CN111653472B - A substance analysis method, device and electrostatic ion trap mass analyzer - Google Patents
A substance analysis method, device and electrostatic ion trap mass analyzer Download PDFInfo
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Abstract
本申请实施例公开了一种物质分析方法、装置和静电离子阱质量分析器，静电离子阱质量分析器包括接口装置和质量分析器，所述方法包括：在待检测物的离子进入接口装置，且第一外部导电体加载有第一电压以及第一内部导电体加载有第二电压的过程中，在第一外部导电体或第一内部导电体加载对应的电压脉冲；当达到预设时间时，将第三电压加载至第二外部导电体以及将第四电压加载至所述第二内部导电体；根据所述离子在所述质量分析器中的运动频率，确定待检测物中是否含有目标物质。该方法中提高了质量分析器的分析灵敏度。
The embodiment of the present application discloses a substance analysis method, a device, and an electrostatic ion trap mass analyzer. The electrostatic ion trap mass analyzer includes an interface device and a mass analyzer. The method includes: when ions of the object to be detected enter the interface device, In the process that the first outer conductor is loaded with the first voltage and the first inner conductor is loaded with the second voltage, a corresponding voltage pulse is loaded on the first outer conductor or the first inner conductor; when the preset time is reached , the third voltage is applied to the second outer conductor and the fourth voltage is applied to the second inner conductor; according to the movement frequency of the ions in the mass analyzer, determine whether the object to be detected contains a target substance. In this method, the analytical sensitivity of the mass analyzer is improved.
Description
Technical Field
The present application relates to the field of data processing, and in particular, to a method and apparatus for mass analysis of a substance, and an electrostatic ion trap mass analyzer.
Background
At present, in the nineties of the twentieth century, mass analysis by utilizing an electrostatic field to realize the binding of ions is proposed, and the device is a Fourier transform electrostatic ion trap mass spectrum. Compared with the traditional magnetic field type Fourier transform ion trap, the Fourier transform electrostatic ion trap mass spectrum can reduce the manufacturing cost and the weight while ensuring the resolution and the quality precision, so that the mass spectrum can be widely applied.
The Fourier electrostatic ion trap mass analyzer can be used for detecting whether the object to be detected contains target substances to be detected.
The Fourier transform electrostatic field ion trap consists of a spindle-shaped inner conductor and a barrel-shaped outer conductor. The two conductors are coaxial and are axisymmetric, and the shape and the size of the conductors are determined by the formula (1).
Here, z is an axial position, and the subscript 1 thereof denotes an inner conductor and 2 denotes an outer conductor. R1,2Is the maximum radius of the corresponding inner and outer conductors. r is the magnitude of the vector in the plane perpendicular to the z direction, with a magnitude of
RmIs the ion trap characteristic radius.
The mathematical form of the potential of the electrostatic field formed by this shape of conductor is given by equation (2):
as shown in the formula (2), the motion of the ion in the Z direction is simple harmonic vibration, and the motion equation is
Frequency of vibration
Because the vibration frequency of the ions in the Z direction is only related to the mass-to-charge ratio, the Fourier transform electrostatic field ion trap adopts the characteristic, and the mass analysis is realized by detecting the image current and the subsequent fast Fourier transform to obtain the corresponding relation between the axial frequency and the mass-to-charge ratio of the ions.
However, the fourier transform electrostatic field ion trap has a problem in practical use. The fourier transform electrostatic field ion trap is an approximately closed mass analyzer, and if the object to be detected includes a target substance to be detected, after the voltage pulse is applied to the interface device, ions corresponding to the target substance enter the mass analyzer from the interface device and then do circular motion in the mass analyzer with low possibility. Therefore, how to improve the possibility that ions corresponding to a target substance perform circular motion in a mass analyzer so as to improve and ensure that the fourier transform electrostatic field ion trap can obtain sufficient analysis sensitivity is a key point for the practical application of the mass spectrum.
Disclosure of Invention
In order to solve the above technical problems, the present application provides a method and an apparatus for analyzing a substance, and an electrostatic ion trap mass analyzer, which improve the chance that ions corresponding to a target substance do circular motion in the mass analyzer, thereby improving the analysis sensitivity of the mass analyzer.
The embodiment of the application discloses the following technical scheme:
in one aspect, the present application provides a material analysis method applied to an electrostatic ion trap mass analyzer, where the electrostatic ion trap mass analyzer includes an interface device and a mass analyzer, where the interface device includes a first outer conductor and a first inner conductor that are located in the same plane and have concentric circular arc shapes, and the first outer conductor and the first inner conductor form a first ion movement space; the mass analyzer comprises a second outer conductor and a second inner conductor, wherein the second outer conductor and the second inner conductor are concentric and arc-shaped and are positioned in the same plane with the interface device, and the second outer conductor and the second inner conductor form a second ion movement space; the first inner conductor and the second outer conductor comprise channels for passing ions; the method comprises the following steps:
loading corresponding voltage pulses on the first external conductor or the first internal conductor in the process that ions of an object to be detected enter the interface device and the first external conductor is loaded with a first voltage and the first internal conductor is loaded with a second voltage;
when a preset time is reached, applying a third voltage to the second outer conductor and applying a fourth voltage to the second inner conductor;
wherein the predetermined time includes a first time for ions to travel from a first circular orbit of the interface device to the first inner conductor and a second time for ions to travel from the first inner conductor to a target location; when the ions are at the target position, the corresponding speed direction is vertical to the corresponding bit vector direction, and the preset time is determined according to the mass number and the electric charge quantity of the target substance;
and determining whether the object to be detected contains the target substance according to the movement frequency of the ions in the mass analyzer.
