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CN107144626B - Ion selectivity photodissociation device, method and instrument - Google Patents

Ion selectivity photodissociation device, method and instrument Download PDF

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CN107144626B
CN107144626B CN201610118198.2A CN201610118198A CN107144626B CN 107144626 B CN107144626 B CN 107144626B CN 201610118198 A CN201610118198 A CN 201610118198A CN 107144626 B CN107144626 B CN 107144626B
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CN107144626A (en
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田明
林茂先
江东
周鸣飞
王冠军
朱治祥
胡修稳
徐春风
张锋
戚丽
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Hefei Meyer Optoelectronic Technology Inc
Fudan University
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Abstract

本发明公开了一种离子选择性光解离装置、方法以及仪器,其中该装置包括:电极组,包括第一电极、第二电极、第三电极以及第四电极,第一电极、第二电极、第三电极以及第四电极依次并行排列,其中每个电极中间均设有圆孔,且每个电极中圆孔的中心同轴,圆孔上设置栅网,栅网用于供离子通过;其中第一电极、第二电极组成质量门,质量门用于选择特定质量数的离子;第二电极、第三电极组成解离区域,用于将通过质量门选择的离子在解离激光的照射下发生解离以产生碎片离子;第二电极、第三电极以及第四电极组成两级加速电场,用于将碎片离子进行加速,以使碎片离子达到离子检测器微通道板。该装置实现了对离子源产生的离子进行高分辨率的选择和分析。

The invention discloses an ion selective photodissociation device, method and instrument, wherein the device includes: an electrode group, including a first electrode, a second electrode, a third electrode and a fourth electrode, the first electrode, the second electrode , the third electrode and the fourth electrode are arranged in parallel in turn, wherein a round hole is arranged in the middle of each electrode, and the center of the round hole in each electrode is coaxial, and a grid is arranged on the round hole, and the grid is used for passing ions; Among them, the first electrode and the second electrode form a mass gate, and the mass gate is used to select ions with a specific mass number; the second electrode and the third electrode form a dissociation area, which is used to irradiate the ions selected by the mass gate in the dissociation laser Dissociation occurs below to generate fragment ions; the second electrode, the third electrode and the fourth electrode form a two-level accelerating electric field, which is used to accelerate the fragment ions so that the fragment ions reach the ion detector microchannel plate. The device realizes high-resolution selection and analysis of ions generated by the ion source.

Description

离子选择性光解离装置、方法以及仪器Ion selective photodissociation device, method and apparatus

技术领域technical field

本发明涉及质谱和光谱分析技术领域,尤其涉及一种离子选择性光解离装置、通过该装置进行离子选择性光解离的方法、以及一种具有该装置的仪器。The invention relates to the technical field of mass spectrometry and spectral analysis, in particular to an ion selective photodissociation device, a method for performing ion selective photodissociation through the device, and an instrument with the device.

背景技术Background technique

目前,作为分析测试科学仪器的突出代表,质谱仪具有灵敏度最高,适用性最强的优势,在科学研究和生产实践中都具有不可替代的重要作用,其应用遍及国计民生和安全信息的各个领域。质谱分析中,待测物质分子经电离后依照不同质荷比(质量与电荷之比)在电磁场控制下按空间位置和时间先后加以区分和定量分析。虽然质谱具有强大的质量分析功能,但该技术在结构测定方面具有很大的局限性,多数情况下无法直接给出被测物种的结构信息,对具有相同质量数但结构不同的同分异构体无法区分,极大地限制了质谱技术在食品安全、生物技术等方面的深入应用。At present, as an outstanding representative of analytical and testing scientific instruments, mass spectrometers have the advantages of the highest sensitivity and the strongest applicability, and play an irreplaceable important role in scientific research and production practice. In mass spectrometry, after ionization, the molecules of the substance to be measured are distinguished and quantitatively analyzed according to the spatial position and time sequence under the control of the electromagnetic field according to different mass-to-charge ratios (ratio of mass to charge). Although mass spectrometry has powerful mass analysis functions, this technology has great limitations in structure determination. In most cases, the structure information of the measured species cannot be directly given. For isomers with the same mass number but different structures The body cannot be distinguished, which greatly limits the in-depth application of mass spectrometry in food safety and biotechnology.

红外光谱是研究物质结构的最有效方法之一,每种分子都有由其组成和结构决定的特征红外光谱,据此可以对分子进行结构分析、物种鉴定以及定量测量。因此研制集红外光谱结构测定和质谱质量分析于一体的红外-质谱联用仪器将具有强大的分析测试功能,并有广泛的应用前景。然而由于传统的红外吸收光谱方法灵敏度低,不适于与质谱技术串联使用于物质结构分析。红外激光解离光谱是近年来发展的高灵敏度振动光谱方法。自从1985年诺贝尔化学奖获得者李远哲等人的红外激光解离谱实验发展到现在,红外激光解离光谱已经成为研究气相小分子及团簇化学的重要手段。红外激光解离谱(InfraredPhotodissociation Spectroscopy:IRPD)实验是通过检测母体离子的碎片强度随辐射红外激光波长变化的关系。对于母体离子AB+,当它吸收若干个红外光子,分子内部能量升高超过某些弱键的解离限,会发生解离,生成中性或者带电的碎片。对于结合能较大的团簇体系,则可以通过红外预解离(Infrared Predissociation Spectroscopy)谱探测其振动频率信息。红外预解离谱首先使研究体系AB+弱吸附n个惰性的信息原子或分子(例如Ar,He,H2等),再使体系与红外激光作用,信息Ar原子的依次解离会降低母体分子的内能,从而获得高分辨的振动谱。Infrared spectroscopy is one of the most effective methods for studying the structure of substances. Each molecule has a characteristic infrared spectrum determined by its composition and structure, based on which molecular structure analysis, species identification and quantitative measurement can be performed. Therefore, the development of an infrared-mass spectrometry instrument that integrates infrared spectroscopic structure determination and mass spectrometry mass analysis will have powerful analytical and testing functions and have broad application prospects. However, due to the low sensitivity of traditional infrared absorption spectroscopy, it is not suitable to be used in series with mass spectrometry for material structure analysis. Infrared laser dissociation spectroscopy is a highly sensitive vibrational spectroscopy method developed in recent years. Since the development of infrared laser dissociation spectroscopy experiments by Li Yuanzhe, the Nobel Prize winner in chemistry in 1985, infrared laser dissociation spectroscopy has become an important means of studying gas phase small molecules and cluster chemistry. The infrared laser dissociation spectroscopy (Infrared Photodissociation Spectroscopy: IRPD) experiment is to detect the relationship between the fragment intensity of the parent ion and the wavelength of the infrared laser radiation. For the parent ion AB+, when it absorbs several infrared photons, the internal energy of the molecule rises beyond the dissociation limit of some weak bonds, dissociation will occur, and neutral or charged fragments will be generated. For the cluster system with large binding energy, its vibrational frequency information can be detected by infrared predissociation (Infrared Predissociation Spectroscopy) spectrum. Infrared pre-dissociation spectroscopy first makes the research system AB+ weakly adsorb n inert information atoms or molecules (such as Ar, He, H2, etc.), and then makes the system interact with infrared lasers. The sequential dissociation of information Ar atoms will reduce the internal content of the parent molecule. capable of obtaining high-resolution vibrational spectra.

