A super-resolution proof of concept in a cycloidal coded aperture miniature mass spectrometer.

RATIONALE: Higher resolution in fieldable mass spectrometers (MS) is desirable in space flight applications to enable resolving isobaric interferences at m/z < 60 u. Resolution in portable cycloidal MS coupled with array detectors could be improved by reducing the slit width and/or by reducing the width of the detector pixels. However, these solutions are expensive and can result in reduced sensitivity. In this paper, we demonstrate high-resolution spectral reconstruction in a cycloidal coded aperture miniature mass spectrometer (C-CAMMS) without changing the slit or detector pixel sizes using a class of signal processing techniques called super-resolution (SR). METHODS: We developed an SR reconstruction algorithm using a sampling SR approach whereby a set of spatially shifted low-resolution measurements are reconstructed into a higher-resolution spectrum. This algorithm was applied to experimental data collected using the C-CAMMS prototype. It was then applied to synthetic data with additive noise, system response variation, and spatial shift nonuniformity to investigate the source of reconstruction artifacts in the experimental data. RESULTS: Experimental results using two ½ pixel shifted spectra resulted in a resolution of ¾ pixel full width at half maximum (FWHM) at m/z = 28 u. This resolution is equivalent to 0.013 u, six times better than the resolution previously published at m/z = 28 for N2 + using C-CAMMS. However, the reconstructed spectra exhibited some artifacts. The results of the synthetic data study indicate that the artifacts are most likely caused by the system response variation. CONCLUSIONS: This paper demonstrates super-resolution spectral reconstruction in C-CAMMS without changing the slit or detector pixel sizes using a sampling SR approach. With improvements, this technique could be used to resolve isobaric interferences in a portable cycloidal MS for space flight applications.

The Long Neglected Cycloidal Mass Analyzer.

In 1938, Walker Bleakney and John A. Hipple first described the cycloidal mass analyzer as the only mass analyzer configuration capable of "perfect" ion focusing. Why has their geometry been largely neglected for many years and how might it earn a respectable place in the world of modern chemical analysis? This Perspective explores the properties of the cycloidal mass analyzer and identifies the lack of suitable ion array detectors as a significant reason why cycloidal mass analyzers are not widely used. The recent development of capacitive transimpedance amplifier array detectors can enable several techniques using cycloidal mass analyzers including spatially coded apertures and single particle mass analysis with a "virtual-slit", helping the cycloidal mass analyzer earn a respectable place in chemical analysis.

Spectral Reconstruction Improvement in a Cycloidal Coded-Aperture Mass Spectrometer.

Spatial aperture coding is a technique used to improve throughput without sacrificing resolution both in optical spectroscopy and sector mass spectrometry (MS). Previous work demonstrated that aperture coding combined with a position-sensitive array detector in a miniature cycloidal mass spectrometer was successful in providing high-throughput, high-resolution measurements. However, due to poor alignment and field nonuniformities, reconstruction artifacts were present. Recently, significant progress was made in eliminating most of the reconstruction artifacts with improved field uniformity and alignment. However, artifacts as large as 1/3 of the main peak were still observed at low mass (<17 u). Such artifacts will reduce accuracy in identification and quantification of analytes, reducing the impact of the throughput advantage gained by using a coded aperture. The artifacts were hypothesized to be a result of a mass dependent in curvature of ions in the ion source. Ions with higher mass (m/z > 17 u) and a larger curvature did not pass through all slits in the coded aperture. Therefore, when reconstructing with a system response derived from the aperture image from a higher mass m/z = 32 u ion, reconstruction artifacts appeared for m/z < 17 u. In this work, two methods were implemented to significantly reduce the presence of artifacts in reconstructed data. First, we modified the reconstruction algorithm to incorporate a mass-dependent system response function across the mass range (10-110 u). This method reduced the size of the artifacts by 82%. Second, to validate the hypothesis that the mass-dependent system response function was a result of differences in curvature of ions in the ion source, we modified the design of the ion source by shifting the coded aperture slits relative to the center of the ionization volume. This method resulted in ions of all masses passing through all slits in the coded aperture, a constant system response function across the entire mass range. Artifacts were reduced by 94%.

Design considerations for a cycloidal mass analyzer using a focal plane array detector.

With the advent of technologies such as ion array detectors and high energy permanent magnet materials, there is renewed interest in the unique focusing properties of the cycloidal mass analyzer and its ability to enable small, high-resolution, and high-sensitivity instruments. However, most literature dealing with the design of cycloidal mass analyzers assumes a single channel detector because at the time of those publications, compatible multichannel detectors were not available. This manuscript introduces and discusses considerations and a procedure for designing cycloidal mass analyzers coupled with focal plane ion array detectors. To arrive at a set of relevant design considerations, we first review the unique focusing properties of the cycloidal mass analyzer and then present calculations detailing how the dimensions and position of the focal plane array detector relative to the ion source determine the possible mass ranges and resolutions of a cycloidal mass analyzer. We present derivations and calculations used to determine the volume of homogeneous electric and magnetic fields needed to contain the ion trajectories and explore the relationship between electric and magnetic field homogeneity on resolving power using finite element analysis (FEA) simulations. A set of equations relating the electric field homogeneity to the geometry of the electric sector electrodes was developed by fitting homogeneity values from 78 different FEA models. Finally, a sequence of steps is suggested for designing a cycloidal mass analyzer employing an array detector.