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%.

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.

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.

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.

Improving the Performance of a Cycloidal Coded-Aperture Miniature Mass Spectrometer.

Cycloidal sector mass analyzers have, in principle, perfect focusing due to perpendicularly oriented uniform electric and magnetic fields, making them ideal candidates for incorporation of spatially coded apertures. We have previously demonstrated a proof-of-concept cycloidal-coded aperture miniature mass spectrometer (C-CAMMS) instrument and achieved a greater than 10-fold increase in throughput without sacrificing resolution, compared with a single slit instrument. However, artifacts were observed in the reconstructed mass spectrum due to nonuniformity in the electric field and misalignment of the detector and the ion source with the mass analyzer focal plane. In this work, we modified the mass analyzer design of the previous C-CAMMS instrument to improve electric field uniformity, improve the alignment of the ion source and the mass analyzer with the detector, and increase the depth-of-focus to further facilitate alignment. A comparison of reconstructed spectra of a mixture of dry air and toluene at different electric fields was performed using the improved C-CAMMS prototype. A reduction in reconstruction artifacts compared to our proof-of-concept C-CAMMS instrument highlights the improved performance enabled by the design changes.

Three-dimensionally-printed anthropomorphic physical phantom for mammography and digital breast tomosynthesis with custom materials, lesions, and uniform quality control region.

Anthropomorphic breast phantoms mimic patient anatomy in order to evaluate clinical mammography and digital breast tomosynthesis system performance. Our goal is to create a modular phantom with an anthropomorphic region to allow for improved lesion and calcification detection as well as a uniform region to evaluate standard quality control (QC) metrics. Previous versions of this phantom used commercial photopolymer inkjet three-dimensional printers to recreate breast anatomy using four surfaces that were fabricated with commercial materials spanning only a limited breast density range of 36% to 64%. We use modified printers to create voxelized, dithered breast phantoms with continuous gradations between glandular and adipose tissues. Moreover, the new phantom replicates the low-end density (representing adipose tissue) using third party material, Jf Flexible, and increases the high-end density to the density of glandular tissue and beyond by either doping Jf Flexible with salts and nanoparticles or using a new commercial resin, VeroPureWhite. An insert design is utilized to add masses, calcifications, and iodinated objects into the phantom for increased utility. The uniform chest wall region provides a space for traditional QC objects such as line pair patterns for measuring resolution and scale bars for measuring printer linearity. Incorporating these distinct design modules enables us to create an improved, complete breast phantom to better evaluate clinical mammography systems for lesion and calcification detection and standard QC performance evaluation.

Multi-carrier channeled polarimetry for photoelastic modulator systems.

Photoelastic modulator-based polarimeters use multi-carrier modulation schemes that are more complicated than the single carriers of rotating optics. Current state-of-the-art reconstruction implementations favor mathematical simplicity by using significantly abridged subsets of channels. In this Letter, we extend our generalized channeled polarimetry principles to address the challenges associated with multi-carrier modulation schemes. We demonstrate the performance forfeited by existing systems through the use of an incomplete set of information channels, as well as propose a set of more optimal system parameters that achieve better reconstruction noise characteristics. The overall improvement corresponds to a better sensitivity of up to a factor of six.

Single-shot memory-effect video.

Imaging through opaque scattering media is critically important in applications ranging from biological and astronomical imaging to metrology and security. While the random process of scattering in turbid media produces scattered light that appears uninformative to the human eye, a wealth of information is contained in the signal and can be recovered using computational post-processing techniques. Recent studies have shown that statistical correlations present in the scattered light, known as 'memory effects', allow for diffraction-limited imaging through opaque media without detailed knowledge of (or access to) the source or scatterer. However, previous methods require that the object and/or scatterer be static during the measurement. We overcome this limitation by combining traditional memory effect imaging with coded-aperture-based computational imaging techniques, which enables us to realize for the first time single-shot video of arbitrary dynamic scenes through dynamic, opaque media. This has important implications for a wide range of real-world imaging scenarios.

Proof of Concept Coded Aperture Miniature Mass Spectrometer Using a Cycloidal Sector Mass Analyzer, a Carbon Nanotube (CNT) Field Emission Electron Ionization Source, and an Array Detector.

Despite many potential applications, miniature mass spectrometers have had limited adoption in the field due to the tradeoff between throughput and resolution that limits their performance relative to laboratory instruments. Recently, a solution to this tradeoff has been demonstrated by using spatially coded apertures in magnetic sector mass spectrometers, enabling throughput and signal-to-background improvements of greater than an order of magnitude with no loss of resolution. This paper describes a proof of concept demonstration of a cycloidal coded aperture miniature mass spectrometer (C-CAMMS) demonstrating use of spatially coded apertures in a cycloidal sector mass analyzer for the first time. C-CAMMS also incorporates a miniature carbon nanotube (CNT) field emission electron ionization source and a capacitive transimpedance amplifier (CTIA) ion array detector. Results confirm the cycloidal mass analyzer's compatibility with aperture coding. A >10× increase in throughput was achieved without loss of resolution compared with a single slit instrument. Several areas where additional improvement can be realized are identified. Graphical Abstract ᅟ.

