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Kojiro, Daniel R.

Publications and source records attributed to Kojiro, Daniel R..

A Tale of Two Small Business Grants: The Best of Times, the Worst of Times from the NASA Ames Small Business Innovative Research (SBIR) Program

The purposes of the SBIR Program are to: stimulate technological innovation in the private sector; strengthen the role of Small Business Concerns (SBCs) in meeting Federal research and development needs; increase the commercial application of these research results; and encourage participation of socially and economically disadvantaged persons and women-owned small businesses. The process can be highly rewarding, providing the small business with resources to pursue research and development with a focus on providing NASA with new and advanced capabilities. We present two examples of how the NASA Ames SBIR Program has addressed these purposes, nurturing innovative ideas from small, businesses into commercially viable products that also address analytical needs in space research. These examples, from the Science Instruments for Conducting Solar System Exploration Subtopic, describe the journey from innovative concept to analytical instrument, one successful and one hampered by numerous roadblocks (including some international intrigue}.

Kojiro, Daniel R.

Instrumentation for in situ sampling and analysis of compounds of interest to Astrobiology in the lower atmosphere and surface of Titan

Instrumentation for exploration of the solar system will require new enabling technology for in situ sample acquisition and analysis of pre-biotic chemistry in extreme planetary environments, such as that encountered at the surface of Titan. The potential use of balloon aero-rovers for Titan places special emphasis on the importance of miniaturization, low power and low usage of consumables. To help meet this need, we are developing a miniature gas chromatograph coupled with a new Mini-Cell ion mobility spectrometer (GC-IMS), and one of us (PMH) has begun development work on a miniaturized cryogenic inlet system with sampling probes for Titan. This instrumentation, and its approach for meeting measurement needs for the analysis of prebiotic chemistry on Titan, will be discussed.

Holland, Paul M.

Miniature GC: Minicell ion mobility spectrometer (IMS) for astrobiology planetary missions

Astrobiology flight experiments require highly sensitive instrumentation for in situ analysis of volatile chemical species and minerals present in the atmospheres and surfaces of planets, moons, and asteroids. The complex mixtures encountered place a heavy burden on the analytical instrumentation to detect and identify all species present. The use of land rovers and balloon aero-rovers place additional emphasis on miniaturization of the analytical instrumentation. In addition, smaller instruments, using tiny amounts of consumables, allow the use of more instrumentation and/or longer mission life for stationary landers/laboratories. We describe here the development of a miniature GC - Minicell Ion Mobility Spectrometer (IMS) under development through NASA's Astrobiology Science and Technology Instrument Development (ASTID) Program and NASA's Small Business Innovative Research (SBIR) Program.

Kojiro, Daniel R.

Miniature Gas Chromatograph (GC): Penning Ionization Electron Spectroscopy (PIES) Instrument for the Trace Analyses of Extraterrestrial Environments

In situ exploration of the solar system to identify its early chemistry as preserved in icy bodies and to look for compelling evidence of astrobiology will require new technology for chemical analysis. Chemical measurements in space flight environments highlight the need for a high level of positive identification of chemical compounds, since re-measurement by alternative techniques for confirmation will not be feasible. It also may not be possible to anticipate all chemical species that are observed, and important species may be present only at trace levels where they can be masked by complex chemical backgrounds. Up to now, the only techniques providing independent sample identification of GC separated components across a wide range of chemical species have been Mass Spectrometry (MS) and Ion Mobility Spectrometry (IMS). We describe here the development of a versatile and robust miniature GC detector based on Penning Ionization Electron Spectroscopy (PIES), for use with miniature GC systems being developed for planetary missions. PIES identifies the sample molecule through spectra related to its ionization potential. The combination of miniature GC technology with the primary identification capabilities of PIES provides an analytical approach ideal for planetary analyses.

Kojiro, Daniel R.

Miniature GC-Minicell Ion Mobility Spectrometer (IMS) for In Situ Measurements in Astrobiology Planetary Missions

Astrobiology flight experiments require highly sensitive instrumentation for in situ analysis of volatile chemical species and minerals present in the atmospheres and surfaces of planets, moons, and asteroids. The complex mixtures encountered place a heavy burden on the analytical instrumentation to detect and identify all species present. The use of land rovers and balloon aero-rovers place additional emphasis on miniaturization of the analytical instrumentation. In addition, smaller instruments, using tiny amounts of consumables, allow the use of more instrumentation and/or ionger mission life for stationary landers/laboratories. The miniCometary Ice and Dust Experiment (miniCIDEX), which combined Gas Chromatography (GC) with helium Ion Mobility Spectrometry (IMS), was capable of providing the wide range of analytical information required for Astrobiology missions. The IMS used here was based on the PCP model 111 IMS. A similar system, the Titan Ice and Dust Experiment (TIDE), was proposed as part of the Titan Orbiter Aerorover Mission (TOAM). Newer GC systems employing Micro Electro- Mechanical System (MEMS) based technology have greatly reduced both the size and resource requirements for space GCs. These smaller GCs, as well as the continuing miniaturization of Astrobiology analytical instruments in general, has highlighted the need for smaller, dry helium IMS systems. We describe here the development of a miniature, MEMS GC-IMS system (MEMS GC developed by Thorleaf Research Inc.), employing the MiniCell Ion Mobility Spectrometer (IMS), from Ion Applications Inc., developed through NASA's Astrobiology Science and Technology Instrument Development (ASTID) Program and NASA s Small Business Innovative Research (SBIR) Program.