In another aspect, the present application provides a mass analyzer for an electrostatic ion trap, the mass analyzer includes an interface device and a mass analyzer, the interface device includes a first outer conductor and a first inner conductor which are located in the same plane and have concentric circular arcs, and the first outer conductor and the first inner conductor form a first ion moving space; the mass analyzer comprises a second outer conductor and a second inner conductor, wherein the second outer conductor and the second inner conductor are concentric and arc-shaped and are positioned in the same plane with the interface device, and the second outer conductor and the second inner conductor form a second ion movement space; the first inner conductor and the second outer conductor comprise channels for passing ions; the device comprises:
the first loading unit is used for loading corresponding voltage pulses on the first external conductor or the first internal conductor in the process that ions of an object to be detected enter the interface device and the first external conductor is loaded with a first voltage and the first internal conductor is loaded with a second voltage;
a second loading unit for loading a third voltage to the second external conductor and a fourth voltage to the second internal conductor when a preset time is reached;
wherein the predetermined time includes a first time for ions to travel from a first circular orbit of the interface device to the first inner conductor and a second time for ions to travel from the first inner conductor to a target location; when the ions are at the target position, the corresponding speed direction is vertical to the corresponding bit vector direction, and the preset time is determined according to the mass number and the electric charge quantity of the target substance;
and the determining unit is used for determining whether the object to be detected contains the target substance according to the motion frequency of the ions in the mass analyzer.
In another aspect, embodiments of the present application provide an electrostatic ion trap mass analyzer, including an interface device and a mass analyzer, where the interface device includes a first outer conductive body and a first inner conductive body which are located in the same plane and have concentric circular arcs, and the first outer conductive body and the first inner conductive body form a first ion motion space; the mass analyzer comprises a second outer conductor and a second inner conductor, wherein the second outer conductor and the second inner conductor are concentric and arc-shaped and are positioned in the same plane with the interface device, and the second outer conductor and the second inner conductor form a second ion movement space; the first inner conductor and the second outer conductor comprise channels for passing ions; the electrostatic ion trap mass analyzer to:
loading corresponding voltage pulses on the first external conductor or the first internal conductor in the process that ions of an object to be detected enter the interface device and the first external conductor is loaded with a first voltage and the first internal conductor is loaded with a second voltage;
when a preset time is reached, applying a third voltage to the second outer conductor and applying a fourth voltage to the second inner conductor;
wherein the predetermined time includes a first time for ions to travel from a first circular orbit of the interface device to the first inner conductor and a second time for ions to travel from the first inner conductor to a target location; when the ions are at the target position, the corresponding speed direction is vertical to the corresponding bit vector direction, and the preset time is determined according to the mass number and the electric charge quantity of the target substance;
and determining whether the object to be detected contains the target substance according to the movement frequency of the ions in the mass analyzer.
According to the technical scheme, the method is applied to the electrostatic ion trap mass analyzer, the electrostatic ion trap mass analyzer comprises an interface device and a mass analyzer, the interface device comprises a first outer conductor and a first inner conductor which are concentric and arc-shaped and located in the same plane, and a first ion motion space is formed by the first outer conductor and the first inner conductor; the mass analyzer comprises a second outer conductor and a second inner conductor, wherein the second outer conductor and the second inner conductor are located in the same plane and are concentric circular arcs, and the second outer conductor and the second inner conductor form a second ion motion space. The first inner conductor and the second outer conductor comprise channels for passing ions; the method comprises the following steps: loading corresponding voltage pulses on the first external conductor or the first internal conductor in the process that ions of an object to be detected enter the interface device, and the first external conductor is loaded with a first voltage and the first internal conductor is loaded with a second voltage; when the preset time is reached, loading a third voltage to a second external conductor and loading a fourth voltage to the second internal conductor; wherein the preset time includes a first time when the ions move from the first circular orbit of the interface device to the first internal conductor and a second time when the ions move from the first internal conductor to the target position; the corresponding speed direction of the ions at the target position is vertical to the corresponding direction of the bit vector, and the preset time is determined according to the mass number and the electric charge quantity of the target substance. And determining whether the object to be detected contains the target substance according to the movement frequency of the ions in the mass analyzer. In the method, a preset time is determined in advance according to a target substance, so that under the condition that an object to be detected comprises the target substance, ions corresponding to the target substance can move to a target position from an interface device, and because the speed direction corresponding to the ions corresponding to the target substance at the target position is vertical to the direction of the corresponding bit vector of the ions at the target position, a condition is provided for the ions to do circular motion in a second ion motion space, a third voltage and a fourth voltage are loaded on a mass analyzer at the moment, the chance that the ions corresponding to the target substance do circular motion in the mass analyzer is improved, and the analysis sensitivity of the mass analyzer is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
Fig. 1 is a schematic diagram of an electrostatic ion trap mass analyzer according to an embodiment of the present disclosure;
FIG. 2 is a flow chart of a method for substance analysis according to an embodiment of the present disclosure;
fig. 3 is a schematic cross-sectional view of an electrostatic ion trap mass analyzer according to an embodiment of the present disclosure;
fig. 4 is a schematic cross-sectional view of another electrostatic ion trap mass analyzer according to an embodiment of the present disclosure;
fig. 5 is a schematic cross-sectional view of another electrostatic ion trap mass analyzer according to an embodiment of the present disclosure;
fig. 6 is a schematic view of a substance analysis device according to an embodiment of the present disclosure.
Detailed Description
Embodiments of the present application are described below with reference to the accompanying drawings.
To facilitate understanding of the technical solutions of the present application, an electrostatic ion trap mass analyzer is described below.
Referring to fig. 1, which shows a schematic diagram of an electrostatic ion trap mass analyzer according to an embodiment of the present application, as shown in fig. 1, the electrostatic ion trap mass analyzer includes an interface device and a mass analyzer, the interface device includes a first outer conductive body and a first inner conductive body which are located in the same plane and have concentric circular arc shapes, and the first outer conductive body and the first inner conductive body form a first ion moving space. The mass analyzer comprises a second outer conductor and a second inner conductor, wherein the second outer conductor and the second inner conductor are concentric and circular arc-shaped and located in the same plane with the interface device, and the second outer conductor and the second inner conductor form a second ion motion space. The mass analyser may also be referred to as a fourier transform electrostatic field ion trap, among others. The first inner conductor and the second outer conductor comprise channels for ions to pass through. I.e. ions may pass through the first and second inner electrical conductors.
