This application claims priority to and the benefit of Chinese Patent Application Serial No. 202210475642.1, filed Apr. 29, 2022, which is incorporated herein in its entirety by reference.
The present invention relates to an analytical instrument, in particular a cycloidal mass spectrometer and a method for adjusting resolution thereof.
A cycloidal mass analyzer or a cycloidal mass spectrometer composed thereof is a type of magnetic mass spectrometry, the basic principle of which has been proposed by Bleakney and Hipple in 1938. The cycloidal mass spectrometer internally distributes a magnetic field and an electric field (EB) that are uniform and orthogonal to each other, the motion trajectory of the ion to be analyzed being cycloid after entering the orthogonal field; whereas the pitch of the cycloid is determined by the mass-to-charge ratio of the ion m/z, and thus can be used for ion mass analysis. The most prominent characteristic of cycloidal mass spectrometers is the so-called “perfect focusing” characteristic in the cycloid plane, i.e.: the pitch of the ion trajectory (or focus position) is independent of the divergence of the velocity magnitude and direction of the incident ion beam; even if there is a wide spread in the velocity magnitude and direction of the incident ion beam, after each pitch, the ion beam is refocused to almost exactly the same size as the original ion beam. This is also an important advantage over other double-focus magnetic mass spectra, which tend to focus only a very small range of velocity divergence.
However, cycloidal mass spectrometers have never gained emphasis over the last 80 years. The main reason is that cycloidal mass spectrometers require very uniform magnetic and electric fields to guarantee resolution; achieving a uniform magnetic field is rather difficult and often requires huge and bulky magnets. Another reason is that cycloidal mass spectrometers focus ions only in the cycloid plane and do not bind the ions in a direction perpendicular to the cycloid plane. The resulting divergence of the ion beam allows the proportion of ions that can reach the detector to be relatively low and the sensitivity of the instrument to be greatly limited. Compared to mass spectrometers using other kinds of mass analyzers, such as ion traps, quadrupoles, time-of-flight mass spectrometers or the like, the performance of cycloidal mass spectrometers at the same volume and weight is often too low to be competitive.
In view of the above problems, the present invention provides a cycloidal mass spectrometer and a method for adjusting resolution thereof capable of solving both the miniaturization, resolution and sensitivity problems of the cycloidal mass spectrometer.
The present invention provides a cycloidal mass spectrometer comprising: a set of magnets, providing a magnetic field; two sets of electrode arrays, opposing to each other parallelly, each set of the electrode array including a plurality of strip electrodes arranged parallelly; at least one DC power supply, providing DC voltages to each set of the electrode array to form a DC electric field, the direction of the electric field being perpendicular to the direction of the magnetic field, and the electric field and the magnetic field superimposed on each other to form an electric-magnetic cross-field; an ion injection unit, configured to inject ions into the electric-magnetic cross-field, wherein said ions travel along a cycloidal trajectory in the electric-magnetic cross-field, in which the magnetic field intensity and the electric field intensity decrease simultaneously within at least part of the region in said cycloidal trajectory..
According to the technical solution, due to the non-uniformity of the magnetic field, the field intensity in the central area of the magnetic field is stronger and more uniform, whereas the intensity of the magnetic field is reduced at the outer region, the broadening of the ion beam due to the non-uniformity of the magnetic field is compensated by reducing the intensity of the electric field in the area of at least part of the cycloidal trajectory of the ion so that smaller magnets can be used to achieve the same or even better resolution than in the case of a uniform magnetic field. In addition, a radial reduction in magnetic field intensity will lead to an axial confining force field, so that ions can be focused in the axial direction, which can significantly improve the efficiency of ion transfer and the detection sensitivity.
In an alternative technical solution of the present invention, in the direction from central area to outer area of the ions' cycloidal trajectory, relative non-uniformity of the electric field formed by reduction of the electric field intensity is higher than relative non-uniformity of the magnetic field formed by reduction of the magnetic field intensity.
According to this technical solution, the construction of the electric field is relatively easy compared to the construction of the magnetic field, such as by adjusting the shape of the electrodes and adjusting the voltage applied to the electrodes to construct a desired electric field, so that the relative non-uniformity of the electric field can be flexibly adjusted according to the relative non-uniformity of the magnetic field to obtain a better compensation effect and a better resolution.
In an alternative technical solution of the invention, the relative non-uniformity of the electric field is twice of that of the magnetic field. In this case, the resolution of the mass spectrometer is not constrained by the non-uniformity of the electric-magnetic cross-field, and the mass spectrometer has a higher resolution.
In an alternative technical solution of the invention, the magnets are magnetic poles of a pair of permanent magnets, and each of the magnetic poles has a length of no more than 150 mm, a width of no more than 150 mm and a thickness of no more than 20 mm.
According to this solution, the size of the magnetic poles is small, which is suitable for miniaturized fabrication of cycloidal mass spectrometers.