Kojiro, Daniel R.

Mars Geochemical Instrument (MarGI): An instrument for the analysis of the Martian surface and the search for evidence of life

The Mars Geochemical Instrument, MarGI, was developed to provide a comprehensive analysis of the rocks and surface material on Mars. The instrument combines Differential Thermal Analysis (DTA) with miniature Gas Chromatography-Ion Mobility Spectrometry (GC-IMS) to identify minerals, the presence and state of water, and organic compounds. Miniature pyrolysis ovens are used to both, conduct DTA analysis of soil or crushed rocks samples, and pyrolyze the samples at temperatures up to 1000 degrees C for GC-IMS analysis of the released gases. This combination of analytical processes and techniques, which can characterize the mineralogy of the rocks and soil, and identify and quantify volatiles released during pyrolysis, has applications across a wide range of target sites including comets, planets, asteroids, and moons such as Titan and Europa. The MarGI analytical approach evolved from the Cometary Ice and Dust Experiment (CIDEX) selected to fly on the Comet Rendezvous Asteroid Flyby Mission (CRAF).

Kojiro, Daniel R.

Analytical Instrument for Determining the Composition of Surface Materials and Ices in the Solar System: Mini-CIDEX to TIDE

Exobiology experiments onboard spacecraft or space probes often require the detection and identification of a wide range of chemical species over vast concentration ranges. These experiments must be carried out under severely limited conditions utilizing minimal resources. The mini-Cometary Ice and Dust Experiment (mini-CIDEX) instrument was developed for the chemical analysis of a cometary environment. It combined a Gas Chromatograph (GC) with a helium-based Ion Mobility Spectrometer (IMS) to fulfill the analytical requirements of a cometary exobiology mission: universal response; ppb sensitivity; low mass, volume, and consumables. Mini-CIDEX has evolved into the Titan Ice and Dust Experiment (TIDE) for the chemical analysis of the surface (liquid and solid) and lower atmosphere of Titan. The complexity of the analyses will be similar to the comet application with a heavier emphasis on organic molecules. TIDE is a component of the Titan Orbiter Aero-Rover Mission (TOAM) proposed to NASA's New Visions Program. Advances to the Mini-CIDEX technology for the Titan application and the analytical capabilities of TIDE will be presented.

Kojiro, Daniel R.

Titan Ice and Dust Experiment (TIDE): Detection and Analysis of Compounds of Interest to Astrobiology in the Lower Atmosphere and Surface of Titan

The Titan Orbiter Aerorover Mission (TOAM) is a proposed concept for the Solar System Exploration Visions Mission, Titan Explorer, a follow-on to the Cassini-Huygens mission. TOAM would use a Titan polar orbiter and a lighter-than-air aerorover to investigate the surface and atmosphere of Titan. Astrobiology issues will be addressed though TOAM investigations including, for example: Distribution and composition of organics (atmospheric, aerosol, surface); Organic chemical processes, their chemical context and energy sources; and Seasonal variations and interactions of the atmosphere and surface. The TIDE instrument will perform in-situ analyses to obtain comprehensive and sensitive molecular and elemental assays of volatile organics in the atmosphere, oceans and surface. TIDE chemical analyses are conducted by a Gas Chromatograph-Ion Mobility Spectrometer (GC-IMS). This TIDE GC-IMS was a component of the mini-Cometary Ice and Dust Experiment (mini-CIDEX) developed for the chemical analysis of a cometary environment. Both the GC and helium IMS of mini-CIDEX have been further developed to better meet the analytical and operational requirements of the TOAM. application. A Micro-ElectroMechanical System (MEMS) GC and Mini-Cell helium IMS are under development to replace their respective mini-CIDEX components, providing similar or advanced analytical capabilities.

Kojiro, Daniel R.