That is, the first external conductor, the first internal conductor, the second external conductor and the second internal conductor are located on the same plane and correspond to the same center O.
The electrostatic ion trap mass analyzer can detect whether the object to be detected comprises the target substance to be detected. Before ions of an object to be detected enter the interface device, the ions may have a suitable kinetic energy, so that when the ions enter the interface device, the ions may perform a circular motion in a first ion motion space, and when the object to be detected includes a target substance, the ions corresponding to the target substance may be pushed to the mass analyzer by applying a voltage pulse to the interface device (for example, applying a corresponding voltage pulse to the first outer conductor or the first inner conductor).
The technical scheme provided by the embodiment of the application can be applied to the mass analyzer of the electrostatic ion trap.
The technical scheme provided by the embodiment of the application can be executed by data processing equipment, and comprises terminal equipment, a server and the like.
Referring to fig. 2, which shows a flowchart of a substance analysis method provided in an embodiment of the present application, as shown in fig. 2, the method includes:
s201: and in the process that the ions of the object to be detected enter the interface device, and the first external conductor is loaded with a first voltage and the first internal conductor is loaded with a second voltage, loading corresponding voltage pulses on the first external conductor or the first internal conductor.
The method provided by the embodiment of the application can be used for detecting whether the object to be detected has the target substance. The target substance may be a substance to be detected, and the substance to be detected may be any substance, such as a mixture of substances or a single substance.
The embodiment of the application does not limit the mode of obtaining the ions of the object to be detected, and a suitable mode can be selected for obtaining.
In this embodiment of the present application, ions may enter an interface device in an electrostatic ion trap mass analyzer through acceleration of an ion source, and in order to make the ions perform circular motion in the interface device, the following initial conditions need to be satisfied, which specifically include:
the interface device, also called electrostatic analyser, is structured like a cylindrical capacitor, comprising a first inner electrical conductor and a first outer electrical conductor. Referring to fig. 3, a schematic cross-sectional view of an electrostatic ion trap mass analyzer according to an embodiment of the present application is shown, for an interface device, where a first external conductive body is included and has a radius R1(unit m) radius of the first inner conductor is R2(unit m); the first voltage corresponding to the first external conductor is U1(unit V) the second voltage corresponding to the first internal conductor is U2(unit V). By applying corresponding voltages to the first outer conductor and the first inner conductor, an electric field can be formed in the first ion movement space to move ions in the space.
Since there is no charge between the two conductors, the Laplace equation can be used
The potential between the two conductors is calculated.
Wherein, within the cylindrical coordinates:
r may refer to a bit vector corresponding to each position in the first ion motion space, i.e., a vector pointing to each position from the center O corresponding to the first external conductor or the first internal conductor.
Integrating twice to obtain u (r) ═ Alnr + B;
and determines the values of a and B based on the boundary conditions.
When R is R1, U is U1, U1 is ainr 1+ B; when R is R2, U is U2 and U1 is ainr 2+ B.
Therefore, the first and second electrodes are formed on the substrate,
thus is provided with
The magnitude of the electric field force on the ions is:
q is the charge quantity carried by the ion, the direction of the electric field force always points to the center O, and the force borne by the ion is only related to r (the radius corresponding to the uniform circular motion).
As shown in FIG. 3, ions of the object enter the interface device from the point P, and the radius corresponding to the incident ions is r0Initial velocity v0The initial speed direction is perpendicular to the applied electric field force. Wherein r is0Is the initial position (in m), r, of the ion entry interface device0＝R2+(R1-R2) And/2, ions of the object to be detected are incident from the center of the entrance of the interface device. The initial kinetic energy of the ions is:
if the ions of the object to be detected enter the interface (electrostatic analyzer), they are subjected to the force of the electric field
Because the initial velocity direction of the ion of the thing to be detected is perpendicular with the electric field force direction, from this doing circular motion, then there is:
therefore, when
During the operation, the ions of the object to be detected do circular motion in the interface device. If the acceleration voltage is changed to the acceleration voltage U of the preceding stage ion acceleratoraccIt can be expressed as:
for example, let U1＝100V，U2＝100V，R1/R 24, when the initial kinetic energy of the ions of the object to be detected is equal to
In this case, the movement of the ions of the object to be detected is circular. Setting U in ion optical simulation software1＝100V，U2＝100V，R1/R 24. When the initial kinetic energy of the ions of the object to be detected is set to 36ev, the ion motion trajectory is circular, and if the initial kinetic energy of the ions is increased, for example, to 37ev, the ion trajectory deviates from the circular trajectory in the above case. If the initial kinetic energy of the ions is reduced, for example, to 35ev, the trajectories of the ions are deviated from the circular trajectories in the above case.
Thus, when an ion of the object to be detected leaves the ion source, the initial kinetic energy of the ion should satisfy the above condition, that is,
so that the first external conductor is applied with a first voltage U after the ions enter the interface device1And the first internal conductor is loaded with a second voltage U2The ions may be caused to move circumferentially within the interface device.
In addition, in this process, the first outer conductor or the first inner conductor may be subjected to a corresponding voltage pulse for applying an additional force to the ions of the object to be detected, pushing them into the mass analyser, in the hope of making a circular movement of the ions in the mass analyser.
In embodiments of the present application, a corresponding voltage pulse may be applied to the first inner conductor of the interface device, and a corresponding voltage pulse may also be applied to the first outer conductor, to cause ions to enter the mass analyser.
If the substance to be detected includes a target substance, in one possible implementation manner, in order to allow ions corresponding to the target substance in the substance to be detected to enter the mass analyzer, the pulse voltage satisfies the following condition:
a third condition determined based on a first radius corresponding to the first outer conductor, a second radius corresponding to the first inner conductor, and the first voltage and the second voltage.
