency signal to a first preset value;
S2，保持所述射频信号频率不变，调整所述射频信号幅度，以使所述射频信号幅度沿特定方向扫描；S2, keeping the frequency of the radio frequency signal unchanged, and adjusting the amplitude of the radio frequency signal so that the amplitude of the radio frequency signal scans along a specific direction;
S3，当所述射频信号幅度调整至第二预设值后，保持所述射频信号幅度不变，调整所述射频信号频率至第二预设值(此第二预设值与射频信号幅度的第二预设值不同)，使所述射频信号频率沿特定方向扫描；S3, when the RF signal amplitude is adjusted to the second preset value, the RF signal amplitude is kept unchanged, and the RF signal frequency is adjusted to the second preset value (the second preset value is different from the second preset value of the RF signal amplitude), so that the RF signal frequency is scanned along a specific direction;
S4，当所述射频信号频率调整至极限值时，停止扫描，输出质量范围检测的结果。S4, when the frequency of the radio frequency signal is adjusted to a limit value, the scanning is stopped and the result of the mass range detection is output.
本实施例中，射频信号频率和射频信号幅度的第一预设值均不在调整的端点上。In this embodiment, the first preset values of the RF signal frequency and the RF signal amplitude are not at the end points of the adjustment.
本实施例提供一种拓宽质谱仪检测质量范围的方法，具体的，本实例以四极杆质量分析器为例，设置四极杆长L，电极表面与四极杆中心的距离为r0，如图4所示，射频电路可升压范围100～500V，频率变化范围200～1000kHz，单次扫描总时间为t2。一个扫描周期分为两个阶段，0～t1时间段内，射频信号频率保持800kHz不变，射频信号幅度线性扫描，从100V线性扫描至500V，电压在t1时刻达到500V，t1～t2时间段内射频信号幅度保持300V，射频信号频率扫描，从1000kHz降至200kHz。整个扫描周期离子按照质荷比从小到大的顺序依次用过四极杆，到达检测器，完成分析过程。此种扫描方式无论是与射频幅度扫描还是射频频率扫描相比，均增大了相同射频条件下的离子质荷比覆盖范围。This embodiment provides a method for broadening the mass detection range of a mass spectrometer. Specifically, this example takes a quadrupole mass analyzer as an example, sets the quadrupole length L, and the distance between the electrode surface and the center of the quadrupole is r 0 . As shown in FIG4 , the RF circuit can boost the voltage range of 100 to 500 V, the frequency range of 200 to 1000 kHz, and the total time of a single scan is t 2 . A scanning cycle is divided into two stages. In the time period of 0 to t 1 , the frequency of the RF signal remains unchanged at 800 kHz, and the RF signal amplitude is linearly scanned from 100 V to 500 V. The voltage reaches 500 V at time t 1. In the time period of t 1 to t 2 , the RF signal amplitude is maintained at 300 V, and the RF signal frequency is scanned from 1000 kHz to 200 kHz. During the entire scanning cycle, the ions pass through the quadrupole in order from small to large mass-to-charge ratio, arrive at the detector, and complete the analysis process. This scanning method increases the mass-to-charge ratio coverage of ions under the same RF conditions, whether compared with RF amplitude scanning or RF frequency scanning.
可见实施例1、2、3中的质谱仪检测质量范围的方法区别于传统的单独射频频率扫描或射频幅度扫描，结合了两种射频扫描模式，利用射频信号幅度和频率与离子质荷比之间的关系，在一个周期内分段进行射频幅度扫描和射频频率扫描，能够在相同的射频放大系统下一定程度上扩增分析范围。It can be seen that the method of detecting mass range by the mass spectrometer in Examples 1, 2, and 3 is different from the traditional single RF frequency scanning or RF amplitude scanning. It combines the two RF scanning modes and utilizes the relationship between the RF signal amplitude and frequency and the mass-to-charge ratio of ions to perform RF amplitude scanning and RF frequency scanning in segments within one cycle, which can expand the analysis range to a certain extent under the same RF amplification system.
以上述依据本申请的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项申请技术思想的范围内，进行多样的变更以及修改。本项申请的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。Based on the above ideal embodiments of this application, the relevant staff can make various changes and modifications without departing from the technical concept of this application through the above description. The technical scope of this application is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.
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