Structure and Performance of Polygonal Electrode Linear Ion Trap

The polygonal electrode linear ion trap (PeLIT) can produce quadrupolar electric field plus some higher order field, which balances the relationship between mass resolution and electrode manufacturing difficulties. The electrodes of PeLIT are relatively simple, but have a good mass resolving power. This study investigated the relationship between the electric field distribution and the ion trap structures, and the performances of PeLIT through theoretical simulation and experimental study. Research results of simulation showed that the polygonal electrode linear ion traps with different structures had different electric field distributions and mass analysis performances. The negative decapole field distorted the performances significantly. The experimental results showed that the mass resolution of reserpine ions (m/z 609) was more than 2500 using a polygonal electrode ion trap. At the same time, mass selective excitation and tandem mass spectrometry experiments were also carried.     

印刷线路板分压离子阱的离子单向出射性能研究

印刷线路板(Printed-Circuit-Board,PCB)分压离子阱是一种新型质量分析器,其突出优点在于内部电场可通过调节射频分压比进行优化.本实验在PCB分压离子阱离子出射方向的两组离散电极上配置了非对称的射频分压,以引入奇次阶场成分,使得射频电场的场中心(即离子运动中心)发生偏移,从而实现离子单向出射.通过数值计算软件SIMION和AXSIM分析了射频分压比差值与其内部电场分布的关系,并模拟离子运动轨迹,得到离子出射情况和模拟质谱峰.模拟结果表明,当两组离散电极的射频分压比差值为20％时,在合适的AC频率条件下,对于m/z=609 Th的离子,PCB分压离子阱的离子单向出射率可达90％以上,且质量分辨率大于2500.本研究可使PCB分压离子阱在基本不损失质量分辨率和使用单检测器模式下,大幅提高离子检测效率,因而在小型化质谱仪应用中具有显著优势.     

Improved ion extraction from a linear octopole ion trap: SIMION analysis and experimental demonstration

Externally generated ions are accumulated in a linear octopole ion trap before injection into our 9.4 T Fourier transform ion cyclotron resonance (FT-ICR) mass analyzer. Such instrumental configuration has previously been shown to provide improved sensitivity, scan rate, and duty cycle relative to accumulated trapping in the ICR cell. However, inefficient ion ejection from the octopole currently limits both detection limit and scan rate. SIMION 7.0 analysis predicts that a dc axial electric field inside the linear octopole ion trap expedites and synchronizes the efficient extraction of the octopole-accumulated ions. Further SIMION analysis optimizes the ion ejection properties of each of three electrode configurations designed to produce a near-linear axial potential gradient. More efficient extraction and transfer of accumulated ions spanning a wide m/z range promises to reduce detection limit and increase front-end sampling rate (e.g., to increase front-end resolution for separation techniques coupled with FT-ICR mass analysis). Addition of the axial field improves experimental signal-to-noise ratio by more than an order of magnitude.     

Optimization of a quadrupole ion storage trap as a source for time‐of‐flight mass spectrometry

Designs of a quadrupole ion trap (QIT) as a source for time‐of‐flight (TOF) mass spectrometry are evaluated for mass resolution, ion trapping, and laser activation of trapped ions. Comparisons are made with the standard hyperbolic electrode ion trap geometry for TOF mass analysis in both linear and reflectron modes. A parallel‐plate design for the QIT is found to give significantly improved TOF mass spectrometer performance. Effects of ion temperature, trapped ion cloud size, mass, and extraction field on mass resolution are investigated in detail by simulation of the TOF peak profiles. Mass resolution (m/Δm) values of several thousand are predicted even at room temperature with moderate extraction fields for the optimized design. The optimized design also allows larger radial ion collection size compared with the hyperbolic ion trap, without compromising the mass resolution. The proposed design of the QIT also improves the ion–laser interaction volume and photon collection efficiency for fluorescence measurements on trapped ions. Copyright © 2011 John Wiley & Sons, Ltd.     

