Multimodal Stigmatic Imaging Mass Spectrometry with Flat-Top Laser Probe: SBIR Phase I Final Technical Report
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36 MATERIALS SCIENCE↗
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Spatial Glycomics and Kidney Disease
Glycans are critical for the kidney's physiological and pathological cellular functions, and our ability to reveal their spatial distributions within tissues has helped us reveal how these carbohydrate moieties are involved in many of these processes. This review discusses the role of different types of glycans in kidney biology and disease, common approaches used for glycan imaging, and how glycan imaging has helped us better understand kidney pathology. Here, we mainly focus on emerging methods using mass spectrometry imaging (MSI) because this technology is untargeted and provides complete information on glycan composition compared to the other methods, such as lectin and metabolite labeling, which are targeted and often inform only on the specific part of a glycan structure. We especially focus on protein N-glycosylation, as this is one of the most common post-translational modifications, and these moieties play a vital role in renal structure and function. The recent advancements in MSI of N-glycans we reviewed have provided new insights into the pathophysiology of the kidney and paved the way for clinical application.
60 APPLIED LIFE SCIENCES↗
Mass Spectral Imaging to Map Plant–Microbe Interactions
Plant–microbe interactions are of rising interest in plant sustainability, biomass production, plant biology, and systems biology. These interactions have been a challenge to detect until recent advancements in mass spectrometry imaging. Plants and microbes interact in four main regions within the plant, the rhizosphere, endosphere, phyllosphere, and spermosphere. This mini review covers the challenges within investigations of plant and microbe interactions. We highlight the importance of sample preparation and comparisons among time-of-flight secondary ion mass spectroscopy (ToF-SIMS), matrix-assisted laser desorption/ionization (MALDI), laser desorption ionization (LDI/LDPI), and desorption electrospray ionization (DESI) techniques used for the analysis of these interactions. Using mass spectral imaging (MSI) to study plants and microbes offers advantages in understanding microbe and host interactions at the molecular level with single-cell and community communication information. More research utilizing MSI has emerged in the past several years. We first introduce the principles of major MSI techniques that have been employed in the research of microorganisms. An overview of proper sample preparation methods is offered as a prerequisite for successful MSI analysis. Traditionally, dried or cryogenically prepared, frozen samples have been used; however, they do not provide a true representation of the bacterial biofilms compared to living cell analysis and chemical imaging. New developments such as microfluidic devices that can be used under a vacuum are highly desirable for the application of MSI techniques, such as ToF-SIMS, because they have a subcellular spatial resolution to map and image plant and microbe interactions, including the potential to elucidate metabolic pathways and cell-to-cell interactions. Promising results due to recent MSI advancements in the past five years are selected and highlighted. The latest developments utilizing machine learning are captured as an important outlook for maximal output using MSI to study microorganisms.
59 BASIC BIOLOGICAL SCIENCES↗
AVIRIS User's Guide
This paper serves as a brief overview of the AVIRIS instrument (Airborne Visible/Infrared Imaging Spectrometer) and its role in the field of imaging spectrometry. Mission planning and flight operations are discussed, and recommendations are given regarding the deployment of ground truth experiments.
AVIRIS↗
Understanding Degradation Mechanisms in SrIrO 3 Oxygen Evolution Electrocatalysts: Chemical and Structural Microscopy at the Nanoscale
Designing acid-stable oxygen evolution reaction electrocatalysts is key to developing sustainable energy technologies such as polymer electrolyte membrane electrolyzers but has proven challenging due to the high applied anodic potentials and corrosive electrolyte. This work showcases advanced nanoscale microscopy techniques supported by complementary structural and chemical characterization to develop a fundamental understanding of stability in promising SrIrO 3 thin film electrocatalyst materials. Cross-sectional high-resolution transmission electron microscopy illustrates atomic-scale bulk and surface structure, while secondary ion mass spectrometry imaging using a helium ion microscope provides the nanoscale lateral elemental distribution at the surface. After accelerated degradation tests under anodic potential, the SrIrO 3 film thins and roughens, but the lateral distribution of Sr and Ir remains homogeneous. A layer-wise dissolution mechanism is hypothesized, wherein anodic potential causes the IrO x -rich surface to dissolve and be regenerated by Sr leaching. Finally, the characterization approaches utilized herein and mechanistic insights into SrIrO 3 are translatable to a wide range of catalyst systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Spatially Resolved Mass Spectrometry at the Single Cell: Recent Innovations in Proteomics and Metabolomics
Biological systems are composed of heterogeneous populations of cells that intercommunicate to form a functional living tissue. Biological function varies greatly across populations of cells, as each single cell has a unique transcriptome, proteome, and metabolome that translates to functional differences within single species and across kingdoms. Over the past decade, substantial advancements in our ability to characterize omic profiles on a single cell level have occurred, including in multiple spectroscopic and mass spectrometry (MS)-based techniques. Of these technologies, spatially resolved mass spectrometry approaches, including mass spectrometry imaging (MSI), have shown the most progress for single cell proteomics and metabolomics. For example, reporter-based methods using heavy metal tags have allowed for targeted MS investigation of the proteome at the subcellular level, and development of technologies such as laser ablation electrospray ionization mass spectrometry (LAESI-MS) now mean that dynamic metabolomics can be performed in situ. In this Perspective, we showcase advancements in single cell spatial metabolomics and proteomics over the past decade and highlight important aspects related to high-throughput screening, data analysis, and more which are vital to the success of achieving proteomic and metabolomic profiling at the single cell scale. Finally, using this broad literature summary, we provide a perspective on how the next decade may unfold in the area of single cell MS-based proteomics and metabolomics.
