Switchable ion focusing screening and fragmentation device
Technical Field
The invention relates to the technical field of mass spectrometers, in particular to a switchable ion focusing screening and fragmentation device.
Background
In accordance with the principle by which mass spectrometers operate, at least one ion focusing device is typically included for efficient transfer of ions from the ion source to the mass analyser. Conventional ion focusing devices mainly include two types: an ion funnel using a stacked ring electrode, a multipole using a quadrupole field or a multipole using a multipole field. The use of ion funnels or multipole rods as transmission devices has certain disadvantages, such as: vacuum tolerance, mass discrimination effects, neutral ion interference, and the like. To some extent, there are instruments that use ion funnels in conjunction with multipole rod technology, but because of the longer transport distances, more ion loss occurs.
In the analysis of complex samples, multi-stage mass spectrometry is often used to obtain more structural information and reduce the influence of non-target ions. Ion collision induced dissociation is an ion fragmentation method widely used at present, and the specific implementation method is to control the ion kinetic energy under the condition of higher air pressure to enable the ion kinetic energy to collide with background gas molecules to further fragment, refocus and transmit the fragmented ions to a mass analyzer for analysis. A more common ion collision induced dissociation device is a linear ion trap developed based on quadrupole technology. However, this approach has problems with neutral particle interference.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art, and providing a switchable ion focusing screening and fragmentation device, which can provide certain screening and fragmentation functions while improving ion transmission efficiency.
The purpose of the invention can be realized by the following technical scheme:
a switchable ion focusing screening and fragmentation device comprises two metal pole piece group arrays which are arranged in series and perpendicular to an ion transmission direction, a power supply device used for supplying power to the two metal pole piece group arrays which are arranged in series, and a connecting device used for fixing the two metal pole piece group arrays which are arranged in series, wherein each metal pole piece group array is respectively provided with at least one group of pole piece groups which are arranged in the axial direction, the power supply device applies sequentially increasing or decreasing direct current voltage to each group of pole piece groups along the ion transmission direction so as to provide ion horizontal kinetic energy control, and meanwhile, the power supply device applies alternating current RF radio frequency voltage to metal electrodes in each group of pole pieces and between groups.
In the two metal pole piece group arrays connected in series, the first metal pole piece group array comprises one or more groups of pole piece groups with the same radius of inscribed circles, the second metal pole piece group array comprises one or more groups of pole piece groups with the same radius of inscribed circles, and each pole piece group of each metal pole piece group array is respectively composed of four metal pole pieces which are uniformly and symmetrically placed and have the same shape.
The power supply device adopts an ion funnel electric field mode, a quadrupole field power supply mode or a power supply mode combining the ion funnel electric field mode and the quadrupole field power supply mode. When the device operates in an ion funnel electric field mode, the directions of alternating current RF radio frequency voltages applied to axially adjacent metal pole pieces in the metal pole piece group array are opposite, the directions of the alternating current RF radio frequency voltages applied to the metal pole pieces in each pole piece group are the same, the metal pole pieces of each pole piece group form an alternating current radio frequency electric field, ions along the transmission direction are subjected to the action of the alternating current radio frequency electric field to reduce the ion kinetic energy, and then the ion cooling focusing is realized. When the device operates in a quadrupole field power supply mode, the directions of alternating current RF radio frequency voltages applied to axially adjacent pole pieces in the metal pole piece group array are the same, the directions of the alternating current RF radio frequency voltages applied between the metal pole pieces in each pole piece group are opposite, an alternating current radio frequency electric field is formed between the metal pole pieces of the pole piece group, and the direct current alternating current voltages are adjusted by combining a Mathieu equation to realize ion screening and focusing, so that target ions pass through the device. When the device operates in a power supply mode combining an ion funnel electric field mode and a quadrupole field power supply mode, the directions of alternating current RF radio frequency voltages applied to axially adjacent metal pole pieces in the metal pole piece group array are opposite, the directions of the alternating current RF radio frequency voltages applied between the metal pole pieces of each pole piece group are opposite, the metal pole pieces of the pole piece groups form a mixed electric field in the two modes, and the ion transmission rate is improved.
Further, when the device is operated in a quadrupole field mode, the gate electrode is used for controlling the rotation motion of ions in the device, and the ions collide with gas molecules and are fragmented under the combination of vacuum conditions.