Development and Investigation of a Mesh-Electrode Linear Ion Trap (ME-LIT) Mass Analyzer

A mesh-electrode linear ion trap (ME-LIT) mass analyzer was developed and its performance was primarily characterized. In conventional linear ion trap mass analyzers, the trapped ions are mass-selected and then ejected in a radial direction by a slot on a trap electrode. The presence of slots can strongly affect the electric field distribution in the ion trapping region and distort the mass analysis performance. To compensate for detrimental electric field effects, the slot is usually designed and fabricated to be as small as possible, and also has very high mechanical accuracy and symmetry. A ME-LIT with several mesh electrodes was built to compensate for the effects caused by slots. Each mesh electrode was fabricated from a plate electrode with a relatively large slot and the slot was covered with a conductive mesh. Our preliminary experimental results show that the ME-LIT could considerably diminish the detrimental electric field effects caused by slots, and increase the mass resolving power and ion detection efficiency. Even with 4-mm-wide slots, a mass resolution in excess of 600 was obtained using the ME-LIT. Mass resolution could be remarkably improved using mesh electrodes in ion traps with asymmetric electrodes. The stability diagram of the ME-LIT was mapped, and highly efficient tandem mass spectrometry was demonstrated. The ME-LIT was qualified as a LIT mass analyzer. The ME-LIT can improve the mass resolution and decrease the requirements of mechanical accuracy and symmetry of slots, so it shows potential for a wide range of practical uses.

A segmented ring,cylindrical ion trap source for time-of-flight mass spectrometry

An ion trap source has been designed for use with time-of-flight (TOF) mass analysis. Two thin diaphragms make up a segmented ring electrode; the end cap electrodes are planar wire mesh. The potential field produced by the rf voltage applied between the ring and end cap electrodes resembles that of the cylindrical ion trap. The trapped ion population for ions created by electron impact exhibits linear growth against a first-order loss that has a time constant of about 50 µs; no ion loss occurs when the electron beam is off. The observed value of q _z at low-mass cutoff for rf ion storage is ?0.84. Pulsed extraction of all ions is accomplished by switching the trap electrodes from rf to voltages required to provide a linear dc extraction field. The TOF flight path includes a wide energy range reflectron. Better than unit mass resolution is achieved through m/z 500 without collisional ion cooling. With an extraction rate of 1 kHz and a recording rate of 4 spectra per second, a linear working curve is obtained between 36 pg and 18 ng of chlorobenzene delivered chromatographically. The system has demonstrated the potential to achieve a very high sample utilization efficiency at high spectral generation rates.     

New approaches to miniaturizing ion trap mass analyzers

Development of miniaturized ion trap (IT) mass analyzers for portable mass spectrometry has taken advantage of the latest technology in conventional machining and microfabrication. Researchers are now turning to new materials, such as polymers and ceramics, as well as alternative electrode shapes and arrangements to create the precisely-shaped electric fields needed for good performance on small-scale devices. Polymer-based construction allows lightweight structures, complex shapes and inexpensive production of small ITs. Simplified electrode arrangements, such as ITs made from two patterned ceramic plates, allow precise electric fields and simplified electrode alignment.     

Experimental evaluation of a hyperbolic ion trap for fourier transform ion cyclotron resonance mass spectrometry

The Penning ion trap, consisting of hyperbolically curved electrodes arranged as an unbroken ring electrode capped by two end electrodes whose interelectrode axis lies along the direction of an applied static magnetic field, has long been used for single-ion trapping. More recently, it has been used in “parametric” mode for ion cyclotron resonance (lCR) detection of off-axis ions. In this article, we describe and test a Penning trap whose ring electrode has been cut into four equal quadrants for conventional dipolar ICR excitation (on one pair of opposed ring quadrants) and dipolar ICR detection (on the other pair). In direct comparisons to a cubic trap, the present hyperbolic trap offers somewhat improved ICR mass spectral peak shape, higher mass resolving power, and comparable frequency shift as a function of trapping voltage. Mass measurement accuracy over a wide mass range is improved twofold and mass discrimination is somewhat worse than for a cubic trap. The relative advantages of parametric, dipolar, and quadrupole modes are briefly discussed in comparison to screened and unscreened cubic traps.     