59 BASIC BIOLOGICAL SCIENCES↗
Optical remote sensing of the earth
In the present assessment of the contributions of optical earth resources remote sensing in the 0.4-15.0 micron region, attention is given to underlying principles, applications to scientific disciplines such as geology, hydrology and oceanography, the recent development history of the requisite sensors, and sensor development trends. Development status characterizations are given for thematic mapping, modular optoelectronic multispectral scanning, the telescope/CCD 'SPOT' program of France, the thermal IR multispectral scanner for mineral signature identification, airborne imaging spectrometry, and the Advanced Visible and IR Imaging Spectrometer that is nearing deployment. Technology development trends and the capabilities they portend are projected.
Goetz, A. F. H.↗
Calibration of the Airborne Visible/Infrared Imaging Spectrometer in the Laboratory
Imaging spectrometry data must be spectrally, radiometrically and geometrically calibrated. This calibration process is validated for in-flight performance of the sensor using a rigorous ground truth campaign.
imaging↗
Spatial metabolomics and lipidomics in kidney disease
Kidney disease is a global health issue that affects over 850 million people, and early detection is key to preventing severe disease and complications. Kidney diseases are associated with complex dysregulation of lipid metabolism. Spatial metabolomics through mass spectrometry imaging (MSI) enables spatial mapping of the lipids in tissue and includes a variety of techniques that can be used to image lipids. In the kidney MSI studies often seek to resolve individual functional tissue units such as glomeruli and proximal tubules. Several different MSI techniques such as matrix-assisted laser desorption/ionization and desorption electrospray ionization have been used to characterize lipids and small molecules in chronic kidney disease, acute kidney injury, genetic kidney disease, and cancer. In this review we provide several examples of how spatial metabolomics data can provide critical information concerning localization of changes in disease states. Additionally, when combined with pathology, measurements, transcriptomics, or proteomics, the metabolomic changes can illuminate underlying mechanisms and provide new clinical insights.
59 BASIC BIOLOGICAL SCIENCES↗
Storage Conditions of Human Kidney Tissue Sections Affect Spatial Lipidomics Analysis Reproducibility
Lipids often are labile, unstable, and tend to degrade overtime, so it is of the upmost importance to study these molecules in their most native state. In this study, we sought to understand the optimal storage conditions for spatial lipidomic analysis of human kidney tissue sections. Specifically, we evaluated human kidney tissue sections on several different days throughout the span of a week using our established protocol for elucidating lipids using high mass resolution matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI). We studied kidney tissue sections stored under five different conditions: open stored at –80 °C, vacuumed sealed and stored at –80 °C, with matrix preapplied before storage at –80 °C, under a nitrogen atmosphere and stored at –80 °C, and at room temperature in a desiccator. Results were compared to data obtained from kidney tissue sections that were prepared and analyzed immediately after cryosectioning. Data was processed using METASPACE. After a week of storage, the sections stored at room temperature showed the largest amount of lipid degradation, while sections stored under nitrogen and at –80 °C retained the greatest number of overlapping annotations in relation to freshly cut tissue. Overall, we found that molecular degradation of the tissue sections was unavoidable over time, regardless of storage conditions, but storing tissue sections in an inert gas at low temperatures can curtail molecular degradation within tissue sections.
