Miniature toroidal radio frequency ion trap mass analyzer

A miniature ion trap mass analyzer is reported. The described analyzer is a 1/5-scale version of a previously reported toroidal radio frequency (rf) ion trap mass analyzer. The toroidal ion trap operates with maximum rf trapping voltages about 1 kVp-p or less; however despite the reduced dimensions, it retains roughly the same ion trapping capacity as conventional 3D quadrupole ion traps. The curved geometry provides for a compact mass analyzer. Unit-mass resolved mass spectra for n-butylbenzene, xenon, and naphthalene are reported and preliminary sensitivity data are shown for naphthalene. The expected linear mass scale with rf amplitude scan is obtained when scanned using a conventional mass-selective instability scan mode combined with resonance ejection.     

Characterization of a serial array of miniature cylindrical ion trap mass analyzers

Two small (5 mm internal radius) cylindrical ion traps (CITs) are arranged in series and operated using a single ion source, detector and radio frequency (rf) trapping signal. Ions are trapped in the first CIT and later transferred to the second by applying a direct current (dc) pulse to the endcap electrode of the first trap. This process is facilitated if a second, appropriately timed, retarding dc pulse is applied to the exit endcap electrode of the second trap. Mesh endcaps are used for the CITs to increase the number of ionizing electrons entering the trap and to maximize the transfer efficiency and detected signal. The transfer efficiency is dependent on the amplitude of the dc potential applied to eject the ions from the first trap, the amplitude of the dc potential applied to retain the ions in the second trap, and the period during which the retarding potential is applied. The amplitude and phase of the rf also affect the transfer process. Ions that readily dissociate upon collision have low transfer efficiencies; more stable ions can be transferred with up to 50% efficiency. Copyright 1999 John Wiley & Sons, Ltd.     

Novel linear ion trap mass analyzer composed of four planar electrodes

A novel linear ion trap mass analyzer was developed using just four elongated planar electrodes, mounted in parallel, and employing an RF potential for ion trapping in the radial and axial directions. Mass analysis was achieved using the mass-selective instability scan with ion ejection in the radial direction. The performance of this new device was characterized in comparison with the 6-electrode rectilinear ion trap (RIT) from which it is derived. The 4-electrode trap gives optimum performance in an asymmetric geometry, just like the original optimized 6-electrode RIT. The strong RF fringing fields at the ends of the RF rods account for axial ion trapping without use of extra electrodes or an axial DC voltage. Field calculations and simulations have been carried out to study the trapping potential inside RITs with various configurations. Demonstrated capabilities include analysis of externally injected ions with mass resolution in excess of 1000 and a mass/charge range of 650 Th as well as tandem mass spectrometry capabilities. The geometric simplicity and performance characteristics of the 4-electrode RIT make it particularly attractive in the development of next generation miniaturized mass spectrometers.     

Ion/molecule reactions performed in a miniature cylindrical ion trap mass spectrometer

A recently constructed miniature mass spectrometer, based on a cylindrical ion trap (CIT) mass analyzer, is used to perform ion/molecule reactions in order to improve selectivity for in situ analysis of explosives and chemical warfare agent simulants. Six different reactions are explored, including several of the Eberlin reaction type (M. N. Eberlin and R. G. Cooks, Org. Mass Spectrom., 1993, 28, 679-687) as well as novel gas-phase Meerwein reactions. The reactions include (1) Eberlin transacetalization of the benzoyl, 2,2-dimethyloximinium, and 2,2-dimethylthiooximinium cations with 2,2-dimethyl-1,3-dioxolane to form 2-phenyl-1,3-dioxolanylium cations, 2,2-dimethylamine-1,3-dioxolanylium cations and the 2,2-dimethylamin-1,3-oxathiolanylium cations, respectively; (2) Eberlin reaction of the phosphonium ion CH3P(O)OCH3+, formed from the chemical warfare agent simulant dimethyl methylphosphonate (DMMP), with 1,4-dioxane to yield the 1,3,2-dioxaphospholanium ion, a new characteristic reaction for phosphate ester detection; (3) the novel Meerwein reaction of the ion CH3P(O)OCH3+ with propylene sulfide forming 1,3,2-oxathionylphospholanium ion; (4) the Meerwein reaction of the benzoyl cation with propylene oxide and propylene sulfide to form 4-methyl-2-phenyl-1,3-dioxolane and its thio analog, respectively; (5) ketalization of the benzoyl cation with ethylene glycol to form the 2-phenyl-1,3-dioxolanylium cation; (6) addition/NO2 elimination involving benzonitrile radical cation in reaction with nitrobenzene to form an arylated nitrile, a diagnostic reaction for explosives detection and (7) simple methanol addition to the C7H7+ ion, formed by NO2 loss from the molecular ion of p-nitrotoluene to form an intact adduct. Evidence is provided that these reactions occur to give the products described and their potential analytical utility is discussed.     

Simulations of ion trapping in a micrometer-sized cylindrical ion trap

We have performed detailed SIMION simulations of ion behavior in micrometer-sized cylindrical ion traps (r0 = 1 microm). Simulations examined the effects of ion and neutral temperature, the pressure and nature of cooling gas, ion mass, trap voltage and frequency, space-charge, fabrication defects, and other parameters on the ability of micrometer-sized traps to store ions. At this size scale voltage and power limitations constrain trap operation to frequencies about 1 GHz and rf amplitudes of tens of volts. Correspondingly, the pseudopotential well depth of traps is shallow, and thermal energies contribute significantly to ion losses. Trapping efficiency falls off gradually as qz approaches 0.908, possibly complicating mass-selective trapping, ejection, or quantitation. Coulombic repulsion caused by multiple ions in a small-volume results in a trapping limit of a single ion per trap. If multiple ions are produced in a trap, all but one ion are ejected within a few microseconds. The remaining ion tends to have favorable trapping parameters and a lifetime about hundreds of microseconds; however, this lifetime is significantly shorter than it would have been in the absence of space-charge. Typical microfabrication defects affect ion trapping only minimally. We recently reported (IJMS 2004, 236, 91-104) on the construction of a massively parallel array of ion traps with dimensions of r0 = 1 microm. The relationship of the simulations to the expected performance of the microfabricated array is discussed.     