将质谱仪和光解离光谱仪结合起来使用的一个最大优点在于,第一,它可以分析选择离子的分子结构。其原理和实验过程是,首先根据质谱学原理,将特定质荷比的离子选择出来,然后再用光源(通常为激光)辐照被选择的离子,获得此种离子的光谱信息。第二,由于质谱是工作在高真空条件下,它可以分析一些在常温常压下不稳定的自由基,离子以及各种由非共价相互作用结合起来的亚稳态分子,如分子团簇等。一些传统光谱学方法无法研究的亚稳态分子可以用质谱-光解离谱联用的方法开展研究。One of the greatest advantages of using mass spectrometers and photodissociation spectrometers in combination is that, first, it can analyze the molecular structure of selected ions. The principle and experimental process are: firstly, according to the principle of mass spectrometry, ions with a specific mass-to-charge ratio are selected, and then a light source (usually a laser) is used to irradiate the selected ions to obtain the spectral information of the ions. Second, since mass spectrometry works under high vacuum conditions, it can analyze some unstable free radicals, ions and various metastable molecules combined by non-covalent interactions, such as molecular clusters Wait. Some metastable molecules that cannot be studied by traditional spectroscopy methods can be studied by mass spectrometry-photodissociation spectroscopy.

由于质谱在质谱仪和光解离谱仪结合使用中的主要作用是分离选择出特定的分子离子,因此,质谱仪的质量分辨能力将决定此研究方法和仪器的性能,比如说,对于质荷比非常相近的两个离子,能否将它们完全分离开是决定研究结果是否具有可靠性的唯一保证。Since the main role of mass spectrometry in the combined use of mass spectrometers and photolysis spectrometers is to separate and select specific molecular ions, the mass resolving power of mass spectrometers will determine the performance of this research method and instrument, for example, for very large mass-to-charge ratios. Whether two ions that are close to each other can be completely separated is the only guarantee to determine whether the research results are reliable.

因此,如何对离子源产生的离子进行高分辨率的选择和分析已经成为亟待解决的问题。Therefore, how to select and analyze the ions generated by the ion source with high resolution has become an urgent problem to be solved.

发明内容Contents of the invention

本发明的目的旨在至少在一定程度上解决上述的技术问题之一。The object of the present invention is to solve one of the above-mentioned technical problems at least to a certain extent.

为此,本发明的第一个目的在于提出一种离子选择性光解离装置。该装置通过一组由四片电极组成的电极组即可实现对离子源产生的离子进行高分辨质量选择和实现高分辨光解离产物质量分析,获得高质量的分子光解离光谱。Therefore, the first object of the present invention is to provide an ion selective photodissociation device. The device can realize high-resolution mass selection of ions generated by an ion source and high-resolution photodissociation product mass analysis through an electrode group composed of four electrodes, and obtain high-quality molecular photodissociation spectra.

本发明的第二个目的在于提出一种通过离子选择性光解离装置进行离子选择性光解离的方法。The second object of the present invention is to propose a method for performing ion selective photodissociation through an ion selective photodissociation device.

本发明的第三个目的在于提出一种仪器。A third object of the invention is to propose an apparatus.

为达上述目的,本发明第一方面实施例的离子选择性光解离装置,包括:电极组,所述电极组设置于离子飞行时间质谱的无场飞行区,所述电极组包括第一电极、第二电极、第三电极以及第四电极,所述第一电极、第二电极、第三电极以及第四电极依次并行排列,其中,每个电极中间均设有圆孔,且所述每个电极中圆孔的中心同轴,所述圆孔上设置栅网,所述栅网用于供离子通过;其中,所述第一电极、第二电极组成质量门,所述质量门用于选择特定质量数的离子;所述第二电极、第三电极组成解离区域,所述解离区域用于将通过所述质量门选择的离子在解离激光的照射下发生解离以产生碎片离子;所述第二电极、第三电极以及第四电极组成两级加速电场,所述两级加速电场用于将所述碎片离子进行加速,以使所述碎片离子达到离子检测器微通道板。In order to achieve the above-mentioned purpose, the ion selective photodissociation device of the embodiment of the first aspect of the present invention includes: an electrode group, the electrode group is arranged in the field-free flight area of the ion time-of-flight mass spectrometer, and the electrode group includes a first electrode , the second electrode, the third electrode and the fourth electrode, the first electrode, the second electrode, the third electrode and the fourth electrode are arranged in parallel in turn, wherein a circular hole is arranged in the middle of each electrode, and each of the electrodes The centers of the circular holes in the two electrodes are coaxial, and a grid is arranged on the circular hole, and the grid is used for passing ions; wherein, the first electrode and the second electrode form a mass gate, and the mass gate is used for Select ions with a specific mass number; the second electrode and the third electrode form a dissociation area, and the dissociation area is used to dissociate the ions selected by the mass gate under the irradiation of a dissociation laser to generate fragments Ions; the second electrode, the third electrode and the fourth electrode form a two-stage accelerating electric field, and the two-stage accelerating electric field is used to accelerate the fragment ions so that the fragment ions reach the ion detector microchannel plate .

根据本发明实施例的离子选择性光解离装置,由依次并行排列的4片电极组成的电极组构成,其中,每个电极中间均设有圆孔,且每个电极中圆孔的中心同轴,圆孔上设置栅网以供离子通过,通过第一电极、第二电极组成的质量门以选择特定质量数的离子,并通过第二电极、第三电极组成的解离区域以将通过质量门选择的离子在解离激光的照射下发生解离以产生碎片离子,以及通过第二电极、第三电极以及第四电极的组成两级加速电场以将碎片离子进行加速,以使碎片离子最终达到离子检测器微通道板。实现了通过一组由四片电极组成的电极组即可实现对离子源产生的离子进行高分辨质量选择和实现高分辨光解离产物质量分析,获得高质量的分子光解离光谱。The ion-selective photodissociation device according to the embodiment of the present invention is composed of an electrode group composed of four electrodes arranged in parallel in turn, wherein a round hole is arranged in the middle of each electrode, and the center of the round hole in each electrode is the same as axis, a grid is set on the circular hole for the ions to pass through, the mass gate composed of the first electrode and the second electrode is used to select ions with a specific mass number, and the dissociation region composed of the second electrode and the third electrode is used to pass through the mass gate. The ions selected by the mass gate are dissociated under the irradiation of the dissociation laser to generate fragment ions, and the fragment ions are accelerated by the two-stage accelerating electric field composed of the second electrode, the third electrode and the fourth electrode, so that the fragment ions Eventually it reaches the ion detector microchannel plate. The high-resolution mass selection of the ions generated by the ion source and the high-resolution photodissociation product mass analysis can be realized through an electrode group composed of four electrodes, and a high-quality molecular photodissociation spectrum can be obtained.

为达上述目的,本发明第二方面实施例的通过离子选择性光解离装置进行离子选择性光解离的方法,所述离子选择性光解离装置为本发明第一方面实施例所述的装置,所述方法包括:在样品选择和解离的过程中,当样品离子为正离子时,所述第二电极上施加负脉冲电压,控制脉冲的时序,使电压下降的时间段内,目标离子通过所述第一电极和所述第二电极,其它时间所述第二电极处于高的正电位,阻拦离子通过,其中,在被选择的离子通过所述第二电极的一瞬间,所述第二电极上电压为正高压;当选择通过的离子通过所述第二电极时,控制所述解离激光轰击所述选择通过的离子,使所述选择通过的离子产生解离,其中,所述解离激光为脉冲式,根据被选择离子的不同,控制所述解离激光的时序以使所述解离激光与离子通过所述第二电极的过程同步;控制所述第三电极上施加直流电压,以使所述第二电极和所述第四电极共同组成所述两级加速电场,以使被解离后的离子再次加速。In order to achieve the above purpose, the method for performing ion selective photodissociation through an ion selective photodissociation device according to the embodiment of the second aspect of the present invention, the ion selective photodissociation device is described in the embodiment of the first aspect of the present invention The device, the method includes: in the process of sample selection and dissociation, when the sample ions are positive ions, apply a negative pulse voltage to the second electrode, control the timing of the pulse, and make the voltage decrease during the time period, the target Ions pass through the first electrode and the second electrode, and the second electrode is at a high positive potential at other times to block the passage of ions, wherein, at the moment when the selected ions pass through the second electrode, the The voltage on the second electrode is a positive high voltage; when the selected ions pass through the second electrode, the dissociation laser is controlled to bombard the selected ions, so that the selected ions are dissociated, wherein, The dissociation laser is pulsed, and the time sequence of the dissociation laser is controlled to synchronize the process of the dissociation laser and ions passing through the second electrode according to the difference of the selected ions; DC voltage, so that the second electrode and the fourth electrode jointly form the two-level accelerating electric field, so that the dissociated ions are accelerated again.