In an alternative technical solution of the present invention, each of the magnetic poles has a length of no more than 60 mm, a width of no more than 60 mm and a thickness of no more than 15 mm.
According to this solution, the size of the magnetic poles is smaller, which is more suitable for miniaturized fabrication of cycloidal mass spectrometers.
In an alternative technical solution of the invention, the electric field intensity in the outer area of the ions' cycloidal trajectory is lower than that in the central area of the ions' cycloidal trajectory.
According to this solution, the reduction of the magnetic field intensity in the radial direction brings about a confining force field in the axial direction, so that the ions can be focused in the axial direction, thereby significantly improving the transfer efficiency of the ions and the sensitivity.
In an alternative technical solution of the invention, each set of the electrode array is segmented along the elongated strip electrodes, and the electric field intensity varies in the direction of the electric field by means of applying different DC voltages to segments of the electrode array.
According to this solution, the desired electric field is constructed by adjusting the voltage applied to the electrodes in a simple manner, and the electric field intensity can be flexibly adjusted to match the magnetic field intensity, thereby obtaining a better compensation effect.
In an alternative embodiment of the invention, the ions' cycloidal trajectory is a cycloidal trajectory having a plurality of periods.
According to this solution, the resolution of the mass spectrometer is improved per one cycle of ion movement, and cycloidal trajectories over multiple cycles are advantageous to significantly increase the resolution of the mass spectrometer.
An alternative embodiment of the present invention comprises a plurality of slits arranged in the ions' cycloidal trajectory.
According to this solution, the plurality of slits facilitates the simultaneous detection of a plurality of ions, and the number of species of detected ions can be flexibly adjusted as desired.
An alternative technical solution of the present invention includes an ion source located upstream of the ion injection unit, and a detector located downstream of the ions' cycloidal trajectory.
In an alternative technical solution of the present invention, a control unit for adjusting dynamically the resolution of a mass spectrum is included, the ion signal detected by the detector is transmitted to a computer to obtain the mass spectrum, and the control unit adjusts the DC voltage value applied to the electrode array according to the resolution of the mass spectrum, until the resolution of the cycloidal mass spectrometer reaches a predetermined value.
According to this solution, the spectral resolution is further adjusted by varying the DC voltage applied to the electrode array until the resolution reaches a predetermined desired value.
The present invention further provides a method for adjusting resolution of a cycloidal mass spectrometer, comprising the steps of:
Cycloidal mass analyzer 100; Magnet 1; Electrode array 2; Strip electrode 21; Ion injection unit 3; Ions' cycloidal trajectory 4; Detector 5; Ion source 6; Computer 7; Control unit 8; DC power supply 9.
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. On the basis of the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making inventive labor fall within the scope of protection of the present invention.
Referring to
In the above manner, due to the non-uniformity of the magnetic field, the field intensity in the central area of the magnetic field is stronger and more uniform, whereas the intensity of the magnetic field is reduced at the outer area, the spread width of the ion beam due to the non-uniformity of the magnetic field is compensated by reducing the intensity of the electric field in the area of at least part of the cycloidal trajectory of the ion so that smaller magnets can be used to achieve the same or even better resolution than in the case of a uniform magnetic field. In addition, a radial (the direction y) reduction in magnetic field intensity will lead to an axial confining force field, so that ions can be focused in the axial direction (the direction Z), which can significantly improve the efficiency of ion transfer and the sensitivity of the final detection.
Specifically, the basic theoretical equation for the cycloidal mass analyzer 100 to perform mass spectrometry is:
where, E is the electric field intensity, B is the magnetic field intensity (magnetic induction strength), and d is so-called “pitch”. Ions of different m/z have different pitches under the same E×B field so that mass spectra can be obtained using an array detector 5, but more often the method is to scan the electric field E so that ions of different m/z pass sequentially through an exit slit to a single point detector 5 to obtain mass spectra. If the initial spread width Δd of an ion, under a uniform magnetic field B and electric field E, the mass spectral resolution R of the ion after passing through one pitch is
From equation (2), the resolution of the mass spectrum depends on the initial spread width Δd and the pitch d of the ion beam; the initial spread width Δd is determined by the entrance slit, while the pitch d is determined by the electric field intensity. In the case where the non-uniformity of the magnetic field B and the electric field E is relatively small, the following formula can be obtained from formulae (1) and (2)
Therefore, obtaining a high resolution requires a very uniform field, as reported for example in the document “J. Am. Soc. Mass Spectrom. 2018, 29, 2, 352-359”, using a magnetic field of 110*90 mm, a magnetic field with a variation (or called “relative non-uniformity”) of <1% in the central area 43*46 mm can be obtained, the trajectory of the ions needs to be confined within the central area in order to obtain a good resolution. With conventional H-type magnet designs, the total weight of the magnet may exceed 9 kg. Even so, the resolution does not exceed 100 for ions with m/z=20. Such performance is difficult to compete with mass analyzers such as an ion trap.
