Properties and performance of a quadrupole mass filter used for resonance ionization mass spectrometry

The performance of commercial quadrupole mass spectrometers (QMS) with a number of imperfections, as compared to the ideal hyperbolic geometry, has been characterized using the computer simulation program version 6.0. The analysis of simulated QMS geometries focuses primarily on modeling of the internal potential, the study of field deviations, and the influence of finite length on performance of the QMS. The computer simulation of ion trajectories in the QMS field yields predictions for optimum working conditions and provides estimates for the resolving power and the maximum isotopic abundance sensitivity. Experimental measurements that confirm these expectations are presented. Optimization of the geometry and various operational parameters of the QMS is an important step in the development of a system for highly selective ultratrace determination using laser-based resonance ionization mass spectrometry.     

A segmented radiofrequency-only quadrupole collision cell for measurements of ion collision cross section on a triple quadrupole mass spectrometer

The gas collision cell of a triple quadrupole mass spectrometer has been modified to consist of ten short quadrupole rod segments that allow an axial field to be applied to the cell in order to make measurements of ion mobility. The radiofrequency (rf)-quadrupole field provides effective radial confinement that greatly reduces diffusional losses at low pressure. The mobilities of mass-selected ions from an ionspray source have been measured at a pressure of 8 × 10^?3 torr at electric fields of 0. 1 to 3 V/cm, and used to calculate the collision cross sections of the ions. The measured cross sections compare well with those measured by other techniques.     

Comparison of ion coupling strategies for a microengineered quadrupole mass filter

The limitations of conventional machining and assembly techniques require that designs for quadrupole mass analyzers with rod diameters less than a millimeter are not merely scale versions of larger instruments. We show how silicon planar processing techniques and microelectromechanical systems (MEMS) design concepts can be used to incorporate complex features into the construction of a miniature quadrupole mass filter chip that could not easily be achieved using other microengineering approaches. Three designs for the entrance and exit to the filter consistent with the chosen materials and techniques have been evaluated. The differences between these seemingly similar structures have a significant effect on the performance. Although one of the designs results in severe attenuation of transmission with increasing mass, the other two can be scanned to m/z = 400 without any corruption of the mass spectrum. At m/z = 219, the variation in the transmission of the three designs was found to be approximately four orders of magnitude. A maximum resolution of M/DeltaM = 87 at 10% peak height has been achieved at m/z = 219 with a filter operated at 6 MHz and constructed using rods measuring (508 +/- 5) microm in diameter.     

Spectrophotometric errors associated with cells of circular cross section

It is shown that the use of spectrophotometric cells having circular cross sections leads to errors that depend on the absorbance, on the ratio of beam width to cell diameter, and on the distance between the center of the beam and the diameter of the cell, but that the nature and magnitude of these errors render them essentially undetectable in practical analytical work.     

Homotopy analysis method to study a quadrupole mass filter

The homotopy analysis method (HAM) is applied to study the behavior of a hyperbolic rods of quadrupole mass filter and a sinusoidal potential form V_ac cos(Ωt). Numerical computation method of a 20th‐order HAM is employed to compare the physical properties of the confined ions with fifth‐order Runge–Kutta method. Also, comparison is made for the first stability region, the ion trajectories in real time, the polar plots, and the ion trajectory in x ? y plan. The results show that the two methods are fairly similar; therefore, the HAM method has potential application to solve linear and nonlinear equations of the charge particle confinement in quadrupole field. Copyright © 2012 John Wiley & Sons, Ltd.     

An improved model of the fringing fields of a quadrupole mass filter

The fringing field region of a quadrupole mass filter is modelled using an iterative finite difference technique to solve Laplace's equation for the electrostatic potential. The results are used to formulate an expression f(z) such that the electrostatic potential of the fringing field, F(x, y, z, t) may be written in the form F(x, y, z, t) = f(z) φ(x, y, t), where φ(x, y, t) is the hyperbolic field of the quadrupole. The function f(z) is expressed in the form f(z) = 1 - exp {- az - bz²}), where a and b are constants and z is in units of r_O, where 2r_O is the spacing of the quadrupole rods. The effect of the distance from the quandrupole rods to the end plate of the quadrupole mass filter, d on f(z) is investigated and the results presented show that for d < 0.125 r_O the function f(z) does not alter significantly.     

