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%.

Proof-of-Concept Vacuum Microelectronic NOR Gate Fabricated Using Microelectromechanical Systems and Carbon Nanotube Field Emitters.

This paper demonstrates a fully integrated vacuum microelectronic NOR logic gate fabricated using microfabricated polysilicon panels oriented perpendicular to the device substrate with integrated carbon nanotube (CNT) field emission cathodes. The vacuum microelectronic NOR logic gate consists of two parallel vacuum tetrodes fabricated using the polysilicon Multi-User MEMS Processes (polyMUMPs). Each tetrode of the vacuum microelectronic NOR gate demonstrated transistor-like performance but with a low transconductance of 7.6 × 10-9 S as current saturation was not achieved due to a coupling effect between the anode voltage and cathode current. With both tetrodes working in parallel, the NOR logic capabilities were demonstrated. However, the device exhibited asymmetric performance due to differences in the CNT emitter performance in each tetrode. Because vacuum microelectronic devices are attractive for use in high radiation environments, to test the radiation survivability of this device platform, we demonstrated the function of a simplified diode device structure during exposure to gamma radiation at a rate of 45.6 rad(Si)/second. These devices represent a proof-of-concept for a platform that can be used to build intricate vacuum microelectronic logic devices for use in high-radiation environments.

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.

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.

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.

Achieving Excellence in Graduate Research: A Guide for New Graduate Students.

A mentoring guide for incoming graduate students has been developed to minimize the time spent reiterating general guidance and "norms" that need to be instilled in new graduate students. This allows principal investigators and senior researchers to provide high value, customized coaching for the individual student which is where the real value of the PhD education is expressed.

Chemical ionization mass spectrometry using carbon nanotube field emission electron sources.

A novel chemical ionization (CI) source has been developed based on a carbon nanotube (CNT) field emission electron source. The CNT-based electron source was evaluated and compared with a standard filament thermionic electron source in a commercial explosives trace detection desktop mass spectrometer. This work demonstrates the first reported use of a CNT-based ion source capable of collecting CI mass spectra. Both positive and negative modes were investigated. Spectra were collected for a standard mass spectrometer calibration compound, perfluorotributylamine (PFTBA), as well as trace explosives including trinitrotoluene (TNT), Research Department explosive (RDX), and pentaerythritol tetranitrate (PETN). The electrical characteristics, lifetime at operating pressure, and power requirements of the CNT-based electron source are reported. The CNT field emission electron sources demonstrated an average lifetime of 320 h when operated in constant emission mode under elevated CI pressures. The ability of the CNT field emission source to cycle on and off can provide enhanced lifetime and reduced power consumption without sacrificing performance and detection capabilities. Graphical Abstract ᅟ.

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.

Implantable, multifunctional, bioresorbable optics.

Advances in personalized medicine are symbiotic with the development of novel technologies for biomedical devices. We present an approach that combines enhanced imaging of malignancies, therapeutics, and feedback about therapeutics in a single implantable, biocompatible, and resorbable device. This confluence of form and function is accomplished by capitalizing on the unique properties of silk proteins as a mechanically robust, biocompatible, optically clear biomaterial matrix that can house, stabilize, and retain the function of therapeutic components. By developing a form of high-quality microstructured optical elements, improved imaging of malignancies and of treatment monitoring can be achieved. The results demonstrate a unique family of devices for in vitro and in vivo use that provide functional biomaterials with built-in optical signal and contrast enhancement, demonstrated here with simultaneous drug delivery and feedback about drug delivery with no adverse biological effects, all while slowly degrading to regenerate native tissue.

Parallel Pool Analysis of Transient Spectroscopy Reveals Origins of and Perspectives for ZnO Hybrid Solar Cell Performance Enhancement Using Semiconducting Surfactants.

Recently, the performance of ZnO nanocrystals as an electron acceptor in a solar cell device was significantly increased by a semiconducting surfactant. Here we show, using transient absorption spectroscopy and a parallel pool analysis, that changes in the quantum efficiency of charge generation account for the performance variation among semiconducting-surfactant-coated, surfactant-coated, and uncoated ZnO nanoparticles. We demonstrate that even better surfactant design to suppress fast recombination could still lead to a further doubling of device efficiency.

Effect of nanoscale SubPc interfacial layer on the performance of inverted polymer solar cells based on P3HT/PC71BM.

The effect of a nanoscale boron subphthalocyanine chloride (SubPc) interfacial layer on the performance of inverted polymer solar cells based on poly (3-hexyl thiophene) (P3HT) and [6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71)BM) was studied. When a 1 nm SubPc layer was introduced between the active layer (P3HT:PC(71)BM) and MoO(x) in the device with ITO/ZnO/P3HT:PC(71)BM/SubPc/MoO(x)/Al configuration, the power conversion efficiency (PCE) was increased from 3.42 (without SubPc) to 3.59%. This improvement is mainly attributed to the enhanced open-circuit voltage from 0.62 to 0.64 V. When the Flory-Huggins interaction parameters were estimated from the solubility parameters through the contact angle measurement, it revealed that the interaction between SubPc and PC(71)BM is more attractive than that between SubPc and P3HT at the interface of P3HT:PC(71)BM/SubPc, through which charges are well transported from the active layer to the anode. This is supported by a decrease of the contact resistance from 5.49 (SubPc 0 nm) to 0.94 MΩ cm (SubPc 1 nm). The photoelectron spectra provide another evidence for the enhanced PCE, exhibiting that the 1 nm thick SubPc layer extracts more photoelectrons from the active layer than other thicknesses.

Formation of colorimetric fingerprints on nano-patterned deterministic aperiodic surfaces.

Periodic gratings and photonic bandgap structures have been studied for decades in optical technologies. The translational invariance of periodic gratings gives rise to well-known angular and frequency filtering of the incident radiation resulting in well-defined scattered colors in response to broadband illumination. Here, we demonstrate the formation of highly complex structural color patterns, or colorimetric fingerprints, in two-dimensional (2D) deterministic aperiodic gratings using dark field scattering microscopy. The origin of colorimetric fingerprints is explained by rigorous full-wave numerical simulations based on the generalized Mie theory. We show that unlike periodic gratings, aperiodic nanopatterned surfaces feature a broadband frequency response with wide angular intensity distributions governed by the distinctive Fourier properties of the aperiodic structures. Finally, we will discuss a range of potential applications of colorimetric fingerprints for optical sensing and spectroscopy.