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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3

GeO{sub x} interfacial layer scavenging remotely induced by metal electrode in metal/HfO{sub 2}/GeO{sub x}/Ge capacitors

The metal gate electrodes of Ni, W, and Pt have been investigated for their scavenging effect: a reduction of the GeO{sub x} interfacial layer (IL) between HfO{sub 2} dielectric and Ge substrate in metal/HfO{sub 2}/GeO{sub x}/Ge capacitors. All the capacitors were fabricated using the same process except for the material used in the metal electrodes. Capacitance-voltage measurements, scanning transmission electron microscopy, and electron energy loss spectroscopy were conducted to confirm the scavenging of GeO{sub x} IL. Interestingly, these metals are observed to remotely scavenge the interfacial layer, reducing its thickness in the order of Ni, W, and then Pt. The capacitance equivalent thickness of these capacitors with Ni, W, and Pt electrodes are evaluated to be 2.7 nm, 3.0 nm, and 3.5 nm, and each final remnant physical thickness of GeO{sub x} IL layer is 1.1 nm 1.4 nm, and 1.9 nm, respectively. It is suggested that the scavenging effect induced by the metal electrodes is related to the concentration of oxygen vacancies generated by oxidation reaction at the metal/HfO{sub 2} interface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Hole scavenger redox potentials determine quantum efficiency and stability of Pt-decorated CdS nanorods for photocatalytic hydrogen generation

We use Pt-decorated CdS nanorods for photocatalytic hydrogen generation in the presence of sacrificial hole scavengers. Both the quantum efficiency for hydrogen generation and the stability of the colloidal nanocrystals in solution improve with increasing redox potential of the hole scavenger. The higher redox potential leads to faster hole scavenging, which increases quantum efficiency and stability since electron hole recombination and oxidation of the CdS become less important. The quantum efficiencies can be tuned over more than an order of magnitude. This finding is important for choosing hole scavengers and for comparing efficiencies and stabilities for different photocatalytic nanosystems.

36 MATERIALS SCIENCE↗

Multiple stable isotope characterization as a forensic tool to distinguish acid scavenger samples

Acid scavengers are frequently used as stabilizer compounds in a variety of applications. When used to stabilize volatile compounds such as nerve agents, the lower volatility and higher stability of acid scavengers make them more persistent in a post-event forensic setting. We are employing compound-specific stable isotope analysis of the carbon, nitrogen, and hydrogen components of three acid scavenging compounds (N,N-diethylaniline, tributylamine, and triethylamine) as a tool for distinguishing between different samples of the stabilizers. Combined analysis of three stable isotopes in these samples improves the technique’s resolving potential, enhancing sample matching capabilities. The compound specific methods developed here can be applied to instances where these compounds are not pure, such as when mixed with an agent or when found as a residue at an event site. Effective sample matching can be crucial for linking compounds at multiple event sites or linking a supply inventory to an event.

08 HYDROGEN↗

Hole-scavenging in photo-driven N 2 reduction catalyzed by a CdS-nitrogenase MoFe protein biohybrid system

The light-driven reduction of dinitrogen (N 2 ) to ammonia (NH 3 ) catalyzed by a cadmium sulfide (CdS) nanocrystal-nitrogenase MoFe protein biohybrid is dependent on a range of different factors, including an appropriate hole-scavenging sacrificial electron donor (SED). Here, the impact of different SEDs on the overall rate of N 2 reduction catalyzed by a CdS quantum dot (QD)-MoFe protein system was determined. The selection of SED was guided by several goals: (i) molecules with standard reduction potentials sufficient to reduce the oxidized CdS QD, (ii) molecules that do not absorb the excitation wavelength of the CdS QD, and (iii) molecules that could be readily reduced by sustainable processes. Earlier studies utilized buffer molecules or ascorbic acid as the SED. The effectiveness of ascorbic acid as SED was compared to dithionite (DT), triethanolamine (TEOA), and hydroquinone (HQ) across a range of concentrations in supporting N 2 reduction to NH 3 in a CdS QD-MoFe protein photocatalytic system. It was found that TEOA supported N 2 reduction rates comparable to those observed for dithionite and ascorbic acid. HQ was found to support significantly higher rates of N 2 reduction compared to the other SEDs at a concentration of 50 mM. A comparison of the rates of N 2 reduction by the biohybrid complex to the standard reduction potential (E o ) of the SEDs reveals that E o is not the only factor impacting the efficiency of hole-scavenging. These findings reveal the importance of the SED properties for improving the efficiency of hole-scavenging in the light-driven N 2 reduction reaction catalyzed by a CdS QD–MoFe protein hybrid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Using multiple data sources to investigate foraging niche partitioning in sympatric obligate avian scavengers