Chemical Detection and Identification Techniques for Exobiology Flight Experiments

Exobiology flight experiments require highly sensitive instrumentation for in situ analysis of the volatile chemical species that occur in the atmospheres and surfaces of various bodies within the solar system. The complex mixtures encountered place a heavy burden on the analytical Instrumentation to detect and identify all species present. The minimal resources available onboard for such missions mandate that the instruments provide maximum analytical capabilities with minimal requirements of volume, weight and consumables. Advances in technology may be achieved by increasing the amount of information acquired by a given technique with greater analytical capabilities and miniaturization of proven terrestrial technology. We describe here methods to develop analytical instruments for the detection and identification of a wide range of chemical species using Gas Chromatography. These efforts to expand the analytical capabilities of GC technology are focused on the development of detectors for the GC which provide sample identification independent of the GC retention time data. A novel new approach employs Penning Ionization Electron Spectroscopy (PIES).

Kojiro, Daniel R.

Analytical/Operational Requirements for the In Situ Chemical Analysis of Cometary and Planetary Environments Using GC-IMS

Exobiology flight experiments require highly sensitive instrumentation for the in situ analysis of the volatile chemical species that occur in the atmospheres and surfaces of various bodies within the solar system. The complex mixtures encountered place a heavy burden on the analytical instrumentation to detect and identify all species present. The minimal resources available onboard for such missions mandate that the instruments provide maximum analytical capabilities with minimal requirements of volume, weight and consumables. The miniCIDEX instrument was developed for the chemical analysis of a cemetery environment. It combined a Gas Chromatograph (GC) with a helium based Ion Mobility Spectrometer (IMS) to fulfill the analytical requirements of a cemetery exobiology mission: universal response; ppb sensitivity; low mass, volume and consumable MiniCIDEX is now a candidate for the chemical analysis instrument of a Titan Aero-rover Mission. The complexity of the analyses will be similar to the comet application with a heavier emphasis on organic molecules. Because the Titan Aero-Rover will be a balloon powered rover, much more attention is placed on the total mass of the instrument package. The GC will likely be a Micro-Electro-Mechanical-System (MEMS) design, smaller than the initial miniCIDEX GC by a factor of ten (with a similar reduction in consumable use). Similar miniaturization of the helium-based IMS will be necessary while maintaining the analytical capabilities. The two mission applications, the analytical requirements, and the evolution of the IMS design to accommodate these requirements will be presented.

Kojiro, Daniel R.

The Hummingbird GC-IMS: In Situ Analysis of a Cometary Nucleus

Comets are of enormous scientific interest for many reasons. They are primitive bodies that date back to the earliest stages of solar system formation and, because of their small size and because they have been stored in the outer reaches of the solar system, their pristine nature has been preserved better than for any other class of body. They are extremely rich in highly volatile elements, many in the form of ices, and are richer in organic matter than any other known solar system body. It is strongly suspected that in addition to their content of primordial solar nebular material, they also incorporate unprocessed matter from the interstellar medium. Impacts by comets occur onto all the planets and satellites, often with major consequences (e.g., the dinosaur extinction event at the KIT boundary), or sometimes just providing a spectacular cosmic event (e.g., the collision of comet Shoemaker-Levy 9 with Jupiter). A mission to analyze a cometary nucleus must be capable of detecting and identifying over 30 molecular species among several different chemical groups. The Hummingbird Mission will rendezvous with, orbit, characterize, and make multiple descents to the nucleus of a comet. Hummingbird will employ a Gas Chromatograph - Ion Mobility Spectrometer (GC-IMS) as part-of a suite of sophisticated instruments for a comprehensive in situ elemental, molecular, and isotopic analysis of the comet.

Kojiro, Daniel R.

Sample Acquisition Techniques for Exobiology Flight Experiments

Exobiology Flight Experiments involve complex analyses conducted in environments far different than those encountered in terrestrial applications. A major part of the analytical challenge is often the selection, acquisition, delivery and, in some cases, processing of a sample suitable for the analytical requirements of the mission. The added complications of severely limited resources and sometimes rigid time constraints combine to make sample acquisition potentially a major obstacle for successful analyses. Potential samples come in a wide range including planetary atmospheric gas and aerosols (from a wide variety of pressures), planetary soil or rocks, dust and ice particles streaming off of a comet, and cemetery surface ice and rocks. Methods to collect and process sample are often mission specific, requiring continual development of innovative concepts and mechanisms. These methods must also maintain the integrity of the sample for the experimental results to be meaningful. We present here sample acquisition systems employed from past missions and proposed for future missions.

Kojiro, Daniel R.

Gas Chromatographic Detectors for Exobiology Flight Experiments

Exobiology flight experiments require highly sensitive instrumentation for in situ chemical analysis of the volatile chemical species that occur in the atmospheres and surfaces of various bodies within the solar system. The complex mixtures encountered place a heavy burden on the analytical instrumentation to detect and identify all species present. Future missions to Mars', comets, or planetary moons such as Europa, will perform experiments with complex analyses. In addition, instrumentation for such missions must perform under severely restricted conditions with limited resources. To meet these analytical requirements, improved methods and highly sensitive yet smaller instruments must continually be developed with increasingly greater capabilities. We describe here efforts to achieve this objective, for past and future missions, through the development of new or the improvement of existing sensitive, miniaturized gas chromatographic detectors.