液相色谱-串联四极杆飞行时间质谱和超高效液相色谱-串联三重四极杆质谱用于检测牛肉中的刚果红

建立了牛肉中刚果红的检测方法。定性方法采用液相色谱-串联四极杆飞行时间质谱对未知物进行质谱谱图库匹配,定量分析采用超高效液相色谱-串联三重四极杆质谱。牛肉样品中的刚果红经液液萃取净化后,采用Agilent ZORBAX Eclipse Plus C₁₈ Rapid Resolution HD色谱柱(50 mm×2.1 mm, 1.8 μm)进行分离,流动相为95%(体积分数)甲醇,流速为0.2 mL/min。AB 4000⁺三重四极杆质谱仪在电喷雾负离子化(ESI)及MRM模式下定量。结果显示,刚果红在0.03~1 mg/L浓度范围内,线性关系良好(相关系数为0.9998),精密度良好(RSD小于5%),回收率为88%~91%,检出限约为0.01 mg/L。本方法快速简便,重现性好,可以为牛肉及其他肉制品中刚果红的定量提供良好的解决方案。     

High performance collision cross section calculation—HPCCS

Since the commercial introduction of Ion Mobility coupled with Mass Spectrometry (IM‐MS) devices in 2003, a large number of research laboratories have embraced the technique. IM‐MS is a fairly rapid experiment used as a molecular separation tool and to obtain structural information. The interpretation of IM‐MS data is still challenging and relies heavily on theoretical calculations of the molecule's collision cross section (CCS) against a buffer gas. Here, a new software (HPCCS ) is presented, which performs CCS calculations using high perfomance computing techniques. Based on the trajectory method, HPCCS can accurately calculate CCS for a great variety of molecules, ranging from small organic molecules to large protein complexes, using helium or nitrogen as buffer gas with considerable gains in computer time compared to publicly available codes under the same level of theory. HPCCS is available as free software under the Academic Use License at https://github.com/cepid-cces/hpccs . © 2018 Wiley Periodicals, Inc.     

Influence of realistic fringing fields on the acceptance of a quadrupole mass filter

The modifications of the x and y acceptances of a quadrupole mass filter due to the influence of realistic fringing fields are calculated using the phase space dynamics approach for a range of ion axial velocities. The results are compared to those obtained from the conventional linear fringing field approximation and experimental data; significant differences are apparent. The quadrupole acceptances are found to be only weakly dependent on the spacing between the quadrupole rod ends and the entrance aperture plate.     

New possibilities and prospects for the development of quadrupole transit time mass spectrometers (monopole,tripole, mass filter)

Potentials of a new operating mode of quadrupole transit time mass spectrometers (monopole, tripole, mass filter) are considered. This new mode was named the three-dimensional focusing mode. The results of numerical simulations of the shape of mass peaks of quadrupole transit time mass spectrometers are presented. The prospects for the drastic improvement of the resolution and sensitivity of these devices in the new mode are shown and substantiated.     

Coupling of a Rydberg electron capture ion source with a quadrupole mass filter

The coupling of a Rydberg electron capture ion source with a Nermag R10-10H quadrupole mass filter is described. Details are given of the addition to this instrument of a creation cell for atoms excited in Rydberg states. Within the Nermag ion source, such atoms allow attachment of electrons of well-defined thermal energy. SF(6) was used for optimization of the main experimental parameters (gas pressures and voltages applied to the electrodes). The procedure by which Rydberg electron attachment was confirmed is described. A polychlorobiphenyl compound was used to illustrate the performance of this ionization technique. Ion formation was observed in the absence of fragmentation.     