The determination of this third condition is described in detail below.
Taking the example of applying the voltage pulse Δ U to the first external conductor of the interface device, the Δ U is applied to change the trajectory of the ions making the circular motion in the interface device to enter the mass analyzer, i.e., the fourier transform electrostatic field ion trap. As shown in FIG. 3, when a voltage pulse was applied when the ions moved to the point P, the voltage of the first external conductor became U1 '(U1'>U1) the ions will move along the dashed line in fig. 3 to point Q on the first internal conductor. At the instant when the first external conductor voltage becomes U1', the kinetic energy of the ions is EpI.e. the aforementioned E0. When the ion moves to the point Q, the kinetic energy of the ion is Eq＝Ep+ΔUq。
At this time, the velocity of the ions at point Q is:
m is the ion mass.
And according to the law of conservation of angular momentum:
mr0v023nθ0＝mR2vQsinθQ；
wherein, theta0Is the angle between the velocity of the ion at point P and the electric field force experienced by the ion, θQIs the angle between the velocity of the ion at the point Q and the electric field force experienced by the ion.
Thus, the method can obtain the product,
since the velocity direction of the ion at the point P is perpendicular to the direction of the applied electric field, s3n θ01. Therefore, the temperature of the molten metal is controlled,
therefore, according to r0，U1’，R1，R2，q，v0Then theta can be calculatedQ. Only when the delta U reaches a certain value, the ion corresponding to the target substance is likely to move to the radius R2If the value of Δ U is not large enough, the ions corresponding to the target substance will not move to radius R2The position of (a). Therefore, according to sin θQThe value range of delta U is determined by less than 1, and ions corresponding to the target substance can be ensured to move to the radius R2The position of (a).
Thus, a value range of Δ U is obtained and recorded as a third condition:
by making the voltage pulse satisfy the third condition, the movement of the ion corresponding to the target substance to a radius of R is improved2And thereby increasing the probability of ions corresponding to the target species entering the mass analyzer.
In order to increase the probability that ions corresponding to the target substance enter the mass spectrometer to make circular motion, in one possible implementation, the voltage pulse satisfies the following condition:
according to a first radius R corresponding to the first external conductor1A second radius R corresponding to the first inner conductor2The first voltage U1The second voltage U2A third radius R corresponding to the second external conductor3And a first condition determined by the charge amount q of the target substance.
And/or the presence of a gas in the gas,
according to a first radius R corresponding to the first external conductor1A second radius R corresponding to the first inner conductor2The first voltage U1The second voltage U2A fourth radius R corresponding to the second inner conductor4And a second condition determined by the charge amount q of the target substance.
The determination of the first and second conditions is described in detail below.
Referring to fig. 4, which shows a schematic cross-sectional view of another electrostatic ion trap mass analyzer provided in the embodiment of the present application, as shown in fig. 4, in order to ensure that the ions do not collide with the second external conductor when entering the mass analyzer, an angle between a speed of the ions at the point Q and an electric field force applied to the ions should satisfy the following condition:
that is to say that the first and second electrodes,
thus, the first condition for obtaining the voltage pulse is:
in order to ensure that the ions corresponding to the target substance do not collide with the second internal conductor when entering the mass analyzer, an included angle between a speed of the ions corresponding to the target substance at the point Q and an electric field force applied to the ions should satisfy the following second condition:
that is to say that the first and second electrodes,
thus, the second condition for obtaining the voltage pulse is:
if the voltage pulse satisfies any one or more of the first and second conditions, the probability that ions corresponding to the target species enter the mass analyzer for circular motion can be increased.
For an electrostatic ion trap mass analyzer, a fixed kinetic energy is set for the mass analyzer, that is, ions moving circularly in the mass analyzer should have a specific kinetic energy, so that the ions are subjected to mass detection by the mass analyzer. Wherein the fixed kinetic energy set for the mass analyzer is
That is, the first optimal incident conditions for ions of the target species to enter the mass analyzer include: initial kinetic energy of ions in tangential direction is
Where k is the field curvature of the electrostatic field in the mass analyzer, i.e., a parameter, and the value of k is determined by the third and fourth voltages and the corresponding radii of the second outer and second inner conductors. RmMay be the ion trap characteristic radius, in m, for the mass analyzer, which is a parameter of the mass analyzer, in an implementation, RmThe values of (a) may be: rmR' may be the radius corresponding to the uniform circular motion of the ions in the mass analyser, 0.032388.
Thus, in one possible implementation, the voltage pulse is determined in a manner that includes:
according to the first outer layerFirst radius R corresponding to the portion conductor1A second radius R corresponding to the first inner conductor2A first voltage U1A second voltage U2Ion trap characteristic radius R corresponding to mass analyzermAnd determining the voltage pulse.
Wherein, in order to ensure that the kinetic energy of the ions corresponding to the target material when entering the mass analyzer can reach the fixed kinetic energy set for the mass analyzer, the kinetic energy of the ions when entering the mass analyzer can reach E after the ions are supplemented with the kinetic energy through the voltage pulse delta UESIT_in。
I.e. the potential difference U between the two conductors based on the interface means, according to the conservation of energy1-U2And the voltage pulse Δ U must satisfy the following condition:
obtain corresponding voltage pulse
And the interface device is applied by this voltage pulse deltau.
S202: when a preset time is reached, a third voltage is applied to the second outer conductor and a fourth voltage is applied to the second inner conductor.
It will be appreciated that the optimal incident conditions for ions of the target species to enter the interface device include: the initial kinetic energy of the ions entering the interface device ensures that they can move circumferentially within the interface device.
In addition, mass analysis of ions by a mass analyzer also has two other optimal incidence conditions, respectively:
the second optimum incidence condition is: the radial initial velocity of the ions is zero, namely the incident velocity direction of the ions incident to the second external conductor is vertical to the bit vector;
the third optimal incidence condition is: the radial acceleration of the ions is zero in magnitude so that the ions can move in a circular motion within the mass analyzer.