Furthermore, the power supply device comprises a direct current power supply group adopting resistance voltage division and an alternating current power supply group adopting a capacitor to isolate direct current.
Furthermore, the connecting device comprises a base, a metal support which is fixed on the base and used for fixing two groups of metal pole piece group arrays, and insulating materials are arranged on the surface of the metal support, and non-metal insulating gaskets which are arranged among the pole piece groups and used for realizing separation.
Furthermore, the direct current voltage is-800- +800V, the alternating current RF radio frequency voltage is-2000- +2000V, and the frequency is 1 KHz-10 MH.
Compared with the prior art, the switchable ion focusing screening and fragmentation device provided by the invention at least comprises the following beneficial effects:
1) when the ion funnel operates in a mixed field mode of a quadrupole field and an ion funnel electric field, a multipole rod ion transmission technology and an ion funnel ion transmission technology can be combined, so that the ion transmission efficiency can be effectively improved;
2) when the ion screening device operates in a quadrupole mode, a Mathieu equation is utilized to adjust proper direct current and alternating current voltage, so that the ion screening effect can be achieved;
3) the invention can simulate the operation of the linear ion trap by matching with the AND gate circuit, and provides the ion fragmentation function.
4) The invention provides various internal shapes of the metal pole piece group, different shapes can be selected according to the use requirement to apply different electric fields, and different electric field application modes are provided to achieve different purposes.
Drawings
FIG. 1 is a schematic diagram of a switchable ion focusing screening and fragmentation apparatus according to an embodiment;
FIG. 2 is a schematic structural diagram of a metal plate set in FIG. 1;
FIG. 3 is a schematic diagram of another embodiment of a switchable ion focusing screening and fragmentation device;
FIG. 4 is a schematic structural view of the convex metal plate set in FIG. 3;
FIG. 5 is a schematic diagram illustrating a third configuration of the switchable ion focusing screening and fragmentation device of the embodiment;
fig. 6 is a schematic structural view of the metal plate assembly with an outer convex hyperboloid shape in fig. 5;
FIG. 7 is a side view of a second metal pole piece array with a concave circular pole piece array and sequentially decreasing inner diameters of the pole piece arrays;
FIG. 8 is a side view structural diagram of a second metal pole piece group array in which pole piece groups are convex circular and the inner diameters of the pole piece groups are sequentially reduced;
FIG. 9 is a side view structural diagram of a second metal pole piece array in which a convex hyperboloid-shaped pole piece group is adopted and the inner diameters of the pole piece groups are sequentially reduced;
FIG. 10 is a schematic diagram of the power supply for the device of the present invention operating in the ion funnel electric field mode;
FIG. 11 is a schematic diagram of the power supply for the device of the present invention operating in quadrupole mode;
FIG. 12 is a schematic diagram of the power supply of the apparatus of the present invention operating in a mixed field mode combining a quadrupole field with an ion funnel field;
FIG. 13 is a mass spectrum obtained when the apparatus of the present invention is used for focusing screening in the example;
FIG. 14 is a mass spectrum obtained by fragmentation of the device of the invention in an example;
the reference numbers in the figures indicate:
1. the device comprises a metal pole piece group array 11, a metal pole piece group 111, a metal pole piece 2, a power supply device 3, a connecting device 31, a base 32, a non-metal insulating gasket 33 and a mounting opening.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of protection of the present invention.
Examples
The invention relates to a switchable ion focusing screening and fragmentation device, which can improve the defects of the existing ion focusing device and effectively solve the problems of large loss and neutral ion interference of ions in the transmission process between different vacuum environments. Meanwhile, based on a structure similar to that of a linear ion trap, the ion screening fragmentation effect can be achieved.
According to actual requirements, when all ion information from an ion source needs to be analyzed, the ion funnel electric field mode can be adopted for operation, so that the ion passing rate is maximized, the loss in the transmission process is reduced, and the sensitivity is increased; when the information of a specific ion in all ions from the ion source needs to be analyzed, the ion source can operate in a quadrupole field mode, and the Mathieu equation is utilized to calculate the appropriate alternating current voltage and direct current voltage, so that only target ions can pass through, and the interference of other non-target ions is reduced; in addition, the device can also provide the function of ion fragmentation when the ion fragment information needs to be analyzed. The switchable ion focusing screening and fragmentation function makes the ion focusing screening and fragmentation function have industrial application value.