根据本发明实施例的离子选择性光解离的方法,通过由四片电极组成的电极组即可实现对离子源产生的离子进行高分辨质量选择和实现高分辨光解离产物质量分析,获得高质量的分子光解离光谱。According to the ion selective photodissociation method of the embodiment of the present invention, the high-resolution mass selection of the ions generated by the ion source and the high-resolution photodissociation product mass analysis can be realized through the electrode group composed of four electrodes, and the obtained High-quality molecular photodissociation spectroscopy.

为达上述目的,本发明第三方面实施例的仪器,包括:激光光源,用于发射激光,以使样品在所述激光作用下电离成离子;离子调制电极,用于在施加脉冲电压下,将经过锥孔垂直正交加速进入离子调制区的离子进入加速电场;偏转电极,用于将经所述加速电场的离子进行偏转以使所述离子进入无场飞行区;本发明第一方面实施例所述的离子选择性光解离装置,所述离子选择性光解离装置置于离子飞行时间质谱的无场飞行区;检测器,用于将经过所述离子选择性光解离装置进行光解离的离子进行处理,以得到被选择的样品离子光解离后的质谱图。In order to achieve the above-mentioned purpose, the instrument of the embodiment of the third aspect of the present invention includes: a laser light source, used to emit laser light, so that the sample is ionized into ions under the action of the laser light; an ion modulation electrode, used for applying a pulse voltage, The ions that are vertically and orthogonally accelerated into the ion modulation area through the cone hole enter the accelerating electric field; the deflection electrode is used to deflect the ions passing through the accelerating electric field so that the ions enter the field-free flight area; the first aspect of the present invention is implemented The ion selective photodissociation device described in the example, the ion selective photodissociation device is placed in the field-free flight area of the ion time-of-flight mass spectrometer; the detector is used to pass through the ion selective photodissociation device The photodissociated ions are processed to obtain photodissociated mass spectra of selected sample ions.

根据本发明实施例的仪器,通过离子选择性光解离装置中由四片电极组成的电极组即可实现对离子源产生的离子进行高分辨质量选择和实现高分辨光解离产物质量分析,获得高质量的分子光解离光谱,从而可以将质谱分析和光解离分析结合起来使用,这样既可以获得分子组成的信息,又可以得到分子结构的信息。According to the instrument of the embodiment of the present invention, the high-resolution mass selection of ions generated by the ion source and the mass analysis of high-resolution photodissociation products can be realized through the electrode group composed of four electrodes in the ion selective photodissociation device, Obtain high-quality molecular photodissociation spectra, so that mass spectrometry and photodissociation analysis can be combined, so that information on molecular composition and molecular structure can be obtained.

本发明附加的方面和优点将在下面的描述中部分给出,部分将从下面的描述中变得明显,或通过本发明的实践了解到。Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.

附图说明Description of drawings

本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解,其中:The above and/or additional aspects and advantages of the present invention will become apparent and comprehensible from the description of the embodiments in conjunction with the following drawings, wherein:

图1是根据本发明一个实施例的离子选择性光解离装置的结构示意图。Fig. 1 is a schematic structural diagram of an ion selective photodissociation device according to an embodiment of the present invention.

图2是根据本发明一个实施例的离子选择性光解离的方法的流程图;Fig. 2 is the flowchart of the method for ion selective photodissociation according to one embodiment of the present invention;

图3是图1中第二电极120的脉冲序列的示例图;以及FIG. 3 is an example diagram of the pulse sequence of the second electrode 120 in FIG. 1; and

图4是根据本发明一个实施例的仪器的结构示意图。Fig. 4 is a schematic structural diagram of an instrument according to an embodiment of the present invention.

具体实施方式Detailed ways

下面详细描述本发明的实施例,所述实施例的示例在附图中示出,其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的,旨在用于解释本发明,而不能理解为对本发明的限制。Embodiments of the present invention are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference numerals designate the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the figures are exemplary and are intended to explain the present invention and should not be construed as limiting the present invention.

下面参考附图描述本发明实施例的离子选择性光解离装置、通过该装置进行离子选择性光解离的方法、以及具有该装置的仪器。The ion selective photodissociation device, the ion selective photodissociation method using the device, and the instrument with the device are described below with reference to the accompanying drawings.

图1是根据本发明一个实施例的离子选择性光解离装置的结构示意图。需要说明的是,本发明实施例的离子选择性光解离装置可应用于质谱和光谱分析技术领域中,可通过本发明实施例的离子选择性光解离装置实现离子的质量选择和光解离后碎片离子的高分辨质量分析。Fig. 1 is a schematic structural diagram of an ion selective photodissociation device according to an embodiment of the present invention. It should be noted that the ion selective photodissociation device of the embodiment of the present invention can be applied in the technical field of mass spectrometry and spectral analysis, and the mass selection and photodissociation of ions can be realized by the ion selective photodissociation device of the embodiment of the present invention High-resolution mass analysis of post-fragment ions.

如图1所示,该离子选择性光解离装置可以包括:电极组100,该电极组100可以设置于离子飞行时间质谱的无场飞行区。需要说明的是,当本发明实施例的离子选择性光解离装置应用于质谱和光谱分析仪器中时,通过飞行时间质谱的不同来决定该装置中的电极组100与质谱和光谱分析仪器中的其他部件的位置关系。例如,对于反射式飞行时间质谱而言,电极组100可位于加速和偏转电极之后,反射电场之前;对于直线式飞行时间质谱而言,电极组100位于加速和偏转电极之后,检测器之前。As shown in FIG. 1 , the ion selective photodissociation device may include: an electrode group 100 , and the electrode group 100 may be arranged in a field-free flight region of an ion time-of-flight mass spectrometer. It should be noted that when the ion selective photodissociation device of the embodiment of the present invention is applied to mass spectrometry and spectral analysis instruments, the difference between the electrode group 100 in the device and the mass spectrometry and spectral analysis instruments is determined by the difference in time-of-flight mass spectrometry. The positional relationship of other components. For example, for reflective time-of-flight mass spectrometry, the electrode set 100 can be located after the acceleration and deflection electrodes, but before the reflected electric field; for linear time-of-flight mass spectrometry, the electrode set 100 can be located after the acceleration and deflection electrodes, and before the detector.