In order to enable ions corresponding to the target species to enter the mass analyser from the interface device, a voltage pulse is applied to a first external conductor or a first internal conductor in the interface device. After the voltage pulse is applied to the electric conductor of the interface device, the motion track of the ion which does circular motion in the interface device changes, and the size of the bit vector of the ion can change along with the time in the motion process. Potential difference U of interface device1-U2And the voltage pulse au of the interface device will determine the initial incident state of the ions into the mass analyser. In order to satisfy the second and third optimum incidence conditions for ions to be analysed in the mass analyser, a delay time, denoted as a predetermined time t, may be created between the application of the voltage pulse by the interface means and the application of a voltage, e.g. a negative high voltage, to the electrical conductors in the mass analysertotal。
Wherein the preset time ttotalIncluding a first time t for ions to orbit from a first circle of the interface device to the first internal electrical conductor1And a second time t from the first inner conductor movement to the target position2. And a preset time ttotalIs determined based on the mass number m of the target substance and the charge amount q.
The corresponding speed direction of the ions at the target position is perpendicular to the corresponding vector direction, and the corresponding vector of the ions at the target position is a vector of a circle center O corresponding to the second external conductor or the second internal conductor pointing to the target position.
Following the first time t1The determination of (2) is described.
In one possible implementation, the first time t1The determination method comprises the following steps:
s301: and determining the radial acceleration of the ions under different bit vectors according to the voltage pulse, the incident position of the ions to the interface device, the first radius corresponding to the first external conductor, the second radius corresponding to the first internal conductor, the mass number and the charge quantity of the target substance.
It can be appreciated that the initial kinetic energy (E) of ions corresponding to the target species entering the interface device0) Comprises the following steps:
the final kinetic energy of the ions corresponding to the target species leaving the interface device, i.e., the initial kinetic energy (E) of the ions entering the mass analyzerESA_out)：
The angle at which ions corresponding to the target species exit the interface device, i.e., the initial angle θ at which ions corresponding to the target species enter the mass analyzerQSatisfies the following conditions:
initial kinetic energy (E) of ions corresponding to the target species entering the mass analyzerESIT_in): the initial kinetic energy of ions corresponding to the target species entering the mass analyser should be as high as possible to enable them to move in a circular motion within the mass analyser, i.e. EESIT_inThe following equation should be satisfied:
referring to fig. 5, which is a schematic cross-sectional view of another electrostatic ion trap mass analyzer provided in the embodiments of the present application, the motion trajectory of the ions is a circle before the voltage pulse is applied by the interface device, as shown in fig. 5. The electric field force of the ions is just equal to the centripetal force required by the ions to do circular motion, r is the position vector of the ions in the interface device, and the size of r is the distance between the position of the ions in the interface device and the corresponding circle center:
at the instant that the voltage pulse is applied by the interface device, the electric field force on the ions corresponding to the target species is increased
At this time, the electric field force applied to the ion corresponding to the target substance is:
therefore, the electric field force of the ion corresponding to the target substance is larger than the centripetal force required by the ion to do circular motion, the electric field force of the ion provides a radial force for the ion besides providing the centripetal force for the ion to do circular motion, and the magnitude of the radial force is that
The direction points to the corresponding circle center of the interface device. Under the action of the force, ions corresponding to the target substance do accelerated motion along the radial direction while doing circular motion. The acceleration of the ions corresponding to the target substance in the radial direction is as follows:
as shown in fig. 5, the radius of motion of the ions decreases after the interface device applies the voltage pulse.
After the interface device applies the voltage pulse, when the magnitude of the motion potential vector of the ion corresponding to the target substance is equal to r, the required centripetal force is
The motion vector is the distance between the position of the ion and the center of the circle corresponding to the interface device.
And according to the law of conservation of angular momentum v0r0＝vr·r·sinθr＝vr⊥r, wherein vrIs the velocity of the target substance when the ion moves to the bit vector of r, thetarIs vrAngle with the vector r, vr⊥Is vrThe component perpendicular to the bit vector r. Therefore, the first and second electrodes are formed on the substrate,
and at this time, the electric field force applied to the ion corresponding to the target substance is as follows:
therefore, the acceleration of the ions corresponding to the target substance in the radial direction is:
and due to
Therefore, ar＝
According to the expression of the acceleration, the acceleration motion of the ion corresponding to the target substance in the radial direction is a variable acceleration motion, and the magnitude of the acceleration is related to the magnitude of the bit vector r.
S302: determining the first time based on the first radius, a location of incidence of ions into the interface device, the second radius, and the radial acceleration.
In the embodiment of the present application, the time for the ions corresponding to the target substance to move from the position vector size r0 to the position vector size r is divided into n equal divisions (n is sufficiently large), and the divided total n +1 time points are t +1 time points respectively0,t1,t2……tn-1,tnThe bit vector corresponding to the n +1 time points is r0(r0),r1,r2……r2n-1, rn(R2) The ion can be scaled from the azimuthal vector to ri-1In-position vector of riThe motion of the part is approximately uniform acceleration linear motion, i is more than 0 and less than or equal to1 is a positive integer.
Thus, the ion dislocation vector size r can be determined by means of calculusi-1(i-1, 2, …, n) to a bit vector of size riThe time of the position of (a) is:
r0-r1＝0+1/2*ar0*Δt2；
r1-r2＝ar0*Δt*Δt+1/2*ar1*Δt2；
r2-r3＝(ar0*Δt+ar1*Δt)+1/2*ar2*Δt2；
…；
rn-2-rn-1＝(ar0*Δt+ar1*Δt+…+arn-3*Δt)*Δt+1/2*arn-2*Δt2；
rn-1-R2＝(ar0*Δt+ar1*Δt+…+arn-2*Δt)*Δt+1/2*arn-1*Δt2。
wherein, ariCan refer to the ion director ri(ii) a corresponding acceleration;
(ar0*Δt+ar1*Δt+…+ariΔ t) may refer to the ion presence vector ri+1At the corresponding speed.