Comparison of equilibrium ion density distribution and trapping force in penning, Paul, and combined ion traps

Starting from the classical Boltzmann distribution, we obtain the ion density distribution in the limit of either high temperature/low density (Coulomb interaction energy much less than ion kinetic energy) or low temperature/high density (kinetic energy much less than Coulomb interaction energy), and the trapping force for an ion cloud in Penning ion cyclotron resonance, Paul (quadrupole), and combined (Paul trap in a uniform axial static magnetic field) traps. At equilibrium (total angular momentum conserved), the ion cloud rotates at a constant frequency in Penning and combined traps. In a Penning trap, the maximum ion density is proportional to B ²/m (B is magnetic field and m is the mass of ions), whereas the maximum ion density in a Paul trap is proportional to (V _rf ² /mΩ² r ₀ ⁴ ), with Mathieu equation axial q value <0.4 to satisfy the pseudopotential approximation. Ion maximum densities in both Penning and Paul ion traps depend on the trapping field (magnetic or electric) and ion mass, but not on ion charge. In a Penning trap at maximum ion density (zero pressure), the radial (but not the axial) trapping potential is mass dependent, whereas both radial and axial potentials in a Paul trap at maximum ion density are mass dependent.     

Ion peak narrowing by applying additional AC voltage (ripple voltage) to FAIMS extractor electrode

The use of a non-uniform electric field in a high-field asymmetric waveform ion mobility spectrometry (FAIMS) analyzer increases sensitivity but decreases resolution. The application of an additional AC voltage to the extractor electrode (“ripple” voltage, U _ripple ) can overcome this effect, which decreases the FAIMS peak width. In this approach, the diffusion ion loss remains minimal in the non-uniform electric field in the cylindrical part of the device, and all ion losses under U _ripple occur in a short portion of their path. Application of the ripple voltage to the extractor electrode is twice as efficient as the applying of U _ripple along the total length of the device.     

Equilibrium space charge distribution in a quadrupole ion trap

A simple model provides a basis for evaluating the ion spatial distribution in a uadrupole (Paul) ion trap and its effect on the total potential (trap potential plus space charge 3 acting on ions in the trap. By combining the pseudopotential approximation introduced by Dehmelt 25 years ago with the assumption of thermal equilibrium (leading to a Boltzmann ion energy distribution), the resulting ion spatial distribution (for ions of a single mass-to-charge ratio) depends only on total number of ions, trap pseudopotential, and temperature. (The equilibrium assumption is justified by the high helium bath gas pressure at which analytical quadrupole ion traps are typically operated.) The electric potential generated by the ion space charge may be generated from Poisson’s equation subject to a Boltzmann ion energy distribution. However, because the ion distribution depends in turn on the total potential, solving for the potential and the ion distribution is no longer a simple boundary condition differential equation problem; an iterative procedure is required to obtain a self-consistent result. For the particularly convenient operating condition, (a _z = -8qU/m? ₀ ² Ω², and q _z =-4qV m? ₀ ² Ω², where U and V are direct current and radiofrequency (frequency, ω) voltages applied to the trap, m/q is ion mass-to-charge ratio, and ?₀ is the radius of the ring electrode at the z=0 midplane], both the pseudopotential and the ion distribution become spherically symmetric. The resulting one-dimensional problem may be solved by a simple optimization procedure. The present model accounts qualitatively for the dependence of total potential and ion distribution on number of ions (higher ion density or lower temperature flattens the total potential and widens the spatial distribution of ions) and pseudopotential (higher pseudopotential increases ion density near the center of the trap without widening the ion spatial distribution).     