其中,如图1所示,电极组100可包括第一电极110、第二电极120、第三电极130以及第四电极140,第一电极110、第二电极120、第三电极130以及第四电极140依次并行排列,其中,每个电极中间均设有圆孔E,且每个电极中圆孔E的中心同轴,圆孔E上设置栅网,栅网用于供离子通过。此外,在本发明的实施例中,每个电极中的圆孔E的大小不做具体限定,例如,每个电极中的圆孔E的大小可以相同,也可以不同,取决于具体的样品离子的选择和解离情况。圆孔E上的栅网的尺寸本发明也不做具体限定,例如,栅网的尺寸大小略大于圆孔E的大小,又如,栅网的大小与圆孔E的大小相同。Wherein, as shown in FIG. 1 , the electrode group 100 may include a first electrode 110, a second electrode 120, a third electrode 130, and a fourth electrode 140, and the first electrode 110, the second electrode 120, the third electrode 130, and the fourth electrode The electrodes 140 are arranged in parallel in sequence, wherein a circular hole E is provided in the middle of each electrode, and the centers of the circular holes E in each electrode are coaxial, and a grid is provided on the circular hole E for the passage of ions. In addition, in the embodiment of the present invention, the size of the circular hole E in each electrode is not specifically limited, for example, the size of the circular hole E in each electrode can be the same or different, depending on the specific sample ions selection and dissociation. The size of the grid on the circular hole E is not specifically limited in the present invention, for example, the size of the grid is slightly larger than the size of the circular hole E, and for another example, the size of the grid is the same as that of the circular hole E.

需要说明的是,在本发明的实施例中,第一电极110、第二电极120、第三电极130以及第四电极140均为平板式电极。此外,第一电极110、第二电极120、第三电极130以及第四电极140的形状可为圆形、长方形或正方形等,可以理解,根据实际需求,电极的形状还可以是其他形状。此外,每个电极的厚度、尺寸大小本发明也不做具体限定,可根据实际需求来决定。It should be noted that, in the embodiment of the present invention, the first electrode 110 , the second electrode 120 , the third electrode 130 and the fourth electrode 140 are all planar electrodes. In addition, the shape of the first electrode 110 , the second electrode 120 , the third electrode 130 and the fourth electrode 140 can be circular, rectangular or square, etc. It can be understood that the shape of the electrodes can also be other shapes according to actual needs. In addition, the thickness and size of each electrode are not specifically limited in the present invention, and can be determined according to actual needs.

如图1所示,第一电极110、第二电极120可以组成质量门,质量门可用于选择特定质量数的离子。第二电极120、第三电极130组成解离区域,解离区域用于将通过质量门选择的离子在解离激光的照射下发生解离以产生碎片离子。As shown in FIG. 1 , the first electrode 110 and the second electrode 120 can form a mass gate, and the mass gate can be used to select ions with a specific mass number. The second electrode 120 and the third electrode 130 form a dissociation area, and the dissociation area is used to dissociate the ions selected by the mass gate under the irradiation of the dissociation laser to generate fragment ions.

如图1所示,第二电极120、第三电极130以及第四电极140组成两级加速电场,两级加速电场用于将碎片离子进行再一次加速,继续飞行,以使碎片离子最终达到离子检测器微通道板(Microchannel Plate,简称为MCP)。As shown in Figure 1, the second electrode 120, the third electrode 130, and the fourth electrode 140 form a two-stage accelerating electric field, and the two-stage accelerating electric field is used to accelerate the fragment ions again and continue to fly so that the fragment ions finally reach the ion Detector Microchannel Plate (MCP for short).

需要说明的是,在本发明的实施例中,依次并行排列的电极间的距离的取值范围可为5毫米~15毫米,其中,第二电极120与第三电极130之间的距离大于第一电极110与第二电极120之间的距离,且第二电极120与第三电极130之间的距离大于第三电极130与第四电极140之间的距离。也就是说,电极间的距离在5毫米~15毫米之间,其中,用于光解离的两个电极间的距离可略大于其它电极间的距离。It should be noted that, in the embodiment of the present invention, the distance between the electrodes arranged in parallel can range from 5 millimeters to 15 millimeters, wherein the distance between the second electrode 120 and the third electrode 130 is greater than the distance between the second electrode 120 and the third electrode 130 . The distance between the first electrode 110 and the second electrode 120 , and the distance between the second electrode 120 and the third electrode 130 is greater than the distance between the third electrode 130 and the fourth electrode 140 . That is to say, the distance between the electrodes is between 5 millimeters and 15 millimeters, and the distance between two electrodes used for photodissociation can be slightly larger than the distance between other electrodes.

举例而言,如图1所示,离子源产生的不同质荷比的一系列样品离子包,按质荷比从大到小依次为A、B、C,通过加速电极和偏转电极后进入无场飞行区。在经过一段时间的自由飞行后,样品离子按照质量数从小到大的顺序依次进入电极110、120、130、140四个电极组成的电极组100。第一电极110、第二电极120组成质量门,用于特定质量数的离子的选择。在第二电极120和第三电极130之间的区域,被选择的特定质量数的离子在解离激光F的照射下发生解离,产生碎片离子G。第二电极120、第三电极130、第四电极140这三个电极组成一个两级加速电场,用于将碎片离子再一次加速,继续飞行,最终到达离子检测器微通道板。最后,经过数据采集系统记录和放大后,再通过后续的仪器处理输出,最终得到的被选择的样品离子光解离后的质谱图。For example, as shown in Figure 1, a series of sample ion packets with different mass-to-charge ratios produced by the ion source are A, B, and C in order from large to small mass-to-charge ratios, and enter the infinite field flight area. After a period of free flight, the sample ions sequentially enter the electrode group 100 composed of four electrodes 110 , 120 , 130 , and 140 in order of mass number from small to large. The first electrode 110 and the second electrode 120 form a mass gate for selecting ions with a specific mass number. In the area between the second electrode 120 and the third electrode 130 , the selected ions with a specific mass number are dissociated under the irradiation of the dissociation laser F to generate fragment ions G. The second electrode 120 , the third electrode 130 , and the fourth electrode 140 form a two-stage accelerating electric field, which is used to accelerate the fragment ions again, continue to fly, and finally reach the ion detector microchannel plate. Finally, after being recorded and amplified by the data acquisition system, and then output through subsequent instrument processing, the mass spectrum of the selected sample ion after photodissociation is finally obtained.

需要说明的是,在本发明的实施例中,在通过本发明实施例的离子选择性光解离装置进行离子选择性光解离的过程中,第一电极110以及第四电极140均为接地电极,第二电极120施加脉冲电压,第三电极130施加直流电压。其中,第二电极120施加的脉冲电压的幅值、方向本发明不做具体限定,可根据样品离子的极性和具体所选择的离子的质量数而具体设置。It should be noted that, in the embodiment of the present invention, during the ion selective photodissociation process performed by the ion selective photodissociation device of the embodiment of the present invention, both the first electrode 110 and the fourth electrode 140 are grounded electrodes, pulse voltage is applied to the second electrode 120, and DC voltage is applied to the third electrode 130. Wherein, the amplitude and direction of the pulse voltage applied by the second electrode 120 are not specifically limited in the present invention, and can be specifically set according to the polarity of the sample ions and the mass number of the specifically selected ions.

综上,本发明实施例的离子选择性光解离装置,在离子选择性光解离的过程中,仅需在同一片电极上施加不同时序的电压来达到质量选择的目的,这种结构设计既能节约高光洁度电极片,降低了制造成本,同时也有利于仪器的微型化。而且,减少了电极片,即减少了电极片上所需要的栅网,从而缩短了离子传输的距离,使得离子传输效率有大幅提高。例如,以5片电极组成的电极组与本发明四片电极组成的电极组相比为例,实验表明,四片电极的数量仍然可以保证60%以上的传输率,而五片电极的传输率只有50%(其中,单片栅网的透过率约在90%)。To sum up, in the ion selective photodissociation device of the embodiment of the present invention, in the process of ion selective photodissociation, it is only necessary to apply voltages of different timings on the same electrode to achieve the purpose of mass selection. This structural design It can not only save high-gloss electrode sheets, reduce the manufacturing cost, but also facilitate the miniaturization of instruments. Moreover, the electrode sheets are reduced, that is, the grids required on the electrode sheets are reduced, thereby shortening the ion transmission distance and greatly improving the ion transmission efficiency. For example, taking an electrode group composed of five electrodes and an electrode group composed of four electrodes in the present invention as an example, experiments show that the number of four electrodes can still guarantee a transmission rate of more than 60%, while the transmission rate of five electrodes Only 50% (among them, the transmittance of the monolithic grid is about 90%).