Three-dimensional monopole - a new ion trap mass analyser with one-dimensional ion sorting

This article describes an axially symmetric ion trap with one-dimensional ion sorting ('three-dimensional (3D) monopole'). The mass spectrometer can be created by substituting one hyperboloid endcap electrode with a cone-shaped electrode, the vertex of the cone coincides with the cross-over point of the asymptotes of the ion trap electrodes. The potential applied to this cone-shaped electrode is equal to the potential at the centre of the electrode system. The stability zone of the 3D monopole has a shape of a narrow band extending along the z boundary; the mass resolution and the quality factor (the product of resolution and sensitivity) are constant within this stability band which also lowers the requirements for the driving voltage stability. The mass resolution obtained 1s 100 measured at 50% peak height and the relative sensitivity is 3 x 10(-5).     

Characterization of bioparticles using a miniature cylindrical ion trap mass spectrometer operated at rough vacuum

A miniature cylindrical ion trap mass spectrometer (CIT-MS) equipped with an inexpensive mechanical pump was constructed, and used to measure the masses of cells and microparticles generated by laser induced acoustic desorption ionization. Compared with a previous lab scale quadrupole ion trap mass spectrometer (QIT-MS), the novel miniature CIT-MS had smaller volume (the radius r(0)=5 mm), simpler ion trap fabrication and overall instrument construction, required a lower trapping voltage, and reduced the weight, power and cost of the instrument. The CIT-MS was calibrated using standard polystyrene beads of 2.982 μm diameter. The CIT-MS was used to measure the total dry weight of human red blood cells (RBCs) from a healthy female adult (2.12×10(13) Da) and a patient with anemia (1.35×10(13) Da). The coefficient of variance (CV) for the healthy individual was 21% and that for the patient was 30.4%. The CIT-MS was also applied to guinea pig RBCs and the total dry weight was determined as 1.34×10(13) Da with a CV of 37.9%. These measurements are consistent with previous QIT-MS measurements. The new miniaturized instrument has potential for applications in field-portable, biological and aerosol analysis.     

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.     

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.     

High-throughput direct-infusion ion trap mass spectrometry: a new method for metabolomics

A fast method was developed to directly infuse raw plant extracts into a linear ion trap mass spectrometer, using the ion trap to isolate and fragment as many ions as possible from the extract. The full mass spectra can be analysed by multivariate statistics to determine discriminating ions, and the fragmentation data allows rapid classification or identification of these ions. The methodology was used to screen a wide range of strains of endophytic fungi in perennial ryegrass seeds for differences in metabolic profiles. The results show that this newly developed methodology is able to determine discriminating ions that can be present in very low concentrations. It also yielded sufficient fragmentation data to classify or identify the discriminating ions.     

Computer simulations of a new three rods ion optic (TRIPOLE) with high focusing and mass filtering capabilities

A novel three rod (tripole) ion optic to which three AC voltages with symmetrically delayed phase shifts were applied to each electrode. We studied its ion guiding, focusing, and mass filtering capabilities by SIMION ver. 7.0 computer simulations. An electric field mathematical model was developed to calculate the pseudopotential of the tripole radial AC force. The tripole showed stable ion guiding for wide ranges of AC amplitude; better collisional focusing than hexapole and octapole and similar focusing as quadrupole (rod pole). Also, the ion optic clearly showed interesting mass filtering potential when the phase shift was asymmetrically delayed. The symmetric shape of the pseudopotential field explained the tripole ion guiding and focusing capabilities. For mass filtering, the pseudopotential was asymmetric and its effect was balanced with DC voltage to separate the ions, depending in their masses. The resolution was much lower than quadrupole but useful when rough filtering was required.     

High-pressure ion trap mass spectrometry

The effects of buffer gas pressure on ion trap stability, mass resolution/calibration, and choice of mass scanning are described. Pressure effects were treated phenomenologically by adding a drag term to the ion equations of motion. The resulting collisional damping enlarges the mass-dependent stability region but reduces the region in which mass-selective resonance ejection can be performed. The pressure effects can be reduced by increasing the frequency of the alternating quadrupole field.     

Ion/molecule reactions for detecting ammonia using miniature cylindrical ion trap mass spectrometers

Gaseous ammonia, a common toxic industrial compound, is not detected readily in ion trap mass spectrometers because its molecular ion falls below the low-mass cutoff (~m/z 40) normally used when examining organic compounds. Instead, reactions of ammonia with halobenzene radical cations were used with internal electron ionization in two cylindrical ion trap miniature mass spectrometers to create a characteristic product ion by which to identify and quantify ammonia. Ammonia showed a linear response over the concentration range studied (parts per million [ppm] to parts per billion [ppb]) with limits of detection of 17 ppm and 220 ppb for experiments involving direct introduction and thermal desorption after pre-concentration, respectively. These values are comparable to ammonia's permissible exposure limit (50 ppm) and odor threshold (5 ppm). Receiver operating characteristic (ROC) curves were used to describe the method sensitivity, the probability of true positives, and the false positive rate for ammonia. A customized reaction scan function was created to select the species available for the ion/molecule reaction and set the amount of time the product ion could be accumulated in the trap. Product ion identity was verified using tandem mass spectrometry. Similar reactions with methylamine, ethylamine and the two nitriles, acetonitrile and benzonitrile, were explored.