Small Business Innovation Research Contract Research Articles

Redox Tolerant Solid Oxide Electrolysis Cathode for CO2 and Steam

The production of oxygen for life support and ascent vehicle propellant oxidant is essential for human expeditions to Mars. OxEon team led the development of solid oxide electrolysis cell (SOEC) stacks for the Mars 2020 mission in collaboration with the Jet Propulsion Laboratory (JPL) and Massachusetts Institute of Technology (MIT). A stack that was installed in the Perseverance Rover has been operated twelve times so far to demonstrate the production of high purity oxygen by electrolyzing Mars atmosphere CO2.Traditionally, SOEC stacks use nickel–zirconia or nickel–ceria composite cathode to reduce the oxidized species. Nickel based electrodes are susceptible to oxidation by the feed gas (CO2 or steam) at the inlet conditions and are often irreversibly damaged during operation and start-up unless reduced species (carbon monoxide or hydrogen) are also present. Oxidation of Ni to NiO causes ~24% volume expansion, and a redox cycle with associated expansion and contraction can result in significant changes to the microstructure and loss of connectivity in the cathode and current collection layers. This challenge was encountered during early stack and testing development for the Mars mission where even short-term exposure to oxidizing dry CO2 feed caused massive performance degradation (12% of initial performance after 15 operational cycles). This necessitated a recycle loop for the stack on the Perseverance Rover that introduces a fraction of the CO-containing tail gas to the inlet to protect the cathode layers from oxidation.A simpler solution than a system recycle loop was desired for future applications. Under a NASA SBIR program OxEon investigated a combination of materials and engineering solutions to improve redox tolerance of the nickel-based cathode so that 100% dry CO2 could be fed directly into a stack without harming the electrode. A modified nickel-based cathode composition with a unique backbone and infiltrated cathode structure was developed and tested in both button cell and stack configurations. The new cathode has been shown to completely tolerate partial and full (i.e., complete oxidation of Ni to NiO before re-reduction) redox cycling, with complete performance recovery occurring in a matter of minutes even after total oxidation. It was also demonstrated that feeding a reducing gas after complete oxidation is not required since the CO generated by the applied voltage during initial CO2 electrolysis reaction is sufficient for self-reduction recovery. This self-recovery feature is particularly attractive for applications where an oxidizing gas feed cannot be easily substituted with a reducing gas feed, such as with Mars O2 generation.In-situ resource utilization (ISRU) of lunar ice and potential Martian ice for O2 and H2 generation is also of significant interest for future space missions. The redox tolerant cathode has been shown to completely tolerate steam oxidation as well, with self-generated H2 resulting in rapid reduction and recovery. Steam redox tolerance was demonstrated in both button cells and stacks and was independently verified by testing at PNNL. The redox tolerant cathode is also capable of rapid thermal cycling with ramp rates as high as 15 °C/min tested with no performance degradation. Improved coking tolerance over the traditional cathode material is an additional robustness feature that allows for higher conversion of CO2, enabling increased O2 production.This work was done under a NASA Small Business Innovation Research Contract No. 80NSSC19C0114. Validation testing at PNNL was performed under a DOE Award No. DE-FE0032105.

The Development of a 3D Printer-Inspired, Microgravity-Compatible Sample Preparation Device for Future Use Inside the International Space Station.

Biological testing on the International Space Station (ISS) is necessary in order to monitor the microbial burden and identify risks to crew health. With support from a NASA Phase I Small Business Innovative Research contract, we have developed a compact prototype of a microgravity-compatible, automated versatile sample preparation platform (VSPP). The VSPP was built by modifying entry-level 3D printers that cost USD 200-USD 800. In addition, 3D printing was also used to prototype microgravity-compatible reagent wells and cartridges. The VSPP's primary function would enable NASA to rapidly identify microorganisms that could affect crew safety. It has the potential to process samples from various sample matrices (swab, potable water, blood, urine, etc.), thus yielding high-quality nucleic acids for downstream molecular detection and identification in a closed-cartridge system. When fully developed and validated in microgravity environments, this highly automated system will allow labor-intensive and time-consuming processes to be carried out via a turnkey, closed system using prefilled cartridges and magnetic particle-based chemistries. This manuscript demonstrates that the VSPP can extract high-quality nucleic acids from urine (Zika viral RNA) and whole blood (human RNase P gene) in a ground-level laboratory setting using nucleic acid-binding magnetic particles. The viral RNA detection data showed that the VSPP can process contrived urine samples at clinically relevant levels (as low as 50 PFU/extraction). The extraction of human DNA from eight replicate samples showed that the DNA extraction yield is highly consistent (there was a standard deviation of 0.4 threshold cycle when the extracted and purified DNA was tested via real-time polymerase chain reaction). Additionally, the VSPP underwent 2.1 s drop tower microgravity tests to determine if its components are compatible for use in microgravity. Our findings will aid future research in adapting extraction well geometry for 1 g and low g working environments operated by the VSPP. Future microgravity testing of the VSPP in the parabolic flights and in the ISS is planned.