根据本发明实施例的离子选择性光解离装置,由依次并行排列的4片电极组成的电极组构成,其中,每个电极中间均设有圆孔,且每个电极中圆孔的中心同轴,圆孔上设置栅网以供离子通过,通过第一电极、第二电极组成的质量门以选择特定质量数的离子,并通过第二电极、第三电极组成的解离区域以将通过质量门选择的离子在解离激光的照射下发生解离以产生碎片离子,以及通过第二电极、第三电极以及第四电极的组成两级加速电场以将碎片离子进行加速,以使碎片离子最终达到离子检测器微通道板。实现了通过一组由四片电极组成的电极组即可实现对离子源产生的离子进行高分辨质量选择和实现高分辨光解离产物质量分析,获得高质量的分子光解离光谱。The ion-selective photodissociation device according to the embodiment of the present invention is composed of an electrode group composed of four electrodes arranged in parallel in turn, wherein a round hole is arranged in the middle of each electrode, and the center of the round hole in each electrode is the same as axis, a grid is set on the circular hole for the ions to pass through, the mass gate composed of the first electrode and the second electrode is used to select ions with a specific mass number, and the dissociation region composed of the second electrode and the third electrode is used to pass through the mass gate. The ions selected by the mass gate are dissociated under the irradiation of the dissociation laser to generate fragment ions, and the fragment ions are accelerated by the two-stage accelerating electric field composed of the second electrode, the third electrode and the fourth electrode, so that the fragment ions Eventually it reaches the ion detector microchannel plate. The high-resolution mass selection of the ions generated by the ion source and the high-resolution photodissociation product mass analysis can be realized through an electrode group composed of four electrodes, and a high-quality molecular photodissociation spectrum can be obtained.

为了实现上述实施例,本发明还提出了一种通过离子选择性光解离装置进行离子选择性光解离的方法,其中,该离子选择性光解离装置为上述任一项实施例所述的装置。In order to realize the above embodiments, the present invention also proposes a method for performing ion selective photodissociation through an ion selective photodissociation device, wherein the ion selective photodissociation device is described in any of the above embodiments installation.

图2是根据本发明一个实施例的离子选择性光解离的方法的流程图。如图2所示,该方法可以包括:Fig. 2 is a flowchart of a method for ion selective photodissociation according to an embodiment of the present invention. As shown in Figure 2, the method may include:

S210,在样品选择和解离的过程中,当样品离子为正离子时,第二电极上施加负脉冲电压,控制脉冲的时序,使电压下降的时间段内,目标离子通过第一电极和第二电极,其它时间第二电极处于高的正电位,阻拦离子通过,其中,在被选择的离子通过第二电极的一瞬间,第二电极上电压为正高压。S210, in the process of sample selection and dissociation, when the sample ions are positive ions, a negative pulse voltage is applied to the second electrode, and the timing of the pulse is controlled so that the target ions pass through the first electrode and the second electrode during the period of voltage drop. At other times, the second electrode is at a high positive potential to block the passage of ions, wherein, at the moment when the selected ions pass through the second electrode, the voltage on the second electrode is a positive high voltage.

S220,当选择通过的离子通过第二电极时,控制解离激光轰击选择通过的离子,使选择通过的离子产生解离,其中,解离激光为脉冲式,根据被选择离子的不同,控制解离激光的时序以使解离激光与离子通过第二电极的过程同步。S220, when the selected ions pass through the second electrode, control the dissociation laser to bombard the selected ions to dissociate the selected ions, wherein the dissociation laser is pulsed, and the dissociation is controlled according to the difference of the selected ions. Timing of the dissociation laser to synchronize the dissociation laser with the passage of ions through the second electrode.

S230,控制第三电极上施加直流电压,以使第二电极和第四电极共同组成两级加速电场,以使被解离后的离子再次加速。S230, controlling the application of a direct current voltage on the third electrode, so that the second electrode and the fourth electrode together form a two-level accelerating electric field, so that the dissociated ions are accelerated again.

为了使得本领域技术人员能够更加清楚地了解本实施例的方法,下面将结合图1以及图3对该方法进行进一步描述。In order to enable those skilled in the art to understand the method of this embodiment more clearly, the method will be further described below with reference to FIG. 1 and FIG. 3 .

举例而言,首先,如图1所示,第一电极和第四电极140均为接地电极,也就是说始终是零电位。在样品选择和解离的过程中,假设样品离子为正离子,以此为例说明第二电极120和第三电极130上的电压分布情况。其中,第二电极120上施加脉冲电压,脉冲电压序列可如图3所示,当如图1中的B离子达到第一电极110以前,第二电极120上的电压为V1,保持V1电压值大于离子的动能,就可以阻挡质荷比小于B的离子,例如离子C。假设在T1时刻,离子B达到第一电极110,此时第二电极120上的电压从V1下降到V2,使V2的电压值比离子动能低一定的数值,即可以让离子B通过第一电极110,并在第一电极110和第二电极120组成的电场作用下实现减速,当离子B通过第二电极120以后,第二电极120的电压迅速上升到V3,阻挡质荷比大于B的离子A。同时用红外激光照射质量选择并减速的离子B,生成碎片离子,第三电极130的电压可以采用直流电压,第二电极120、第三电极130以及第四电极140共同组成两级加速电场,使碎片离子和母离子获得额外的动能,而实现分离。For example, first, as shown in FIG. 1 , both the first electrode and the fourth electrode 140 are ground electrodes, that is to say, they are always at zero potential. In the process of sample selection and dissociation, it is assumed that the sample ions are positive ions, and the voltage distribution on the second electrode 120 and the third electrode 130 is described as an example. Wherein, a pulse voltage is applied on the second electrode 120, and the pulse voltage sequence can be as shown in Figure 3. Before the B ion in Figure 1 reaches the first electrode 110, the voltage on the second electrode 120 is V1, and the voltage value of V1 is maintained. Ions whose mass-to-charge ratio is smaller than B, such as ion C, can be blocked if the kinetic energy is greater than the ion. Assuming that at time T1, the ion B reaches the first electrode 110, at this time the voltage on the second electrode 120 drops from V1 to V2, so that the voltage value of V2 is lower than the ion kinetic energy by a certain value, that is, the ion B can pass through the first electrode 110, and under the action of the electric field composed of the first electrode 110 and the second electrode 120, the deceleration is realized. When the ion B passes through the second electrode 120, the voltage of the second electrode 120 rises rapidly to V3, blocking the ions whose mass-to-charge ratio is greater than B a. Simultaneously, the mass-selected and decelerated ion B is irradiated with an infrared laser to generate fragment ions. The voltage of the third electrode 130 can be a DC voltage, and the second electrode 120, the third electrode 130 and the fourth electrode 140 together form a two-stage accelerating electric field, so that Fragment ions and precursor ions gain additional kinetic energy to achieve separation.