However, the inventor realized that the resolution is not related to the non-uniformity of the E×B field over the full area, but rather to the non-uniformity of the E×B field over the area where the ion trajectory is located, and more precisely, to the non-uniformity of the E×B field over the width of the ion beam for ions of the same m/z along the cycloidal trajectory. That is, even though the E×B field is non-uniform over the full field area, i.e., the field experienced by a single ion during flight is non-uniform, if the spread width of the ion beam is not large, the resolution is not necessarily affected; further, by using a dedicated designed, non-uniform electric field, it is possible to compensate the ion beam spreading due to the non-uniformity of the magnetic field, so that smaller magnets can be used with the same or even better resolution than in the case of a uniform field. Also the following formula can be obtained from formulae (1) and (2),
According to formula (4), when the difference of
gets close to 0, the resolution R gets higher, accordingly, in a preferred embodiment of the present invention, the relative non-uniformity of electric field
(ΔE being the amount of variation in electric field intensity) is higher than the relative non-uniformity of magnetic field
(ΔB being the amount of variation in magnetic field intensity), mainly because of that the construction of the electric field is relatively easy compared to the construction of the magnetic field, such as by adjusting the shape of the electrodes and adjusting the voltage applied to the electrodes to construct a desired electric field, so that the relative non-uniformity of the electric field can be flexibly adjusted according to the relative non-uniformity of the magnetic field to obtain a better compensation effect and a better resolution. Further, when satisfied
i.e., tne relative non-uniformity of the electric field is twice of that of the magnetic field, the resolution will no longer be constrained by the E×B field non-uniformity.
In a preferred embodiment of the invention, the magnets are magnetic poles of a pair of permanent magnets, and each of the magnetic poles has a length of no more than 150 mm, a width of no more than 150 mm and a thickness of no more than 20 mm. The embodiments of the present invention achieve higher resolution by compensating the non-uniformity of the magnetic field with an electric field, and thus require relatively low uniformity to the magnetic field, do not require the use of a large volume of the magnetic field, and thus are suitable for miniaturization of cycloidal mass spectrometer. Further, each of the magnetic poles has a length of no more than 60 mm, a width of no more than 60 mm and a thickness of no more than 15 mm. Embodiments of the present invention allow for the use of smaller magnetic poles, allowing for miniaturization of cycloidal mass spectrometer.
As shown in
The results of computer simulations show that with an entrance slit of 100 μm, a magnetic field intensity of 0.7 T, the structure can achieve a resolution of around 500 for ions with m/z=500, i.e. essentially a unit mass resolution. If conventional uniform voltage-dividing resistor chain is used, the resolution is only about 300. In addition, the magnetic field has a variation in intensity in the plane xy (or along the radial direction), such as a decrease in the field intensity in the outer area. The decrease in the field intensity in the radial direction will lead to a confining force field in the axial direction (i.e., direction z), so that the ions can be focused in the direction z, which can significantly increase the efficiency of ion transfer and the detection sensitivity.
In a preferred embodiment of the invention, the electric field intensity in the outer area of the ions' cycloidal trajectory 4 is lower than that in the central area of the ions' cycloidal trajectory 4. The ions can be confined in the central area of the electric field, thereby obtaining better resolution.
In a preferred embodiment of the present invention, multiple slits arranged on the ions' cycloidal trajectory 4 are included. Multiple slits can facilitate detection of multiple ions simultaneously, allowing flexibility in adjusting the number of species detected as needed.
Referring to
In a second embodiment of the present invention, the relative non-uniformity of the magnet 1 is compensated with the electric field along the x-axis direction by adding a set of electrodes on each of the left and right sides of each set of electrode arrays 2 in the x-axis direction so that the size of the magnet 1 is reduced to a length of no more than 40 mm, a width of no more than 40 mm, and a thickness of no more than 10 mm.
As shown in
Referring to
In the case where the uniformity of the magnetic field and the electric field is guaranteed, a long period of ion movement is beneficial to improve the resolution; in multi-cycle motion, however, the sensitivity is significantly reduced due to axial diffusion; moreover, the multi-cycle motion obviously requires a larger volume of magnet 1 for movement of the ions. Whereas in the embodiment of the present invention, since the electric field intensity and the magnetic field intensity are simultaneously reduced, the electric field can compensate for the ion beam spreading due to the magnetic field non-uniformity and improve the resolution, therefore, the magnet 1 can be used with a relatively small volume while guaranteeing higher resolution and sensitivity. As shown in
Referring to
Referring to
While the present invention has been described with reference to the preferred embodiments, it is not intended to limit the present invention, and it is intended to cover various modifications, equivalents, and improvements within the spirit and principles of the present invention.
Number | Date | Country | Kind |
---|---|---|---|
202210475642.1 | Apr 2022 | CN | national |