Adding the n equations to obtain:
r0-R2＝[(n-1)*ar0+(n-2)*ar1+…+2arn-3+1*arn-2]*Δt2+1/2(ar0+ar1+ …+arn-2+arn-1)*Δt2；
each time interval Δ t is:
x＝[(n-1)*ar0+(n-2)*ar1+…+2arn-3+1*arn-2]+ 1/2(ar0+ar1+…+arn-2+arn-1)；
therefore, the first time t1Comprises the following steps:
y＝[(n-1)*ar0+(n-2)*ar1+…+2arn-3+1*arn-2]+ 1/2(ar0+ar1+…+arn-2+arn-1)；
then according to
T1 values for ions of different mass numbers m can be obtained.
In a particular implementation, the first time t for an ion of mass number m may be determined by the computing device according to the formula for first time t1 and the acceleration formula described above with respect to first time t11。
When n is sufficiently large, the ion vector r can be approximated0Motion to orientation vector R2A first time t required1。
In a possible implementation manner, the determining manner of the second time may include:
s401: and determining the incident angle of the ions moving to the second external conductor according to the voltage pulse, the first radius corresponding to the first external conductor, the second radius corresponding to the first internal conductor, the first voltage, the second voltage and the charge quantity of the target substance.
The voltage pulse, the first radius corresponding to the first outer conductor, the second radius corresponding to the first inner conductor, the first voltage, the second voltage, and the charge amount of the target substance may be calculated according to a formula
Determining the angle of incidence θ of ions moving to the second external conductorQ。
S402: and determining the second time according to a third radius corresponding to the second external conductor, the incident angle, the characteristic radius of the ion trap corresponding to the mass analyzer, the mass number of the target substance and the charge amount.
Referring to fig. 5, which shows a schematic cross-sectional view of another electrostatic ion trap mass analyzer provided in this embodiment of the present application, as shown in fig. 5, since an angle between an exit velocity direction of ions corresponding to a target substance when the ions enter the mass analyzer at a point Q and a direction of a bit vector R3 is smaller than 90 °, that is, the ions corresponding to the target substance do not reach an optimal incident angle. Therefore, the third voltage and the fourth voltage, i.e., the negative high voltage, are not applied just when the ions corresponding to the target substance enter the mass analyzer to bind the ions entering the mass analyzer.
When the ions corresponding to the target substance enter the mass analyzer from the point Q, they move linearly at a constant speed v, and when the ions move to the target position, i.e., the point B in fig. 5, the direction of the speed v of the ions is perpendicular to the direction of the bit vector of the ions, so that the optimal incident angle of the ions is satisfied. The bit vector may refer to a vector in which a center of a circle corresponding to the mass analyzer (i.e., a center of a circle corresponding to the second external conductive body or the second internal conductive body) points to a target position of the ion.
At this time, by applying a voltage to the mass analyzer, that is, applying a third voltage to the second external conductor and applying a fourth voltage to the second internal conductor, ions corresponding to the target substance are bound, so that the ions corresponding to the target substance make uniform circular motion in the second ion motion space.
Therefore, the second time when the ions corresponding to the target substance make uniform linear motion from the moment when the ions enter the mass analyzer to the moment when the voltage is applied to the mass analyzer is equal to
QB＝R3sinθQThereby, the speed of uniform linear motion is performed
Thereby, the second time
In a specific implementation, the determination of the preset time may be performed according to the following parameters, so as to execute the methods of S201 to S203.
System parameters for the interface device: voltage of interface device first external conductor (unit V): u shape1(ii) a Voltage of the interface device first internal conductor (unit V): u shape2(ii) a Radius of the interface first external conductor (unit m): r10.03 percent; electrode radius (unit m) within the interface: r20.02; initial position of ion entry into interface device (in m): r is0＝R2+(R1-R2) 2 (ions incident from the center of the interface device entrance); interface device potential difference (unit V): delta U inside and outside being U1-U2(ii) a Voltage pulse of interface device (unit V): Δ U; unit charge capacity: q is 1.602 x 10-19; ion mass number: m ═ 10^ -3 (280 ^ 10^ -3)/(6.022 ^ 10^ 23).
System parameters for the mass analyzer: mass analyzer second external conductor voltage (in V): u shape30; mass analyzer second internal conductor voltage (in V): u shape4-1000; mass analyzer second outer conductor radius (in m): r30.02; mass analyser second inner conductor radius (in m): r40.0075; initial position of ion entry into mass analyser (in m): r is1R3sin θ Q (θ is the angle at which ions exit the interface); ion trap characteristic radius (in m): rm＝0.032388。
As described above, the velocity direction of the ions exiting the interface device and entering the mass analyzer at a moment is not perpendicular to the bit vector of the ion position, which does not satisfy the optimal incident angle of the ions entering the mass analyzer (i.e. the velocity direction of the ions is perpendicular to the bit vector), so that a delay time, i.e. a preset time t, is required after the voltage pulse is applied to the interface devicetotalA negative high voltage is applied to the mass analysis.
Preset time ttotalIncluding a first time t1And a second time t2After the interface device applies voltage pulse, the target substance corresponds toThe ions first make an elliptical-like motion in the interface device, wherein the applied voltage pulse may be large enough to ensure that the minimum vector of the ions is less than or equal to R2. Ions corresponding to the target species are equal to R in magnitude from the time the interface device applies the voltage pulse to the ions moving to the bit vector2The time taken for the moment of (a) is a first time t1。
Ions corresponding to the target species exit the interface device, enter the mass analyzer, and begin at a velocity of about
And performing uniform linear motion, and applying voltage such as negative high voltage to the second external conductor and the second internal conductor of the mass analyzer when the ions corresponding to the target substance move to the moment that the speed direction is vertical to the direction of the bit vector at the target position.