稳定图的测定与矩形离子阱质谱性能分析

从理论上讲, 离子阱质谱仪的性能是由阱内电场分布决定的,而电场分布又是由组成离子阱的电极几何结构和离子阱工作电压决定的. 对于矩形离子阱, 即使不考虑其几何结构的偏差, 其阱内的电场分布一般也很复杂. 在矩形离子阱内, 除四极电场外, 还包含多种成分的其他各种高阶场, 它们直接影响离子在阱内的运动轨迹和离子阱质谱的性能. 由于各种电场成分对离子阱内离子运动的影响非常复杂, 还很难从数学上给出精确的解析解, 使得目前从理论上还无法预测高阶场成分对质谱性能的影响. 本工作通过测定不同几何结构的矩形离子阱的稳定图, 从实验上比较了不同场半径, 即不同电场分布条件下的离子阱质谱性能的差别. 实验中, 通过改变离子阱的几何比例结构, 详细测定了不同结构的矩形离子阱的稳定图特征, 并与实验测得的质谱分析结果进行比较. 同时, 我们还详细介绍了矩形离子阱质谱的稳定图的测定方法, 并根据得到的不同情况下的稳定图结构分析了离子阱的质谱性能. 研究结果表明： 可以通过比较试验得到的稳定图结构来判断其离子阱质谱仪的性能如质量分辨能力等. 此外, 实验结果还发现： 对于y方向拉伸结构的矩形离子阱, 其实验绘制得到的是不完整的稳定图. 但根据稳定图边界的特点, 通过采用四极直流电压调制的方法, 可以对y方向拉伸结构的矩形离子阱的性能进行改善, 极大地提高了阱的质量分辨能力.     

Novel ion traps using planar resistive electrodes: Implications for miniaturized mass analyzers

In radiofrequency ion traps, electric fields are produced by applying time-varying potentials between machined metal electrodes. The electrode shape constitutes a boundary condition and defines the field shape. This paper presents a new approach to making ion traps in which the electrodes consist of two ceramic discs, the facing surfaces of which are lithographically imprinted with sets of concentric metal rings and overlaid with a resistive material. A radial potential function can be applied to the resistive material such that the potential between the plates is quadrupolar, and ions are trapped between the plates. The electric field is independent of geometry and can be optimized electronically. The trap can produce any trapping field geometry, including both a toroidal trapping geometry and the traditional Paul-trap field. Dimensionally smaller ion trajectories, as would be produced in a miniaturized ion trap, can be achieved by increasing the potential gradient on the resistive material and operating the trap at higher frequency, rather than by making any physical changes to the trap or the electrodes. Obstacles to miniaturization of ion traps, such as fabrication tolerances, surface smoothness, electrode alignment, limited access for ionization or ion injection, and small trapping volume are addressed using this design.     

Simulation of Electric Potentials and Ion Motion in Planar Electrode Structures for Lossless Ion Manipulations (SLIM)

We report a conceptual study and computational evaluation of novel planar electrode structures for lossless ion manipulations (SLIM). Planar electrode SLIM components were designed that allow for flexible ion confinement, transport, and storage using a combination of radio frequency (rf) and DC fields. Effective potentials can be generated that provide near ideal regions for confining and manipulating ions in the presence of a gas. Ion trajectory simulations using SIMION 8.1 demonstrated the capability for lossless ion motion in these devices over a wide m/z range and a range of electric fields at low pressures (e.g., a few Torr). More complex ion manipulations (e.g., turning ions by 90^o and dynamically switching selected ion species into orthogonal channels) are also shown feasible. The performance of SLIM devices at ~4 Torr pressure for performing ion mobility-based separations (IMS) is computationally evaluated and compared with initial experimental results, and both are also shown to agree closely with experimental and theoretical IMS performance for a conventional drift tube design. Graphical Abstract