The device comprises two groups of metal pole piece group arrays, a power supply device and a connecting device.
The two groups of metal pole piece groups are connected in series and are arranged in a direction perpendicular to the ion transmission direction. The first metal pole piece group array comprises one or more axially arranged pole piece groups with the same inscribed circle radius, and the second metal pole piece group array comprises one or more axially arranged pole piece groups with the constantly changing inscribed circle radius. As a preferred scheme, the second metal pole piece group array is arranged behind the first metal pole piece group array, and the distance between the pole piece groups of the two groups of metal pole piece group arrays, the distance between the last group of pole piece group of the first metal pole piece group array and the distance between the first group of pole piece group of the second metal pole piece group array are the same. The pole pieces of the first metal pole piece group array and the second metal pole piece group array are stainless steel, aluminum alloy or printed circuit boards.
As shown in fig. 2, each of the plate groups of each of the metal plate group arrays is composed of four metal plates 111 which are uniformly and symmetrically arranged and have the same shape, and the radius of the inscribed circle of each of the metal plate groups ranges from 0.1 cm to 10 cm. The inner shape of the metal pole piece 111 is convex round, concave round or convex hyperboloid for generating the required electric field. Each metal pole piece 111 is provided with a projection provided toward the outside for applying a voltage. The thickness size range of the metal pole piece group is as follows: 0.1-1 cm. The interval size range among the metal pole piece groups is as follows: 0.1-2 cm. The change rule of the radius of the inscribed circle of the second metal pole piece group array follows a linear, parabolic or hyperbolic rule. Fig. 7 to 9 show side view structures of a second metal pole piece group array which adopts pole piece groups with three different shapes and the radius of the inscribed circle of the pole piece group is reduced in sequence.
The power supply device provides direct current and alternating current voltages for the first metal pole piece group array and the second metal pole piece group array, applies sequentially increasing or decreasing direct current voltage to each pole piece group along the ion transmission direction to provide ion horizontal kinetic energy control, and meanwhile, the electrification of the RF radio frequency voltage applied to the metal electrodes in the pole piece groups and between the metal electrodes can be controlled according to different working modes. The direct current voltage can be freely adjusted according to the control requirement of the ion horizontal kinetic energy, and the RF alternating current voltage can be freely adjusted according to different requirements of an operation mode, focusing fragmentation and the like. The power supply part adopts a printed circuit board to weld a resistor for voltage division and a capacitor for DC blocking, in the embodiment, the DC voltage is 15V-80V, the RF voltage is 200Vpp, and the RF frequency is 400 kHz.
Preferably, the power supply device includes a printed circuit board, a resistor for voltage division and a capacitor for dc blocking. The range of the applied direct current voltage is-800 to +800V, the applied radio frequency RF voltage is-2000 to +2000V, and the frequency is 1kHz to 10 MHz.
In this embodiment, as shown in fig. 1 to fig. 2, the metal pole piece set array 1 is perpendicular to the ion transmission direction, in this embodiment, the metal pole piece set array 1 is composed of 20 metal pole piece sets 11, wherein the first metal pole piece set array includes 10 pole piece sets with the same radius of the inner tangent circle, and the second metal pole piece set array includes 10 pole piece sets with the radius of the inner tangent circle reduced by the parabolic line. In this embodiment, as shown in fig. 3 to 6, each metal plate set 11 may also be a convex round shape or a convex hyperboloid shape. The convex circular metal pole piece set shown in fig. 4 is the lowest in processing and installation difficulty, and provides the performance slightly inferior to that of the convex hyperbolic metal pole piece set shown in fig. 6 when the quadrupole field mode is operated, and the metal pole piece set shown in fig. 2 can provide the maximum transmission efficiency when the ion funnel electric field mode is operated. The device can be designed into different shapes according to actual requirements.
The power supply device supplies power to the metal plate group array 1, provides three different RF ac radio frequency connection modes as shown in fig. 10-12 according to different working modes, and fig. 10 is a power supply schematic diagram of the device operating in an ion funnel electric field mode; FIG. 11 is a schematic diagram of the power supply for the device of the present invention operating in quadrupole mode; fig. 12 is a schematic diagram of the power supply of the inventive device operating in a mixed field mode combining a quadrupole field with an ion funnel field.