可以看出,四片电极的组合即实现了离子的质量选择和光解离后碎片离子的高分辨质量分析。由于每一片电极上必须装载栅网以均匀电场,尽管栅网对离子的传输效率有一定影响,而四片电极的数量仍然可以保证60%以上的传输率。其中,第二电极和第三电极上的施加电压需根据具体的样品离子具体设置,其电压可以从200伏到4000伏不等,范围不受限制。It can be seen that the combination of four electrodes realizes mass selection of ions and high-resolution mass analysis of fragment ions after photodissociation. Since each electrode must be loaded with a grid to uniform the electric field, although the grid has a certain influence on the transmission efficiency of ions, the number of four electrodes can still ensure a transmission rate of more than 60%. Wherein, the applied voltage on the second electrode and the third electrode needs to be set according to specific sample ions, and the voltage can range from 200 volts to 4000 volts, and the range is not limited.

根据本发明实施例的方法,通过由四片电极组成的电极组即可实现对离子源产生的离子进行高分辨质量选择和实现高分辨光解离产物质量分析,获得高质量的分子光解离光谱。According to the method of the embodiment of the present invention, the high-resolution mass selection of the ions generated by the ion source and the high-resolution photodissociation product mass analysis can be realized through the electrode group composed of four electrodes, and high-quality molecular photodissociation can be obtained. spectrum.

为了实现上述实施例,本发明还提出了一种仪器。In order to realize the above embodiments, the present invention also proposes an instrument.

图4是根据本发明一个实施例的仪器的结构示意图。如图4所示,该仪器可以包括:激光光源410、离子调制电极420、偏转电极430、离子选择性光解离装置440以及检测器450。需要说明的是,图4给出的是离子选择性光解离装置位于一个直线式的飞行时间质谱的无场飞行区的示例,而该示例仅是为了更好对本发明的理解而给出的一种示例,而并不能作为是对本发明的具体限定。Fig. 4 is a schematic structural diagram of an instrument according to an embodiment of the present invention. As shown in FIG. 4 , the instrument may include: a laser light source 410 , an ion modulation electrode 420 , a deflection electrode 430 , an ion selective photodissociation device 440 and a detector 450 . It should be noted that what Figure 4 provides is an example in which the ion selective photodissociation device is located in the field-free flight region of a linear time-of-flight mass spectrometer, and this example is only given for a better understanding of the present invention An example, rather than a specific limitation of the present invention.

其中,激光光源410用于发射激光,以使样品在激光作用下电离成离子。离子调制电极420用于在施加脉冲电压下,将经过锥孔411垂直正交加速进入离子调制区的离子进入加速电场421。偏转电极430用于将经加速电场421的离子进行偏转以时离子进入无场飞行区。置于离子飞行时间质谱的无场飞行区的离子选择性光解离装置440,该离子选择性光解离装置440的具体功能描述可参照上述任一个实施例所述的装置的功能描述。检测器450用于将经过离子选择性光解离装置440进行光解离的离子进行处理,以得到被选择的样品离子光解离后的质谱图。Wherein, the laser light source 410 is used to emit laser light, so that the sample is ionized into ions under the action of the laser light. The ion modulation electrode 420 is used to enter the ions that are vertically and orthogonally accelerated into the ion modulation area through the cone hole 411 into the accelerating electric field 421 under the application of a pulse voltage. The deflection electrode 430 is used to deflect the ions accelerated by the electric field 421 so that the ions enter the field-free flight region. The ion selective photodissociation device 440 placed in the field-free flight region of the ion time-of-flight mass spectrometer, the specific functional description of the ion selective photodissociation device 440 can refer to the functional description of the device described in any one of the above embodiments. The detector 450 is used to process the ions photodissociated by the ion selective photodissociation device 440 to obtain the mass spectrum of the selected sample ions after photodissociation.

举例而言,如图4所示,样品L在激光光源410(或者高压脉冲放电等其他离子源)作用下电离成离子M,经过锥孔411后,正交加速进入到离子调制区,在离子调制电极420上施加的脉冲电压下,离子进入加速电场421中,经过加速,通过偏转电极430后,进入无场飞行区。在离子的飞行途径中,置有电极组,该电极组由第一电极110、第二电极120、第三电极130和第四电极140组成,用于选择离子并进行光解离,解离激光N以脉冲的形式进入第二电极120和第三电极130之间的区域,与被选择的指定的离子作用。解离后的离子离开第四电极140后,继续在无场区飞行,最终到达离子检测器微通道板(MCP)450,经过数据采集系统记录和放大后,再通过后续的仪器处理和输出,最终得到的样品离子光解离后的质谱图,进而获得高质量的分子光解离光谱。For example, as shown in Figure 4, the sample L is ionized into ions M under the action of the laser light source 410 (or other ion sources such as high-voltage pulse discharge), and after passing through the cone hole 411, it is accelerated orthogonally into the ion modulation area. Under the pulse voltage applied to the modulating electrode 420 , the ions enter the accelerating electric field 421 , are accelerated, pass through the deflecting electrode 430 , and enter the field-free flight zone. In the flight path of ions, an electrode group is placed, which is composed of a first electrode 110, a second electrode 120, a third electrode 130 and a fourth electrode 140, which are used to select ions and perform photodissociation, the dissociation laser N enters the region between the second electrode 120 and the third electrode 130 in the form of pulses, and interacts with the selected specified ions. After the dissociated ions leave the fourth electrode 140, they continue to fly in the field-free area, and finally arrive at the ion detector microchannel plate (MCP) 450. After being recorded and amplified by the data acquisition system, they are processed and output by subsequent instruments. Finally, the mass spectrum of the sample ion after photodissociation is obtained, and then a high-quality molecular photodissociation spectrum is obtained.

下面给出一个具体实施方式的描述。在该实施例中,四片电极组成的电极组的结构如下:电极组由4片直径为90毫米、厚度为0.5毫米的圆片电极组成。每片电极中心开有直径为15毫米的圆孔,第二电极120与第三电极130的间距为15毫米,其它电极间距为5.5毫米。圆孔上粘有栅网,栅网尺寸为0.32mm×0.32mm。电极组位于一个直线式的飞行时间质谱的无场飞行区中,电极组距离加速和偏转电极1.4米,距离检测器0.6米。A description of a specific embodiment is given below. In this embodiment, the structure of the electrode group composed of four electrodes is as follows: the electrode group consists of four disc electrodes with a diameter of 90 mm and a thickness of 0.5 mm. A circular hole with a diameter of 15 mm is opened in the center of each electrode, the distance between the second electrode 120 and the third electrode 130 is 15 mm, and the distance between the other electrodes is 5.5 mm. A grid is glued on the round hole, and the size of the grid is 0.32mm×0.32mm. The electrode group is located in the field-free flight region of a linear time-of-flight mass spectrometer, the electrode group is 1.4 meters away from the acceleration and deflection electrodes, and 0.6 meters away from the detector.

第一电极110、第二电极120、第三电极130和第四电极140组合的电压分布如下,以样品离子为正离子为例,第一电极110和第四电极140为接地电极,保持零电位,第二电极120上施加脉冲高压,例如,第二电极120在大多数时间内始终保持在2500V的直流电位上,直到需要选择的离子要通过时,电压迅速降低至1900V,待选择的离子通过第二电极120后,迅速升高至2500V。The voltage distribution of the combination of the first electrode 110, the second electrode 120, the third electrode 130 and the fourth electrode 140 is as follows, taking the sample ions as positive ions as an example, the first electrode 110 and the fourth electrode 140 are ground electrodes, maintaining zero potential , a pulsed high voltage is applied on the second electrode 120, for example, the second electrode 120 is kept at a DC potential of 2500V for most of the time, until the ions to be selected pass through, the voltage drops rapidly to 1900V, and the ions to be selected pass through After the second electrode 120, it is rapidly raised to 2500V.