Effects of Magnetic and Electric Field Uniformity on Coded Aperture Imaging Quality in a Cycloidal Mass Analyzer.

Cycloidal mass analyzers are unique sector mass analyzers as they exhibit perfect double focusing, making them ideal for incorporating spatial aperture coding, which can increase the throughput of a mass analyzer without affecting the resolving power. However, the focusing properties of the cycloidal mass analyzer depend on the uniformity of the electric and magnetic fields. In this paper, finite element simulation and charged particle tracing were used to investigate the effect of field uniformity on imaging performance of a cycloidal mass analyzer. For the magnetic field, we evaluate a new permanent magnet geometry by comparing it to a traditional geometry. Results indicate that creating an aperture image in a cycloidal mass spectrometer with the same FWHM as the slit requires less than 1% variation in magnetic field strength along the ion trajectories. The new magnet design, called the opposed dipole magnet, has less than 1% field variation over an area approximately 62 × 65 mm; nearly twice the area available in a traditional design of similar size and weight. This allows ion imaging across larger detector arrays without loss of resolving power. In addition, we compare the aperture imaging quality of a traditionally used cycloidal mass spectrometer electric design with a new optimized design with improved field uniformity. Graphical abstract ᅟ.

Coded Apertures in Mass Spectrometry.

The use of coded apertures in mass spectrometry can break the trade-off between throughput and resolution that has historically plagued conventional instruments. Despite their very early stage of development, coded apertures have been shown to increase throughput by more than one order of magnitude, with no loss in resolution in a simple 90-degree magnetic sector. This enhanced throughput can increase the signal level with respect to the underlying noise, thereby significantly improving sensitivity to low concentrations of analyte. Simultaneous resolution can be maintained, preventing any decrease in selectivity. Both one- and two-dimensional (2D) codes have been demonstrated. A 2D code can provide increased measurement diversity and therefore improved numerical conditioning of the mass spectrum that is reconstructed from the coded signal. This review discusses the state of development, the applications where coding is expected to provide added value, and the various instrument modifications necessary to implement coded apertures in mass spectrometers.

Experimental demonstration of an adaptive architecture for direct spectral imaging classification.

Spectral imaging is a powerful tool for providing in situ material classification across a spatial scene. Typically, spectral imaging analyses are interested in classification, though often the classification is performed only after reconstruction of the spectral datacube. We present a computational spectral imaging system, the Adaptive Feature-Specific Spectral Imaging Classifier (AFSSI-C), which yields direct classification across the spatial scene without reconstruction of the source datacube. With a dual disperser architecture and a programmable spatial light modulator, the AFSSI-C measures specific projections of the spectral datacube which are generated by an adaptive Bayesian classification and feature design framework. We experimentally demonstrate multiple order-of-magnitude improvement of classification accuracy in low signal-to-noise (SNR) environments when compared to legacy spectral imaging systems.

Compatibility of Spatially Coded Apertures with a Miniature Mattauch-Herzog Mass Spectrograph.

In order to minimize losses in signal intensity often present in mass spectrometry miniaturization efforts, we recently applied the principles of spatially coded apertures to magnetic sector mass spectrometry, thereby achieving increases in signal intensity of greater than 10× with no loss in mass resolution Chen et al. (J. Am. Soc. Mass Spectrom. 26, 1633-1640, 2015), Russell et al. (J. Am. Soc. Mass Spectrom. 26, 248-256, 2015). In this work, we simulate theoretical compatibility and demonstrate preliminary experimental compatibility of the Mattauch-Herzog mass spectrograph geometry with spatial coding. For the simulation-based theoretical assessment, COMSOL Multiphysics finite element solvers were used to simulate electric and magnetic fields, and a custom particle tracing routine was written in C# that allowed for calculations of more than 15 million particle trajectory time steps per second. Preliminary experimental results demonstrating compatibility of spatial coding with the Mattauch-Herzog geometry were obtained using a commercial miniature mass spectrograph from OI Analytical/Xylem.

Order of Magnitude Signal Gain in Magnetic Sector Mass Spectrometry Via Aperture Coding.

Miniaturizing instruments for spectroscopic applications requires the designer to confront a tradeoff between instrument resolution and instrument throughput [and associated signal-to-background-ratio (SBR)]. This work demonstrates a solution to this tradeoff in sector mass spectrometry by the first application of one-dimensional (1D) spatially coded apertures, similar to those previously demonstrated in optics. This was accomplished by replacing the input slit of a simple 90° magnetic sector mass spectrometer with a specifically designed coded aperture, deriving the corresponding forward mathematical model and spectral reconstruction algorithm, and then utilizing the resulting system to measure and reconstruct the mass spectra of argon, acetone, and ethanol. We expect the application of coded apertures to sector instrument designs will lead to miniature mass spectrometers that maintain the high performance of larger instruments, enabling field detection of trace chemicals and point-of-use mass spectrometry.

Two-dimensional aperture coding for magnetic sector mass spectrometry.