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阶梯电极离子阱质量分析器的结构与性能

本研究从理论上优化了一种新型结构的线型离子阱质量分析器-阶梯电极离子阱质量分析器,它是由2对阶梯电极与1对端盖电极组成。与传统平板电极矩形离子阱长阶梯电极离子阱相比,具有调节电场分布的优点,同时在几何结构设计上更接近于双曲面电极结构,但比双曲面电极更容易加工。通过改变阶梯电极结构的高度、宽度、场半径比例等几何参数,实现了对离子阱内部电场分布的优化,从而实现离子阱性能的优化。理论模拟研究结果表明,根据几何结构和电场分布优化获得的阶梯电极离子阱质量分析器(X0×Y0=9 mm×5 mm),可以在225 Da/ s 扫速下获得10150的质量分辨率。阶梯电极离子阱结构简单,分辨能力明显高于矩形离子阱。初步的实验结果表明,阶梯电极离子阱具有较好的串级质谱分析性能。     

Rapid analysis of polychlorinated biphenyls in the gas phase with resonance-enhanced two-photon ionization: optimal injection of ions into the ion-trap storage/time-of-flight mass spectrometer.

LI-IT-TOFMS (laser ionization/ion-trap storage/time-of-flight mass spectrometry) is expected to be a powerful tool for environmental monitoring. In the research reported here, real-time LI-IT-TOFMS measurements were carried out on gaseous 2-4 chlorinated PCBs in order to evaluate the applicability of an environmental monitoring method. With respect to ion-trap storage for PCBs, we found that the effect was due to the driving RF voltage on the ring electrode in the ion trap. For PCBs ions produced by laser irradiation, we observed that it was more efficient to reach the center of the ion trap by using a gated RF voltage rather than by using a continuous RF voltage. The ion trajectories in the ion trap were simulated by SIMION 7.0. We found that the voltage of the exit end cap electrode affected both the number of ions trapped and the orbit of ions inside the trap cell. Optimization of this parameter was performed using both simulated and experimental results. The achievable PCBs sensitivity for real-time (1 min) measurement using the LI-IT-TOFMS method was found to be in the pptV range (<0.01 mg/m3N) by means of a comparison with the conventional gas sampling/GS-MS method. A satisfactory proportional relationship was confirmed between the laser-based and conventional results.     

Ion trajectories in an electrostatic ion guide for external ion source fourier transform ion cyclotron resonance mass spectrometry

An electrostatic ion guide (EIG) that consists of concentric cylinder and central wire electrodes can transport ions efficiently from an external ion source to an ion cyclotron resonance (ICR) ion trap for mass analysis, with several advantages over current injection methods. Because the electrostatic force of the EIG captures ions in a stable orbit about the wire electrode, ions with initially divergent trajectories may be redirected toward the ICR ion trap for improved ion transmission efficiency. SIMION trajectory calculations (ion kinetic energy, 1–200 eV; elevation angle, 0.30 °; azimuthal angle, 0.360°) predict that ions of m/z 1000 may be transmitted through a strong (0.01 → 3.0-T) magnetic field gradient. Judicious choice of ion source position and EIG potential minimizes the spread in ion axial kinetic energy at the ICR ion trap. Advantages of the EIG include large acceptance angle, even for ions that have large initial kinetic energy and large radial displacement with respect to the central z-axis, low ion extraction voltage (5–20 V), and efficient trapping because ions need not be accelerated to high velocity to pass through the magnetic field gradient.     

CID of singly charged antioxidants applied in lubricants by means of a 3D ion trap and a linear ion trap-Orbitrap mass spectrometer

The aim of this study was to investigate the fragmentation behavior induced by low‐energy collision‐induced dissociation (LE‐CID) of four selected antioxidants applied in lubricants, by two different types of ion trap mass spectrometers: a three‐dimensional ion trap (3D‐IT) and a linear IT (LIT) Orbitrap MS. Two sterically hindered phenols and two aromatic amines were selected as model compounds representing different antioxidant classes and were characterized by positive‐ion electrospray ionization (ESI) and LE‐CID. Various types of molecular ions (e.g. [M]^+?, [M + H]⁺, [M + NH₄]⁺ or [M + Na]⁺) were used as precursor ions generating a significant number of structurally relevant product ions. Furthermore, the phenolic compounds were analyzed by negative‐ion ESI. For both IT types applied for fragmentation, the antioxidants exhibited the same unusual LE‐CID behavior: (1) they formed stable radical product ions and (2) C? C bond cleavages of aliphatic substituents were observed and their respective cleavage sites depended on the precursor ion selected. This fragmentation provided information on the type of structural isomer usually not obtainable for branched aliphatic substituents utilizing LE‐CID. Comparing the two instruments, the main benefit of applying the LIT‐Orbitrap was direct access to elemental composition of product ions enabling unambiguous interpretation of fragmentation trees not obtainable by the 3D‐IT device (e.g. loss of isobaric neutrals). It should be emphasized that the types of product ions formed do not depend on the type of IT analyzer applied. For characterizing degradation products of antioxidants, the LIT‐Orbitrap hybrid system, allowing the determination of accurate m/z values for product ions, is the method of choice. Copyright © 2011 John Wiley & Sons, Ltd.     