When the ion funnel electric field mode operates, the directions of the RF voltages applied to the axially adjacent pole pieces in the same metal pole piece group array are opposite, and the directions of the RF voltages between the pole piece groups are the same, so that an alternating-current radio-frequency electric field is formed between the pole piece groups. When the quadrupole field mode operates, the directions of RF voltages applied to axially adjacent pole pieces in the same metal pole piece group array are the same, the directions of the RF voltages of all adjacent pole pieces in the pole piece group are opposite, and an alternating-current radio-frequency electric field is formed between the pole pieces of the pole piece group; when the mixed field mode operation combining the quadrupole field and the ion funnel electric field is operated, the directions of the RF voltages of the adjacent pole pieces in the same pole piece group and each pole piece group are opposite.
When the power supply connection is as shown in fig. 10, when the device operates in an ion funnel electric field mode, the electric field can be used for enabling ions to be subjected to the action of an alternating-current radio-frequency electric field along the transmission direction to reduce the ion kinetic energy so as to achieve the effect of ion cooling and focusing, and the applied voltage can be optimized aiming at different target ions according to the difference of ion mass-to-charge ratios and collision cross sections, so that the ion transmission efficiency is maximized. When the power supply connection is as shown in fig. 11, the device operates in a quadrupole mode, and can adjust a suitable dc/ac voltage by using a Mathieu equation to achieve an ion screening and focusing effect, so that only target ions can pass through the device as the prior art, which is not described in detail in this embodiment; when the ion-generating device is matched with the gate electrode, the ion can be controlled to rotate in the device, and the ion can collide with gas molecules under proper vacuum conditions, so that the fragmentation effect is achieved. When the power supply is connected as shown in fig. 12, the device operates in a mixed field mode of a quadrupole field and an ion funnel field, and can provide an electric field combining the former two modes to provide better ion cooling focusing effect, so that the ion transmission efficiency is further optimized. The switchable ion focusing screening and fragmentation device provided by the invention can switch different working modes according to requirements.
Different results can be obtained by adopting different working modes, and referring to fig. 13 and 14, different mass spectrograms obtained when the embodiment of the invention plays a focusing screening role and a fragmentation role can be obtained. Fig. 13 is a mass spectrogram of a reserpine sample obtained by matching with a mass spectrometer when the focusing and screening device is used for focusing and screening, wherein the visible spectrogram is relatively pure, a reserpine peak with an M/Z of 609 is obviously visible, and interference peak values of the rest parts are relatively low. FIG. 14 is a mass spectrum of a reserpine sample obtained by cooperation with a mass spectrometer when the fragmentation function is performed, and it can be seen that a plurality of reserpine fragment ion peaks are detected in addition to the reserpine peak with an M/Z of 609.
The connection means comprises a base 31, a metal bracket and a non-metallic insulating gasket 32. The metal support is provided with a surface insulating material (not shown in the figures) and fixed on the base 31, and the pole pieces of each group of the two groups of metal pole piece group arrays are provided with mounting openings 33 for mounting on the metal support. The metal bracket is provided with an installation mechanism matched with the installation opening in position and size, and the two groups of metal pole piece group arrays are fixed through the installation opening and the installation mechanism. The pole piece groups are isolated by adopting a non-metal insulating gasket 32.
In this embodiment, as a preferred scheme, the metal bracket is a cylindrical metal bracket with a surface insulating material, correspondingly, the mounting opening is circular, and the size of the mounting opening is matched with the corresponding cylindrical mounting structure of the metal bracket, and the design of the cylindrical metal bracket and the circular mounting opening can provide a more stable and reliable connection relationship.
When the ion funnel operates in a mixed field mode of a quadrupole field and an ion funnel electric field, a multipole rod ion transmission technology and an ion funnel ion transmission technology can be combined, so that the ion transmission efficiency can be effectively improved; when the ion screening device operates in a quadrupole mode, a Mathieu equation is utilized to adjust proper direct current and alternating current voltage, so that the ion screening effect can be achieved; and the work of the linear ion trap is simulated through the cooperation of the AND gate circuit, and the ion fragmentation function is provided. The invention provides various internal shapes of the metal pole piece group, different shapes can be selected according to the use requirement to apply different electric fields, and different electric field application modes are provided to achieve different purposes.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and those skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope of the invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.