The time from the moment when the ions corresponding to the target substance exit from the interface device and enter the mass analyzer to the moment when the voltage is applied to the mass analyzer is the second time t2。
Therefore, a delay time t is required from the application of the voltage pulse from the interface device to the application of the voltage to the mass analyzertotal＝t1+t2。
S203: and determining whether the object to be detected contains the target substance according to the movement frequency of the ions in the mass analyzer.
The present application does not limit the determination manner of S203, and it can be determined whether the object to be detected contains the target substance according to the movement frequency of the ions in the mass analyzer according to the manner in the related art.
According to the technical scheme, the method is applied to the electrostatic ion trap mass analyzer, the electrostatic ion trap mass analyzer comprises an interface device and a mass analyzer, the interface device comprises a first outer conductor and a first inner conductor which are concentric and arc-shaped and located in the same plane, and a first ion motion space is formed by the first outer conductor and the first inner conductor; the mass analyzer comprises a second outer conductor and a second inner conductor, wherein the second outer conductor and the second inner conductor are located in the same plane and are concentric circular arcs, and the second outer conductor and the second inner conductor form a second ion motion space. The first inner conductor and the second outer conductor comprise channels for passing ions; the method comprises the following steps: loading corresponding voltage pulses on the first external conductor or the first internal conductor in the process that ions of an object to be detected enter the interface device, and the first external conductor is loaded with a first voltage and the first internal conductor is loaded with a second voltage; when the preset time is reached, loading a third voltage to a second external conductor and loading a fourth voltage to the second internal conductor; wherein the preset time includes a first time when the ions move from the first circular orbit of the interface device to the first internal conductor and a second time when the ions move from the first internal conductor to the target position; the corresponding speed direction of the ions at the target position is vertical to the corresponding direction of the bit vector, and the preset time is determined according to the mass number and the electric charge quantity of the target substance. Determining the mass of the ions from the frequency of movement of the ions in the mass analyser. In the method, a preset time is determined in advance according to a target substance, so that under the condition that an object to be detected comprises the target substance, ions corresponding to the target substance can move to a target position from an interface device, and because the speed direction corresponding to the ions corresponding to the target substance at the target position is vertical to the direction of the corresponding bit vector of the ions at the target position, a condition is provided for the ions to do circular motion in a second ion motion space, a third voltage and a fourth voltage are loaded on a mass analyzer at the moment, the chance that the ions corresponding to the target substance do circular motion in the mass analyzer is improved, and the analysis sensitivity of the mass analyzer is further improved.
A substance analysis device is provided in the embodiments of the present application, referring to fig. 6, which shows a schematic diagram of a substance analysis device provided in the embodiments of the present application, as shown in fig. 6, applied to an electrostatic ion trap mass analyzer, the electrostatic ion trap mass analyzer includes an interface device and a mass analyzer, the interface device includes a first outer conductive body and a first inner conductive body which are located in the same plane and have concentric circular arcs, and the first outer conductive body and the first inner conductive body form a first ion movement space; the mass analyzer comprises a second outer conductor and a second inner conductor, wherein the second outer conductor and the second inner conductor are concentric and arc-shaped and are positioned in the same plane with the interface device, and the second outer conductor and the second inner conductor form a second ion movement space; the first inner conductor and the second outer conductor comprise channels for passing ions; the device comprises:
a first loading unit 601, configured to load a corresponding voltage pulse on the first external conductor or the first internal conductor in a process that ions of an object to be detected enter the interface device, and a first voltage is loaded on the first external conductor and a second voltage is loaded on the first internal conductor;
a second loading unit 602, configured to load a third voltage to the second external conductor and a fourth voltage to the second internal conductor when a preset time is reached;
wherein the predetermined time includes a first time for ions to travel from a first circular orbit of the interface device to the first inner conductor and a second time for ions to travel from the first inner conductor to a target location; when the ions are at the target position, the corresponding speed direction is vertical to the corresponding bit vector direction, and the preset time is determined according to the mass number and the electric charge quantity of the target substance;
a determining unit 603, configured to determine whether the object to be detected contains a target substance according to a moving frequency of the ions in the mass analyzer.
In one possible implementation, the voltage pulse satisfies the following condition:
a first condition determined based on a first radius corresponding to the first outer conductor, a second radius corresponding to the first inner conductor, the first voltage, the second voltage, a third radius corresponding to the second outer conductor, and a charge amount of the target substance;
and/or the presence of a gas in the gas,
and a second condition determined based on a first radius corresponding to the first outer conductor, a second radius corresponding to the first inner conductor, the first voltage, the second voltage, a fourth radius corresponding to the second inner conductor, and a charge amount of the target substance.
In one possible implementation, the voltage pulse satisfies the following condition:
a third condition determined based on a first radius corresponding to the first outer conductor, a second radius corresponding to the first inner conductor, and the first voltage and the second voltage.
In one possible implementation, the voltage pulses are determined as follows:
and determining the voltage pulse according to a first radius corresponding to the first outer conductor, a second radius corresponding to the first inner conductor, the first voltage, the second voltage and the characteristic radius of the ion trap corresponding to the mass analyzer.
In a possible implementation manner, the determining manner of the first time includes:
determining the radial acceleration of the ions under different bit vectors according to the voltage pulse, the incident position of the ions to the interface device, the first radius corresponding to the first external conductor, the second radius corresponding to the first internal conductor, the mass number and the charge amount of the target substance;
determining the first time based on the first radius, a location of incidence of ions into the interface device, the second radius, and the radial acceleration.
In a possible implementation manner, the determining manner of the second time includes:
determining an incident angle of the ions moving to the second outer conductor according to the voltage pulse, the first radius corresponding to the first outer conductor, the second radius corresponding to the first inner conductor, the first voltage, the second voltage and the charge amount of the target substance;
and determining the second time according to a third radius corresponding to the second external conductor, the incident angle, the characteristic radius of the ion trap corresponding to the mass analyzer, the mass number of the target substance and the charge amount.