Simulated ion trajectory and induced signal in ion cyclotron resonance ion traps. Effect of ion initial axial position on ion coherence,induced signal,and radial or z ejection in a cubic trap

The effects of ion initial axial position on coherence of ion motion, induced ion cyclotron resonance (ICR) signal. and radial and z ejection have been evaluated by numerical simulation for a cubic Fourier transform-ion cyclotron resonance ion trap. For a given initial ion cyclotron phase and radius, ions of different initial z position are shown to be excited to significantly different ion cyclotron radii (and ultimately radially ejected at significantly different excitation amplitude-duration products). Ion initial z displacement from the trap midplane affects observed ICR signal magnitude in two ways: (1) for the same postexcitation cyclotron radius, an ion with larger initial z displacement induces a smaller ICR signal and (2) an ion with larger initial z displacement is excited to a smaller cyclotron radius. We also evaluate the induced ICR signal as a function of excitation amplitude-duration product for spatially uniform or Gaussian ion initial z distributions. In general, if the excitation waveform contains components at frequency, 2 ω_z or (ω₊ + 2 ω_z, in which ω_z is the axial C“trapping”) oscillation frequency, then ejection occurs axially. However, the resulting excitation amplitude-duration product for such axial ejection is significantly higher (factor of, ～ 4) than that required for radial ejection (at ω₊) for ions of small initial radius. The present results offer the first explanation of how, even if the ion is initially at rest on the z axis (i.e., zero excitation electric field amplitude on the z axis), z ejection (axial ejection) may nevertheless occur if the excitation waveform contains frequency components at ω₊ + 2ω_z and/or 2_{w z} Namely, our simulations reveal that off-resonant excitation pushes ions away from the z axis, after which the ions are exposed to z excitation and eventual z ejection.     

Identification and quantification of atractylenolide I and atractylenolide III in Rhizoma Atractylodes Macrocephala by liquid chromatography–ion trap mass spectrometry

Rhizoma Atractylodes Macrocephala (RAM) is an important traditional Chinese medicinal herb that is used for treatment of dyspepsia and anorexia. The active ingredients, atractylenolide I (AO‐I) and atractylenolide III (AO‐III), were identified by direct‐injection ion trap‐mass spectrometry (IT‐MS) for collecting MSⁿ spectra. The major fragment ions of AO‐I and AO‐III were confirmed by MSⁿ both in negative ion mode and in positive ion mode. The possible main cleavage pathway of fragment ions was studied. The determinations of AO‐I and AO‐III were accomplished by liquid chromatography (LC) with UV and MS. The analytes provided good signals corresponding to the protonated molecular ions [M + H]⁺ and product ions. The precursor ions and product ions for quantification of AO‐III and AO‐I were m/z 249 → 231 and m/z 233 → 215, respectively, using selected ion monitoring by LC‐IT‐MS. Two methods were evaluated for a number of validation characteristics (repeatability, limit of detection, calibration range, and recovery). MS provides a high selectivity and sensitivity for determination of AO‐III and AO‐I in positive mode. After optimization of the methods, separation, identification and quantification of the two components in RAM were comprehensively tested by HPLC with UV and MS. Copyright © 2012 John Wiley & Sons, Ltd.