60 APPLIED LIFE SCIENCES↗
A New View of Mars
During the last 8 years the US has successfully sent 2 major spacecraft to Mars 1z?der= planet. The Mars Global Surveyor spacecraft (IGS), which started operating at Mars in Sept 1977 and Mars Odyssey spacecraft that started operating in Jan 2002, are both operational and collecting data, including 1.5 meter pixel imagery, them spectrometry, magnetometry, altimeter/radiometry, gamma ray and neutron counts. imaging spectrometry, and gravity. The two orbiters are conceptually similar to Earth orbiting spacecraft in that their primary purpose is to observe, monitor, and measure a variety of parameters about the planet and report any changes that might be occurring on the surfaces and in the atmosphere. As a result we now have detailed physical descriptions of the shape, topography, magnetism. surface roughness, thermal inertia, atmospheric pressure and temperature, the distribution of hydrogen in the top meter of the crust, models for the planetary interior based upon data, and an image set that portrays much of the history of the past 3 billion years. understand how the planet came to be this way.
Smith, David E.↗
A Fast-Pass, Desorption Electrospray Ionization Mass Spectrometry Strategy for Untargeted Metabolic Phenotyping
Desorption electrospray ionization mass spectrometry imaging (DESI-MSI) provides direct analytical readouts of small molecules that can be used to characterize the metabolic phenotypes of genetically engineered bacteria. In an effort to accelerate the time frame associated with the screening of mutant libraries, we have developed a high-throughput DESI-MSI analytical workflow implementing a single raster line-scan strategy that facilitates the collection of location-resolved molecular information from engineered strains on a subminute time scale. Evaluation of this “Fast-Pass” DESI-MSI phenotyping workflow on analytical standards demonstrated the capability of acquiring full metabolic profiling information with a throughput of ~40 s per sample. This Fast-Pass strategy was implemented in the analysis of genetically edited Escherichia coli strains that have been engineered to produce various free-fatty acids (FFAs) for applications relevant to biofuels. Due to the untargeted nature of DESI-MSI, the investigation of these strains yielded molecular information for both global metabolites and targeted detection of accumulated bioproducts, allowing simultaneous readouts of strain-specific chemical profiles and comparative measurements of FFA production levels.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The Shuttle Imaging Spectrometer Experiment (SISEX)
The concept of the imaging spectrometer is becoming established as a major new thrust in remote sensing of the earth. For several years, JPL has operated the airborne imaging spectrometer on a NASA C-130; this instrument has demonstrated the direct identification of surface materials using imaging spectrometry. An advanced aircraft instrument, the airborne visible/infrared imaging spectrometer (AVIRIS), began operation on a NASA U-2 in 1987. The Shuttle Imaging Spectrometer Experiment (SISEX) was conceived as the next step in the sequence, and would provide a relatively inexpensive demonstration of the concept in earth orbit. This paper describes the design and development status of SISEX and the status of the enabling technology.
Herring, Mark↗
Deep Learning on Multimodal Chemical and Whole Slide Imaging Data for Predicting Prostate Cancer Directly from Tissue Images
Prostate cancer is one of the most common cancers globally and is the second most common cancer in the male population in the US. Here we develop a study based on correlating the hematoxylin and eosin (H&E)-stained biopsy data with MALDI mass-spectrometric imaging data of the corresponding tissue to determine the cancerous regions and their unique chemical signatures and variations of the predicted regions with original pathological annotations. We obtain features from high-resolution optical micrographs of whole slide H&E stained data through deep learning and spatially register them with mass spectrometry imaging (MSI) data to correlate the chemical signature with the tissue anatomy of the data. We then use the learned correlation to predict prostate cancer from observed H&E images using trained coregistered MSI data. This multimodal approach can predict cancerous regions with ~80% accuracy, which indicates a correlation between optical H&E features and chemical information found in MSI. Further, we show that such paired multimodal data can be used for training feature extraction networks on H&E data which bypasses the need to acquire expensive MSI data and eliminates the need for manual annotation saving valuable time. Two chemical biomarkers were also found to be predicting the ground truth cancerous regions. This study shows promise in generating improved patient treatment trajectories by predicting prostate cancer directly from readily available H&E-stained biopsy images aided by coregistered MSI data.