(Invited) Electrochemical Production of Oxygen and Fuel on Mars

The production of oxygen for life support and ascent vehicle propellant oxidant is essential for human expeditions to Mars. Solid oxide electrolysis (SOXE) stacks are capable of reducing carbon dioxide and water available on Mars to produce high purity oxygen. They can electrolyze CO2 or water separately or co-electrolyze CO2 and water together to produce oxygen and fuels such as methane for propulsion. OxEon’s team led the development of SOXE stacks in collaboration with the Jet Propulsion Laboratory (JPL) and Massachusetts Institute of Technology (MIT). The work resulted in delivering a set of flight qualified stacks to JPL. A packaged stack has been installed on the rover that is scheduled for launch next year for the Mars 2020 mission. The Mars Oxygen ISRU Experiment (MOXIE) will demonstrate the feasibility of producing high purity oxygen from Mars atmosphere carbon dioxide using a SOXE stack. Since delivering the stacks, the OxEon team has designed and begun fabricating SOXE stacks of the cell area required for a manned Mars mission. Under the NASA NextSTEP-2 ISRU activity, this platform will be tested with conditions targeting the ISRU application. MOXIE testing was focused on the case of atmospheric ISRU for oxygen evolution at the anode and did not make use of the CO byproduct gas at the cathode.. In 2019, OxEon will demonstrate CO2-steam co-electrolysis to produce carbon monoxide and hydrogen (synthesis gas) on the cathode and high purity oxygen at the anode. The synthesis gas will be converted to methane in an OxEon developed methanation reactor as an alternative to a water electrolysis coupled Sabatier system. In addition, OxEon is investigating a combination of materials and engineering solutions to improve redox tolerance of nickel-based cathode. Traditionally, SOXE stacks use nickel – zirconia or nickel – ceria composite cathode. Nickel based electrodes are susceptible to oxidation by the feed gas (CO2 or steam) at the inlet conditions unless reducing species (carbon monoxide or hydrogen) are also present. Button cell tests show that the new, modified cathode material exhibits good redox stability over multiple redox cycles with only a minor loss of performance after each cycle. Initial tests also show that under certain operating conditions the loss of performance can be recovered. Implementation of a redox tolerant cathode will eliminate the need for complex recycle loop that introduces a fraction of the product gases to the inlet in order to prevent nickel oxidation. Acknowledgement: NextSTEP ISRU work is supported under NASA Contract 8-HQTR19C0006. The redox tolerant cathode work is done under a NASA Small Business Innovation Research Contract No. 80NSSC18P1940. The work related to MOXIE was based on support from NASA through JPL’s prime contract, under JPL subcontract number 1515459.

Decreasing the Toxicity of Radiation Therapy: Radioprotectors and Radiomitigators Being Developed by the National Cancer Institute Through Small Business Innovation Research Contracts

The use of radioprotectors and radiomitigators could improve the therapeutic index of radiation therapy. With the intention of accelerating translation of radiation-effect modulators (radioprotectors and mitigators), the Radiation Research Program and SBIR (Small Business Innovation Research) Development Center within the National Cancer Institute issued 4 Requests for Proposals (RFPs) from 2010 to 2013. Twelve SBIR contract awards in total were made in response to the 4 RFPs from September 2011 through September 2014. Here, we provide an update on the status of SBIR contract projects for the development of radiation-effect modulators. To assess the status of research and development efforts under the 4 RFPs on radiation-effect modulators, we searched PubMed for research articles, google.com for published abstracts, clinicaltrials.gov for ongoing or completed clinical trials, and company websites for press releases and other news. All information obtained and reported here is publicly available and thus protects the intellectual property of the investigators and companies. Of the 12 SBIR projects funded, 5 (42%) transitioned successfully from phase 1 to phase 2 SBIR funding, and among the Fast-Track contracts, this rate was 100% (3 of 3). The Internet search identified 3 abstracts and 6 publications related to the aims of the SBIR contracts. One-third of the companies (4 of 12) have successfully launched a total of 8 clinical trials to demonstrate the safety and efficacy of their investigational agents. Two drugs are in clinical trials for their indication as a radioprotector, and 2 drugs are under evaluation for their anticancer properties (an immunomodulator and a small molecule inhibitor). The National Cancer Institute's SBIR has provided pivotal funding to small businesses for the development of radioprotectors and radiomitigators, which resulted in multiple early-phase clinical trials. Longer follow-up is needed to determine the full impact of these novel therapeutics that enter clinical practice.

Radioprotectors and Radiomitigators for Improving Radiation Therapy: The Small Business Innovation Research (SBIR) Gateway for Accelerating Clinical Translation.

Although radiation therapy is an important cancer treatment modality, patients may experience adverse effects. The use of a radiation-effect modulator may help improve the outcome and health-related quality of life (HRQOL) of patients undergoing radiation therapy either by enhancing tumor cell killing or by protecting normal tissues. Historically, the successful translation of radiation-effect modulators to the clinic has been hindered due to the lack of focused collaboration between academia, pharmaceutical companies and the clinic, along with limited availability of support for such ventures. The U.S. Government has been developing medical countermeasures against accidental and intentional radiation exposures to mitigate the risk and/or severity of acute radiation syndrome (ARS) and the delayed effects of acute radiation exposures (DEARE), and there is now a drug development pipeline established. Some of these medical countermeasures could potentially be repurposed for improving the outcome of radiation therapy and HRQOL of cancer patients. With the objective of developing radiation-effect modulators to improve radiotherapy, the Small Business Innovation Research (SBIR) Development Center at the National Cancer Institute (NCI), supported by the Radiation Research Program (RRP), provided funding to companies from 2011 to 2014 through the SBIR contracts mechanism. Although radiation-effect modulators collectively refer to radioprotectors, radiomitigators and radiosensitizers, the focus of this article is on radioprotection and mitigation of radiation injury. This specific SBIR contract opportunity strengthened existing partnerships and facilitated new collaborations between academia and industry. In this commentary, we assess the impact of this funding opportunity, outline the review process, highlight the organ/site-specific disease needs in the clinic for the development of radiation-effect modulators, provide a general understanding of a framework for gathering preclinical and clinical evidence to obtain regulatory approval and provide a basis for broader venture capital needs and support from pharmaceutical companies to fully capitalize on the advances made thus far in this field.