第三电极130上施加直流电压,与第二电极120、第四电极140共同组成两级加速电场,使碎片离子和母离子获得额外的动能,而实现分离。A DC voltage is applied to the third electrode 130 to form a two-stage accelerating electric field together with the second electrode 120 and the fourth electrode 140 , so that fragment ions and parent ions can obtain additional kinetic energy to achieve separation.

根据本发明实施例的仪器,通过离子选择性光解离装置中由四片电极组成的电极组即可实现对离子源产生的离子进行高分辨质量选择和实现高分辨光解离产物质量分析,获得高质量的分子光解离光谱,从而可以将质谱分析和光解离分析结合起来使用,这样既可以获得分子组成的信息,又可以得到分子结构的信息。According to the instrument of the embodiment of the present invention, the high-resolution mass selection of ions generated by the ion source and the mass analysis of high-resolution photodissociation products can be realized through the electrode group composed of four electrodes in the ion selective photodissociation device, Obtain high-quality molecular photodissociation spectra, so that mass spectrometry and photodissociation analysis can be combined, so that information on molecular composition and molecular structure can be obtained.

在本发明的描述中,需要理解的是,术语“中心”、“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发明和简化描述,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发明的限制。In describing the present invention, it is to be understood that the terms "center", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate The orientation or positional relationship is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the referred device or element must have a specific orientation or be configured in a specific orientation. and operation, and therefore should not be construed as limiting the invention.

此外,术语“第一”、“第二”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”的特征可以明示或者隐含地包括至少一个该特征。在本发明的描述中,“多个”的含义是至少两个,例如两个,三个等,除非另有明确具体的限定。In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, the features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In the description of the present invention, "plurality" means at least two, such as two, three, etc., unless otherwise specifically defined.

在本说明书的描述中,参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外,在不相互矛盾的情况下,本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。In the description of this specification, descriptions with reference to the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features described in connection with the embodiment or example , structure, material or feature is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the described specific features, structures, materials or characteristics may be combined in any suitable manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine different embodiments or examples and features of different embodiments or examples described in this specification without conflicting with each other.

流程图中或在此以其他方式描述的任何过程或方法描述可以被理解为,表示包括一个或更多个用于实现特定逻辑功能或过程的步骤的可执行指令的代码的模块、片段或部分,并且本发明的优选实施方式的范围包括另外的实现,其中可以不按所示出或讨论的顺序,包括根据所涉及的功能按基本同时的方式或按相反的顺序,来执行功能,这应被本发明的实施例所属技术领域的技术人员所理解。Any process or method descriptions in flowcharts or otherwise described herein may be understood to represent modules, segments or portions of code comprising one or more executable instructions for implementing specific logical functions or steps of the process , and the scope of preferred embodiments of the invention includes alternative implementations in which functions may be performed out of the order shown or discussed, including substantially concurrently or in reverse order depending on the functions involved, which shall It is understood by those skilled in the art to which the embodiments of the present invention pertain.

在流程图中表示或在此以其他方式描述的逻辑和/或步骤,例如,可以被认为是用于实现逻辑功能的可执行指令的定序列表,可以具体实现在任何计算机可读介质中,以供指令执行系统、装置或设备(如基于计算机的系统、包括处理器的系统或其他可以从指令执行系统、装置或设备取指令并执行指令的系统)使用,或结合这些指令执行系统、装置或设备而使用。就本说明书而言,"计算机可读介质"可以是任何可以包含、存储、通信、传播或传输程序以供指令执行系统、装置或设备或结合这些指令执行系统、装置或设备而使用的装置。计算机可读介质的更具体的示例(非穷尽性列表)包括以下:具有一个或多个布线的电连接部(电子装置),便携式计算机盘盒(磁装置),随机存取存储器(RAM),只读存储器(ROM),可擦除可编辑只读存储器(EPROM或闪速存储器),光纤装置,以及便携式光盘只读存储器(CDROM)。另外,计算机可读介质甚至可以是可在其上打印所述程序的纸或其他合适的介质,因为可以例如通过对纸或其他介质进行光学扫描,接着进行编辑、解译或必要时以其他合适方式进行处理来以电子方式获得所述程序,然后将其存储在计算机存储器中。The logic and/or steps represented in the flowcharts or otherwise described herein, for example, can be considered as a sequenced listing of executable instructions for implementing logical functions, can be embodied in any computer-readable medium, For use with instruction execution systems, devices, or devices (such as computer-based systems, systems including processors, or other systems that can fetch instructions from instruction execution systems, devices, or devices and execute instructions), or in conjunction with these instruction execution systems, devices or equipment used. For the purposes of this specification, a "computer-readable medium" may be any device that can contain, store, communicate, propagate or transmit a program for use in or in conjunction with an instruction execution system, device or device. More specific examples (non-exhaustive list) of computer-readable media include the following: electrical connection with one or more wires (electronic device), portable computer disk case (magnetic device), random access memory (RAM), Read Only Memory (ROM), Erasable and Editable Read Only Memory (EPROM or Flash Memory), Fiber Optic Devices, and Portable Compact Disc Read Only Memory (CDROM). In addition, the computer-readable medium may even be paper or other suitable medium on which the program can be printed, since the program can be read, for example, by optically scanning the paper or other medium, followed by editing, interpretation or other suitable processing if necessary. The program is processed electronically and stored in computer memory.

应当理解,本发明的各部分可以用硬件、软件、固件或它们的组合来实现。在上述实施方式中,多个步骤或方法可以用存储在存储器中且由合适的指令执行系统执行的软件或固件来实现。例如,如果用硬件来实现,和在另一实施方式中一样,可用本领域公知的下列技术中的任一项或他们的组合来实现:具有用于对数据信号实现逻辑功能的逻辑门电路的离散逻辑电路,具有合适的组合逻辑门电路的专用集成电路,可编程门阵列(PGA),现场可编程门阵列(FPGA)等。It should be understood that various parts of the present invention can be realized by hardware, software, firmware or their combination. In the embodiments described above, various steps or methods may be implemented by software or firmware stored in memory and executed by a suitable instruction execution system. For example, if implemented in hardware, as in another embodiment, it can be implemented by any one or combination of the following techniques known in the art: Discrete logic circuits, ASICs with suitable combinational logic gates, programmable gate arrays (PGAs), field programmable gate arrays (FPGAs), etc.

本技术领域的普通技术人员可以理解实现上述实施例方法携带的全部或部分步骤是可以通过程序来指令相关的硬件完成,所述的程序可以存储于一种计算机可读存储介质中,该程序在执行时,包括方法实施例的步骤之一或其组合。Those of ordinary skill in the art can understand that all or part of the steps carried by the methods of the above embodiments can be completed by instructing related hardware through a program, and the program can be stored in a computer-readable storage medium. During execution, one or a combination of the steps of the method embodiments is included.

此外,在本发明各个实施例中的各功能单元可以集成在一个处理模块中,也可以是各个单元单独物理存在,也可以两个或两个以上单元集成在一个模块中。上述集成的模块既可以采用硬件的形式实现,也可以采用软件功能模块的形式实现。所述集成的模块如果以软件功能模块的形式实现并作为独立的产品销售或使用时,也可以存储在一个计算机可读取存储介质中。In addition, each functional unit in each embodiment of the present invention may be integrated into one processing module, each unit may exist separately physically, or two or more units may be integrated into one module. The above-mentioned integrated modules can be implemented in the form of hardware or in the form of software function modules. If the integrated modules are realized in the form of software function modules and sold or used as independent products, they can also be stored in a computer-readable storage medium.