60 APPLIED LIFE SCIENCES↗
Mapping playa evaporite minerals with AVIRIS data - A first report from Death Valley, California
The feasibility of using imaging spectrometry in studies of playa evaporites is demonstrated by mapping efflorescent salt crusts in Death Valley (California), using Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) data and a recently developed least-squares spectral band-fitting algorithm. It is shown that it was possible to remotely identify eight different saline minerals, including three borates that have not been previously reported for the Death Valley efflorescent crusts: hydroboracite, pinnoite, and rivadavite. The three borates are locally important phases in the crusts; at least one of them, rivadavite, appears to be forming directly from brine.
Crowley, James K.↗
Retrieval of Temperature and Species Distributions from Multispectral Image Data of Surface Flame Spread in Microgravity
Weight, size, and power constraints severely limit the ability of researchers to fully characterize temperature and species distributions in microgravity combustion experiments. A powerful diagnostic technique, infrared imaging spectrometry, has the potential to address the need for temperature and species distribution measurements in microgravity experiments. An infrared spectrum imaged along a line-of-sight contains information on the temperature and species distribution in the imaged path. With multiple lines-of-sight and approximate knowledge of the geometry of the combustion flowfield, a three-dimensional distribution of temperature and species can be obtained from one hyperspectral image of a flame. While infrared imaging spectrometers exist for collecting hyperspectral imagery, the remaining challenge is retrieving the temperature and species information from this data. An initial version of an infrared analysis software package, called CAMEO (Combustion Analysis Model et Optimizer), has been developed for retrieving temperature and species distributions from hyperspectral imaging data of combustion flowfields. CAMEO has been applied to the analysis of multispectral imaging data of flame spread over a PMMA surface in microgravity that was acquired in the DARTFire program. In the next section of this paper, a description of CAMEO and its operation is presented, followed by the results of the analysis of microgravity flame spread data.
Annen, K. D.↗
Spatial Modulation Improves Performance in CTIS
Suitably formulated spatial modulation of a scene imaged by a computed-tomography imaging spectrometer (CTIS) has been found to be useful as a means of improving the imaging performance of the CTIS. As used here, "spatial modulation" signifies the imposition of additional, artificial structure on a scene from within the CTIS optics. The basic principles of a CTIS were described in "Improvements in Computed- Tomography Imaging Spectrometry" (NPO-20561) NASA Tech Briefs, Vol. 24, No. 12 (December 2000), page 38 and "All-Reflective Computed-Tomography Imaging Spectrometers" (NPO-20836), NASA Tech Briefs, Vol. 26, No. 11 (November 2002), page 7a. To recapitulate: A CTIS offers capabilities for imaging a scene with spatial, spectral, and temporal resolution. The spectral disperser in a CTIS is a two-dimensional diffraction grating. It is positioned between two relay lenses (or on one of two relay mirrors) in a video imaging system. If the disperser were removed, the system would produce ordinary images of the scene in its field of view. In the presence of the grating, the image on the focal plane of the system contains both spectral and spatial information because the multiple diffraction orders of the grating give rise to multiple, spectrally dispersed images of the scene. By use of algorithms adapted from computed tomography, the image on the focal plane can be processed into an image cube a three-dimensional collection of data on the image intensity as a function of the two spatial dimensions (x and y) in the scene and of wavelength (lambda). Thus, both spectrally and spatially resolved information on the scene at a given instant of time can be obtained, without scanning, from a single snapshot; this is what makes the CTIS such a potentially powerful tool for spatially, spectrally, and temporally resolved imaging. A CTIS performs poorly in imaging some types of scenes in particular, scenes that contain little spatial or spectral variation. The computed spectra of such scenes tend to approximate correct values to within acceptably small errors near the edges of the field of view but to be poor approximations away from the edges. The additional structure imposed on a scene according to the present method enables the CTIS algorithms to reconstruct acceptable approximations of the spectral data throughout the scene.
Bearman, Gregory H.↗
Ultrasonic Imaging Of Deep Arteries
Swept-frequency sound replaces pulsed sound. Ultrasonic medical instrument produces images of peripheral and coronary arteries with resolutions higher and at depths greater than attainable by previous ultrasonic systems. Time-delay-spectrometry imager includes scanning, image-processing, and displaying equipment. It sweeps in frequency from 0 to 10 MHz in 20 ms, pauses for 5 ms, and repeats sweep. Intended for use in noninvasive detection and measurement of atherosclerotic lesions.
Rooney, James A.↗