Kojiro, Daniel R.

Development of Ion Mobility Spectrometry for Exobiology Flight Experiments

Ion Mobility Spectrometry (IMS) can provide gas chromatography with sample identification independent of sample retention time, with minimal interface. Initial commercial methods of IMS however, did not possess sufficient analytical capabilities and presented operational parameters which were unsuitable for exobiology missions. Subsequent development of IMS technology, with the focus on exobiology analytical requirements and mission imposed operational limitations, has produced an IMS interfaced with a GC capable of fulfilling the analytical requirements of several exobiology missions. Future exobiology missions will require further development of the IMS, particularly in the areas of overall instrument miniaturization and complex sample identification. The evolution of the exobiology focused IMS will be presented up to the current prototype design, which is a component of several proposed exobiology instruments. Areas of future development will also be discussed.

Kojiro, Daniel R.

The mini-CIDEX GC/IMS: Analysis of cometary ice and dust

Comets are recognized as among the most scientifically important objects in the solar system. They are presumed relics of the early primitive material in the solar nebula and are believed to have provided a general enrichment of volatiles to the inner solar system. The Cometary Coma Chemical Composition (C4) Mission, a proposed Discovery-Class Mission, will analyze materials released into the coma, providing information leading to the understanding of the chemical composition and make-up of the cometary nucleus. As one of two scientific instruments in the C4 spacecraft, an advanced and streamlined version of the Cometary Ice and Dust Experiment (CIDEX), a mini-CIDEX, will employ an X-Ray Fluorescence (XRF) spectrometer to determine bulk elemental composition of cometary dust grains and a Gas Chromatograph/Ion Mobility Spectrometer (GC/IMS) for determination of the molecular composition of dust and ices following stepwise pyrolysis and combustion. A description of the mini-CIDEX IMS will be provided as well as data from analyses conducted using the mini-CIDEX breadboard instrument.

Kojiro, Daniel R.

A Helium GC/IMS for the Analysis of Extraterrestrial Volatiles in Exobiology Flight Experiments

For exobiology experiments on board spacecraft or space probes, a wide range of chemical species often must be detected and identified. The limited amount of power and space available for flight instruments severely limits the number of instruments that can be flown on any given mission. It is important then, that these experiments utilize instrumentation with universal response, so that all species of interest can be analyzed. Instrumentation to fulfill the analytical requirements of exobiology experiments has been developed utilizing Gas Chromatography - Ion Mobility Spectrometry. The Gas Chromatograph (GC) combines columns developed specifically for the complex mixtures anticipated with highly sensitive Metastable Ionization Detectors (a type of Helium Ionization Detector). To satisfy the limitations placed on resources, the Ion Mobility Spectrometer (IMS) uses the same ultra high purity helium as the GC. This GC-MS provides the analytical capability to fulfill a wide range of exobiology flight experiment applications and has been included on a proposed Discovery Mission and proposals for both Lander and Orbiter of the European Space Agency's Rosetta Comet Mission. A data base of helium IMS spectra is now being built for these future applications.

Kojiro, Daniel R.

Determination of C1-C4 alkanes by ion mobility spectrometry

Results are presented from a comparison between two ion-mobility-spectrometer (IMS) methods of sample ionisation: a conventional IMS with very dry helium and an IMS using metastable helium ionization. As one of the tests, a mixture of several hydrocarbons expected to be the components of Titan's atmosphere (made of ethane, ethylene, acetylene, propane, n-butane, isobutane, and propyne in concentrations from 20 to 200 ppm) was analyzed by both methods. Results from the dry-He IMS showed that the dry-helium approach was more adequate for the analysis of these gases than the metastable-helium IMS approach. In the metastable-He approach, in which several versions of He ionization reaction were tested, the spectra produced were not as clear as the conventional IMS spectra, due to the fact that the strong electric field introduced in the reaction region to generate metastable helium affected the gating, resolution, and collection of the ions.

Kojiro, Daniel R.

Modulated-Voltage Metastable-Ionization Detector

New detector retains sensitivity of conventional ones but automatically reduces voltage to prevent current saturation at higher values, enabling quantitative determination of relative concentrations approaching 100 percent. Detector includes feedback circuitry to prevent current saturation. When detector current begins to exceed threshold, detector high voltage reduced to keep current from rising much more. Recorder output shows detector-current and voltage-reduction signals from gas mixture with constituents both above and below threshold concentration. Those above threshold cause both current and voltage-reduction peaks. Those below threshold give rise to current peaks only.

Carle, Glenn C.