上述提到的存储介质可以是只读存储器,磁盘或光盘等。尽管上面已经示出和描述了本发明的实施例,可以理解的是,上述实施例是示例性的,不能理解为对本发明的限制,本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。The storage medium mentioned above may be a read-only memory, a magnetic disk or an optical disk, and the like. Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and those skilled in the art can make the above-mentioned The embodiments are subject to changes, modifications, substitutions and variations.

Claims (7)

1.一种离子选择性光解离装置,其特征在于,包括:1. An ion selective photodissociation device, characterized in that, comprising: 电极组,所述电极组设置于离子飞行时间质谱的无场飞行区,所述电极组包括第一电极、第二电极、第三电极以及第四电极,所述第一电极、第二电极、第三电极以及第四电极依次并行排列,其中,每个电极中间均设有圆孔,且所述每个电极中圆孔的中心同轴,所述圆孔上设置栅网,所述栅网用于供离子通过;其中,所述栅网的尺寸大小不小于所述圆孔的尺寸大小;An electrode group, the electrode group is arranged in the field-free flight region of the ion time-of-flight mass spectrometer, the electrode group includes a first electrode, a second electrode, a third electrode and a fourth electrode, the first electrode, the second electrode, The third electrode and the fourth electrode are arranged in parallel sequentially, wherein a circular hole is arranged in the middle of each electrode, and the center of the circular hole in each electrode is coaxial, and a grid is arranged on the circular hole, and the grid is Used to allow ions to pass through; wherein, the size of the grid is not smaller than the size of the circular hole; 其中,所述第一电极、第二电极组成质量门,所述质量门用于选择特定质量数的离子;Wherein, the first electrode and the second electrode form a mass gate, and the mass gate is used to select ions of a specific mass number; 所述第二电极、第三电极组成解离区域,所述解离区域用于将通过所述质量门选择的离子在解离激光的照射下发生解离以产生碎片离子;The second electrode and the third electrode form a dissociation area, and the dissociation area is used to dissociate the ions selected by the mass gate under the irradiation of a dissociation laser to generate fragment ions; 所述第二电极、第三电极以及第四电极组成两级加速电场,所述两级加速电场用于将所述碎片离子进行加速,以使所述碎片离子达到离子检测器微通道板。The second electrode, the third electrode and the fourth electrode form a two-stage accelerating electric field, and the two-stage accelerating electric field is used to accelerate the fragment ions so that the fragment ions reach the ion detector microchannel plate. 2.如权利要求1所述的离子选择性光解离装置,其特征在于,在通过所述离子选择性光解离装置进行离子选择性光解离的过程中,所述第一电极以及所述第四电极均为接地电极,所述第二电极施加脉冲电压,所述第三电极施加直流电压。2. ion selective photodissociation device as claimed in claim 1, is characterized in that, in the process of carrying out ion selective photodissociation by said ion selective photodissociation device, said first electrode and said first electrode The fourth electrodes are all ground electrodes, pulse voltage is applied to the second electrode, and DC voltage is applied to the third electrode. 3.如权利要求1所述的离子选择性光解离装置,其特征在于,所述第一电极、第二电极、第三电极以及第四电极均为平板式电极。3 . The ion selective photodissociation device according to claim 1 , wherein the first electrode, the second electrode, the third electrode and the fourth electrode are all planar electrodes. 4.如权利要求1所述的离子选择性光解离装置,其特征在于,所述第一电极、第二电极、第三电极以及第四电极的形状为圆形、或长方形。4. The ion selective photodissociation device according to claim 1, characterized in that, the shapes of the first electrode, the second electrode, the third electrode and the fourth electrode are circular or rectangular. 5.如权利要求1所述的离子选择性光解离装置,其特征在于,所述依次并行排列的电极间的距离的取值范围为5毫米~15毫米,其中,所述第二电极与所述第三电极之间的距离大于所述第一电极与所述第二电极之间的距离,且所述第二电极与所述第三电极之间的距离大于所述第三电极与所述第四电极之间的距离。5. The ion-selective photodissociation device according to claim 1, characterized in that, the range of the distance between the successively parallel electrodes is 5 millimeters to 15 millimeters, wherein the second electrode and The distance between the third electrodes is greater than the distance between the first electrode and the second electrode, and the distance between the second electrode and the third electrode is greater than the distance between the third electrode and the second electrode The distance between the fourth electrodes. 6.一种通过如权利要求1至5中任一项所述的离子选择性光解离装置进行离子选择性光解离的方法,其特征在于,包括以下步骤:6. A method for carrying out ion selective photodissociation by the ion selective photodissociation device according to any one of claims 1 to 5, characterized in that, comprising the following steps: 在样品选择和解离的过程中,当样品离子为正离子时,所述第二电极上施加负脉冲电压,控制脉冲的时序,使电压下降的时间段内,目标离子通过所述第一电极和所述第二电极,其它时间所述第二电极处于高的正电位,阻拦离子通过,其中,在被选择的离子通过所述第二电极的一瞬间,所述第二电极上电压为正高压;In the process of sample selection and dissociation, when the sample ions are positive ions, a negative pulse voltage is applied to the second electrode, and the timing of the pulse is controlled so that the target ions pass through the first electrode and the The second electrode, at other times, the second electrode is at a high positive potential to block the passage of ions, wherein, at the moment when the selected ions pass through the second electrode, the voltage on the second electrode is a positive high voltage ; 当选择通过的离子通过所述第二电极时,控制所述解离激光轰击所述选择通过的离子,使所述选择通过的离子产生解离,其中,所述解离激光为脉冲式,根据被选择离子的不同,控制所述解离激光的时序以使所述解离激光与离子通过所述第二电极的过程同步;When the selected ions pass through the second electrode, the dissociation laser is controlled to bombard the selected ions to dissociate the selected ions, wherein the dissociation laser is pulsed, according to Depending on the selected ions, controlling the timing of the dissociation laser to synchronize the process of the dissociation laser and ions passing through the second electrode; 控制所述第三电极上施加直流电压,以使所述第二电极和所述第四电极共同组成所述两级加速电场,以使被解离后的离子再次加速。Applying a DC voltage to the third electrode is controlled so that the second electrode and the fourth electrode jointly form the two-level accelerating electric field, so that the dissociated ions are accelerated again. 7.一种仪器,其特征在于,包括:7. An instrument, characterized in that, comprising: 激光光源,用于发射激光,以使样品在所述激光作用下电离成离子;A laser light source for emitting laser light so that the sample is ionized into ions under the action of the laser light; 离子调制电极,用于在施加脉冲电压下,将经过锥孔垂直正交加速进入离子调制区的离子进入加速电场;The ion modulation electrode is used to enter the ions that are vertically and orthogonally accelerated into the ion modulation area through the cone hole into the accelerating electric field under the applied pulse voltage; 偏转电极,用于将经所述加速电场的离子进行偏转以使所述离子进入无场飞行区;a deflection electrode, configured to deflect ions passing through the accelerating electric field so that the ions enter a field-free flight zone; 如权利要求1至5中任一项所述的离子选择性光解离装置,所述离子选择性光解离装置置于离子飞行时间质谱的无场飞行区;The ion selective photodissociation device according to any one of claims 1 to 5, said ion selective photodissociation device is placed in the field-free flight region of ion time-of-flight mass spectrometry; 检测器,用于将经过所述离子选择性光解离装置进行光解离的离子进行处理,以得到被选择的样品离子光解离后的质谱图。The detector is used to process the ions photodissociated by the ion selective photodissociation device, so as to obtain the mass spectrum of the selected sample ions after photodissociation.
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