Inductively coupled plasma mass spectrometry with a quadrupole mass filter operated in the third stability region

An inductively coupled plasma mass spectrometer system is described in which the quadrupole mass filter is operated in the third stability region with Mathieu parameters (a, q)=(3, 3). Operation at the upper tip of this region is found to give generally better sensitivity and resolution than operation at the lower tip. A limiting resolution at half height of 4000 at m/z 59 is possible with operation at the upper tip. This resolution is insufficient to separate atomic ions from molecular ions of the same nominal mass except in favorable cases. However, operation at moderate resolution (R _1/2=500 to 1000) is found to give very high abundance sensitivity (>10⁷). The results suggest that the third stability region may be advantageous for specialized applications of inductively coupled plasma mass spectrometry.     

Peak splitting with a quadrupole mass filter operated in the second stability region

Peak splitting or structure has been studied for a quadrupole mass filter operated in the second stability region with Mathieu parameters (a,q) ≈ (0.02.7.55). Two sources of peak splitting are considered and modeled theoretically: nonlinear resonances caused by field imperfections and ion collection effects caused by the periodic properties of ion motion in the quadrupole field. The conditions for the appearance of the nonlinear resonances and ion collection effects are derived and presented in terms of the β variables which determine the frequencies of ion oscillation. Comparisons of calculated peak structure to experimental peak shapes show that ion collection effects dominate, at least for the experimental conditions reported here. It is also shown that neither nonlinear resonances nor ion collection effects can distort the peak at high resolution.     

A double quadrupole for mass spectrometry/mass spectrometry

A double quadrupole mass spectrometer has been constructed to study unimolecular and collision-induced dissociation products from mass-selected ions. The two quadrupoles are closely coupled and the dissociation products sampled from a 2.5-mm interquadrupole region. Spectra obtained on the double quadrupole instrument are compared with published data obtained with triple quadrupole and reversed-sector (MIKE) mass spectrometers. The results indicate that the simple double quadrupole spectrometer is a highly efficient device which is a viable alternative to more complex quadrupole or sector instruments for obtaining dissociation spectra of mass-selected ions.     

Upper stability island of the quadrupole mass filter with amplitude modulation of the applied voltages

Modulation of the voltages applied to a quadrupole mass filter (QMF), either RF or RF and DC, leads to splitting of the stability region into islands of stability. The ion optical properties, such as transmission, resolving power and peak tails of the first upper stability islands have been investigated by numerical simulation of ion trajectories. The dependence of the location of this island on the amplitude of the modulation and the parameter nu = omega/Omega = Q/P where omega is modulation frequency, Omega is main angular radio frequency, and Q and P are integers, is calculated in detail. Different methods of adjusting the QMF resolution are examined. It is found that operation at the upper and lower tips of the stability islands created by amplitude modulation of the RF voltage is preferred, because of the technical simplicity of this method and a reduction of the required separation time. Amplitude modulation improves the performance of a QMF constructed with round rods, in comparison to perfect quadrupole fields. For example, with amplitude modulation of the RF, to reach a resolution of R(0.1) = 1200 requires only about 75 RF cycles of ion motion in a quadrupole field created by round rods.     

Prediction of mass transfer coefficient with suction for turbulent flow in cross flow ultrafiltration

Sherwood number relations for the prediction of the mass transfer coefficient for developing concentration boundary layer have been obtained for turbulent flow regime from first principles. The common flow modules, namely, rectangular channel, tubular and radial cross flow are considered. The relationships developed include the effect of suction through the membrane. Relevant relations for the estimation of mass transfer coefficient for cross flow ultrafiltration are formulated. The proposed Sherwood relations are used in conjunction with the osmotic pressure model to predict the permeate flux in osmotic pressure governed ultrafiltration. The simulated results are compared with the experimental data obtained from the literature. A detailed parametric study has been performed to observe the effects of the operating conditions on the filtration performance in terms of the permeate quantity and quality.