In mass spectrometer design, there has been a historic belief that there exists a fundamental trade-off between instrument size, throughput, and resolution. When miniaturizing a traditional system, performance loss in either resolution or throughput would be expected. However, in optical spectroscopy, both one-dimensional (1D) and two-dimensional (2D) aperture coding have been used for many years to break a similar trade-off. To provide a viable path to miniaturization for harsh environment field applications, we are investigating similar concepts in sector mass spectrometry. Recently, we demonstrated the viability of 1D aperture coding and here we provide a first investigation of 2D coding. In coded optical spectroscopy, 2D coding is preferred because of increased measurement diversity for improved conditioning and robustness of the result. To investigate its viability in mass spectrometry, analytes of argon, acetone, and ethanol were detected using a custom 90-degree magnetic sector mass spectrometer incorporating 2D coded apertures. We developed a mathematical forward model and reconstruction algorithm to successfully reconstruct the mass spectra from the 2D spatially coded ion positions. This 2D coding enabled a 3.5× throughput increase with minimal decrease in resolution. Several challenges were overcome in the mass spectrometer design to enable this coding, including the need for large uniform ion flux, a wide gap magnetic sector that maintains field uniformity, and a high resolution 2D detection system for ion imaging. Furthermore, micro-fabricated 2D coded apertures incorporating support structures were developed to provide a viable design that allowed ion transmission through the open elements of the code.

Direct rapid-prototyping fabrication of computer-generated volume holograms in the millimeter-wave and terahertz regime.

Computer-generated volume holograms (CGVHs) are gradient refractive index (GRIN) devices that consist of a superposition of multiple periodic diffraction gratings. Fabrication of these components for the visible range is difficult due to the small length-scale requirements but is more tenable in the terahertz (THz), as the length scales become more practical (≥ 10-5 m). We successfully utilized polymer-based 3D additive rapid-prototyping technology to fabricate, to our knowledge, the world's first 3D THz CGVH in approximately 50 minutes, using $12 of consumables. This demonstration suggests that this technique could be extended to fabricate THz volumetric optics with arbitrary electromagnetic profiles.

Computational optical sensing and imaging: introduction to feature issue.

The 2012 Computational Optical Sensing and Imaging (COSI) conference of the Optical Society of America was one of six colocated meetings composing the Imaging and Applied Optics Congress held in Monterey, California, 24-28 June. COSI, together with the Imaging Systems and Applications, Optical Sensors, Applied Industrial Optics, and Optical Remote Sensing of the Environment conferences, brought together a diverse group of scientists and engineers sharing a common interest in measuring and processing of information carried by optical fields. This special feature includes several papers based on presentations given at the 2012 COSI conference as well as independent contributions, which together highlight several important trends.

Information-theoretic analysis of a stimulated-Brillouin-scattering-based slow-light system.

We use an information-theoretic method developed by Neifeld and Lee [J. Opt. Soc. Am. A 25, C31 (2008)] to analyze the performance of a slow-light system. Slow-light is realized in this system via stimulated Brillouin scattering in a 2 km-long, room-temperature, highly nonlinear fiber pumped by a laser whose spectrum is tailored and broadened to 5 GHz. We compute the information throughput (IT), which quantifies the fraction of information transferred from the source to the receiver and the information delay (ID), which quantifies the delay of a data stream at which the information transfer is largest, for a range of experimental parameters. We also measure the eye-opening (EO) and signal-to-noise ratio (SNR) of the transmitted data stream and find that they scale in a similar fashion to the information-theoretic method. Our experimental findings are compared to a model of the slow-light system that accounts for all pertinent noise sources in the system as well as data-pulse distortion due to the filtering effect of the SBS process. The agreement between our observations and the predictions of our model is very good. Furthermore, we compare measurements of the IT for an optimal flattop gain profile and for a Gaussian-shaped gain profile. For a given pump-beam power, we find that the optimal profile gives a 36% larger ID and somewhat higher IT compared to the Gaussian profile. Specifically, the optimal (Gaussian) profile produces a fractional slow-light ID of 0.94 (0.69) and an IT of 0.86 (0.86) at a pump-beam power of 450 mW and a data rate of 2.5 Gbps. Thus, the optimal profile better utilizes the available pump-beam power, which is often a valuable resource in a system design.

Terahertz electromagnetic crystal waveguide fabricated by polymer jetting rapid prototyping.

An all-dielectric THz waveguide has been designed, fabricated and characterized. The design is based on a hollow-core electromagnetic crystal waveguide, and the fabrication is implemented via polymer-jetting rapid prototyping. Measurements of the waveguide power loss factor show good agreement with simulation. As an initial example, a waveguide with propagation loss of 0.03 dB/mm at 105 GHz is demonstrated.

Novel Applications of Rapid Prototyping in Gamma-ray and X-ray Imaging.

Advances in 3D rapid-prototyping printers, 3D modeling software, and casting techniques allow for the fabrication of cost-effective, custom components in gamma-ray and x-ray imaging systems. Applications extend to new fabrication methods for custom collimators, pinholes, calibration and resolution phantoms, mounting and shielding components, and imaging apertures. Details of the fabrication process for these components are presented, specifically the 3D printing process, cold casting with a tungsten epoxy, and lost-wax casting in platinum.