The embodiment of the application provides an electrostatic ion trap mass analyzer, which comprises an interface device and a mass analyzer, wherein the interface device comprises a first outer conductor and a first inner conductor which are concentric and arc-shaped and are positioned in the same plane, and the first outer conductor and the first inner conductor form a first ion motion space; the mass analyzer comprises a second outer conductor and a second inner conductor, wherein the second outer conductor and the second inner conductor are concentric and arc-shaped and are positioned in the same plane with the interface device, and the second outer conductor and the second inner conductor form a second ion movement space; the first inner conductor and the second outer conductor comprise channels for passing ions; the electrostatic ion trap mass analyzer to:
loading corresponding voltage pulses on the first external conductor or the first internal conductor in the process that ions of an object to be detected enter the interface device and the first external conductor is loaded with a first voltage and the first internal conductor is loaded with a second voltage;
when a preset time is reached, applying a third voltage to the second outer conductor and applying a fourth voltage to the second inner conductor;
wherein the predetermined time includes a first time for ions to travel from a first circular orbit of the interface device to the first inner conductor and a second time for ions to travel from the first inner conductor to a target location; when the ions are at the target position, the corresponding speed direction is vertical to the corresponding bit vector direction, and the preset time is determined according to the mass number and the electric charge quantity of the target substance;
and determining whether the object to be detected contains the target substance according to the movement frequency of the ions in the mass analyzer.
In one possible implementation, the voltage pulse satisfies the following condition:
a first condition determined based on a first radius corresponding to the first outer conductor, a second radius corresponding to the first inner conductor, the first voltage, the second voltage, a third radius corresponding to the second outer conductor, and a charge amount of the target substance;
and/or the presence of a gas in the gas,
and a second condition determined based on a first radius corresponding to the first outer conductor, a second radius corresponding to the first inner conductor, the first voltage, the second voltage, a fourth radius corresponding to the second inner conductor, and a charge amount of the target substance.
In one possible implementation, the voltage pulse satisfies the following condition:
a third condition determined based on a first radius corresponding to the first outer conductor, a second radius corresponding to the first inner conductor, and the first voltage and the second voltage.
In one possible implementation, the voltage pulses are determined as follows:
and determining the voltage pulse according to a first radius corresponding to the first outer conductor, a second radius corresponding to the first inner conductor, the first voltage, the second voltage and the characteristic radius of the ion trap corresponding to the mass analyzer.
In a possible implementation manner, the determining manner of the first time includes:
determining the radial acceleration of the ions under different bit vectors according to the voltage pulse, the incident position of the ions to the interface device, the first radius corresponding to the first external conductor, the second radius corresponding to the first internal conductor, the mass number and the charge amount of the target substance;
determining the first time based on the first radius, a location of incidence of ions into the interface device, the second radius, and the radial acceleration.
In a possible implementation manner, the determining manner of the second time includes:
determining an incident angle of the ions moving to the second outer conductor according to the voltage pulse, the first radius corresponding to the first outer conductor, the second radius corresponding to the first inner conductor, the first voltage, the second voltage and the charge amount of the target substance;
and determining the second time according to a third radius corresponding to the second external conductor, the incident angle, the characteristic radius of the ion trap corresponding to the mass analyzer, the mass number of the target substance and the charge amount.
According to the technical scheme, the method is applied to the electrostatic ion trap mass analyzer, the electrostatic ion trap mass analyzer comprises an interface device and a mass analyzer, the interface device comprises a first outer conductor and a first inner conductor which are concentric and arc-shaped and located in the same plane, and a first ion motion space is formed by the first outer conductor and the first inner conductor; the mass analyzer comprises a second outer conductor and a second inner conductor, wherein the second outer conductor and the second inner conductor are located in the same plane and are concentric circular arcs, and the second outer conductor and the second inner conductor form a second ion motion space. The first inner conductor and the second outer conductor comprise channels for passing ions; the method comprises the following steps: loading corresponding voltage pulses on the first external conductor or the first internal conductor in the process that ions of an object to be detected enter the interface device, and the first external conductor is loaded with a first voltage and the first internal conductor is loaded with a second voltage; when the preset time is reached, loading a third voltage to a second external conductor and loading a fourth voltage to the second internal conductor; wherein the preset time includes a first time when the ions move from the first circular orbit of the interface device to the first internal conductor and a second time when the ions move from the first internal conductor to the target position; the corresponding speed direction of the ions at the target position is vertical to the corresponding direction of the bit vector, and the preset time is determined according to the mass number and the electric charge quantity of the target substance. And determining whether the object to be detected contains the target substance according to the movement frequency of the ions in the mass analyzer. In the method, a preset time is determined in advance according to a target substance, so that under the condition that an object to be detected comprises the target substance, ions corresponding to the target substance can move to a target position from an interface device, and because the speed direction corresponding to the ions corresponding to the target substance at the target position is vertical to the direction of the corresponding bit vector of the ions at the target position, a condition is provided for the ions to do circular motion in a second ion motion space, a third voltage and a fourth voltage are loaded on a mass analyzer at the moment, the chance that the ions corresponding to the target substance do circular motion in the mass analyzer is improved, and the analysis sensitivity of the mass analyzer is further improved.
As can be seen from the above description of the embodiments, those skilled in the art can clearly understand that all or part of the steps in the above embodiment methods can be implemented by software plus a necessary general hardware platform. Based on such understanding, the technical solution of the present application may be essentially or partially implemented in the form of a software product, which may be stored in a storage medium, such as a ROM/RAM, a magnetic disk, an optical disk, etc., and includes several instructions for enabling a computer device (which may be a personal computer, a server, or a network communication device such as a media gateway, etc.) to execute the method according to the embodiments or some parts of the embodiments of the present application.
It should be noted that, in the present specification, the embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments may be referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
It is further noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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| WO2020106310A1 (en) * | 2018-11-20 | 2020-05-28 | The Trustees Of Indiana University | Orbitrap for single particle mass spectrometry |
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