As carrion feeders competing for a limited and ephemeral resource, avian scavengers are ideal model organisms to study mechanisms of niche partitioning. Previous work has focused on observations of species’ interactions at carcasses, and although fruitful, the inclusion of behavior beyond that at carcasses, such as movement patterns, could yield a more comprehensive understanding of mechanisms of foraging niche partitioning. Our goal was to assess how differences in physiological, morphological, and social characteristics between sympatric black vultures ( Coragyps atratus ) and turkey vultures ( Cathartes aura ) manifest interspecific variation in movement patterns, foraging habitats, and carcass use to reduce direct competition. Both species are obligate scavengers that co-occur across much of the New World. Turkey vultures are solitary foragers with enhanced olfactory capabilities and wings optimized for energy-efficient low-altitude soaring. Black vultures are aggressive, heavier bodied, and forage socially. We assessed interspecific variation in carcass exploitation using experimental carcass trials encompassing a range of habitats, carcass sizes, and seasons, and used GPS telemetry to compare how soaring conditions influenced daily space use and diurnal patterns of movement activity for each species. Turkey vultures occurred more often at small (i.e., rabbit) carcasses, and those obscured by forest cover than black vultures, and were the first vultures recorded at 94% of carcasses visited by both species. Both species increased movement rates and daily ranges when soaring conditions were favorable; however, turkey vultures had higher travel rates regardless of soaring conditions. Our results suggest the olfactory sense of turkey vultures allows them to locate smaller and visually obscured carcasses more efficiently than black vultures, facilitated by wing morphology that allows them to forage over large areas efficiently. Socially foraging black vultures appear specialized at locating larger carcasses in open habitats, which does not require as much foraging flight as turkey vultures. Our study illustrates how inclusion of movement ecology into niche partitioning studies provides a more complete understanding of the mechanisms of coexistence in avian scavenger guilds. This approach may provide important information to guide conservation efforts, such as supplemental feeding, of imperiled vulture species.

54 ENVIRONMENTAL SCIENCES↗

Radiolytic degradation of n -dodecane: Insights from time resolved pulsed electron radiolysis using aromatic scavengers

This study uses time-resolved picosecond pulsed electron radiolysis and transient absorbance spectroscopy to investigate early radiolytic processes in n-dodecane, a prototypical organic solvent for reprocessing used nuclear fuel (UNF). The primary radical cation, solvated electron, and excited states in neat n-dodecane are formed and consumed on timescales that are difficult to observe directly. Aromatic solutes, biphenyl and benzophenone, were utilized as scavengers to convert these short-lived species into longer-lived, optically detectable transient products to serve as indirect probes of the fraction of the initial n-dodecane radiolytic products that can be intercepted before undergoing ultrafast decay or competing reactions. The transient absorbance spectra of these scavengers and their radiolytic products were analyzed. Results indicate that while biphenyl and benzophenone effectively capture several radiolytic species, they do not fully scavenge all n-dodecane excited states, suggesting potential inefficiencies or additional side reactions. This study provides insight into the formation and accessibility of radiation-induced excited states and charge carriers in n-dodecane, which play a key role in the degradation of solvent extraction systems used in UNF reprocessing.

58 GEOSCIENCES↗

RNA helicase DDX5 participates in oxLDL-induced macrophage scavenger receptor 1 expression by suppressing mRNA degradation

Highlights: • RNA helicase DDX5 positively regulates macrophage lipid uptake. • Macrophages scavenger receptor 1(MSR1) mRNA is stabilized by DDX5. • The m{sup 6}a modification of MSR1 mRNA was regulated by interaction of mettl3 and DDX5. • Degradation of MSR1 mRNA was suppressed by m{sup 6}a modification on mRNA. The DEAD box protein DDX5, an ATP-dependent RNA helicase, plays an important role in transcriptional regulation and is associated with solid tumors and leukemia. However, its role in oxLDL-induced lipid uptake in macrophages remains unclear. In this study, we detected the expression of DDX5 mRNA and protein in oxidized low-density lipoprotein (oxLDL)-treated human primary macrophages that were induced from monocytes isolated from human peripheral blood with or without several chemical inhibitors using quantitative real-time PCR (qRT-PCR) or Western blotting. We found that oxLDL induced DDX5 expression to be independent of both the MAPK and NF-κB pathways. We also found that DDX5 promoted macrophage lipid uptake by evaluating the fluorescence intensity of engulfed dil-oxLDL. Various scavenger receptors that participate in lipid uptake were detected in siR-DDX5 transfected macrophages using qRT-PCR and Western blotting. Macrophage scavenger receptor A (MSR1) was found to be involved the upregulation of DDX5-mediated lipid uptake. Through the use of a dual luciferase reporter assay system and incubation with cycloheximide (CHX) MG132 and actidione (ActD), we found that DDX5 promoted MSR1 protein expression by stabilizing MSR1 mRNA. Moreover, the mechanism involved in DDX5 regulation of MSR1 mRNA was also explored using mass spectrum analysis; Immunoprecipitations (IPs) and RNA- Immunoprecipitations (R-IPs) revealed that mettl3 was involved in DDX5-mediated MSR1 mRNA stabilization. In addition, we also demonstrated that DDX5 inhibited mettl3 to catalyze m{sup 6}a methylation in MSR1 mRNA, which contributed to the maintenance of MSR1 mRNA stability. In conclusion, ox-LDL promotes DDX5 expression in macrophages, which interacts with mettl3 to stabilize MSR1 mRNA by decreasing the m{sup 6}a modification of MSR1 mRNA, ultimately promoting lipid uptake in macrophages.

60 APPLIED LIFE SCIENCES↗

Novel mechanism for scavenging of hypochlorite involving a periplasmic methionine-rich peptide and methionine sulfoxide reductase

Reactive chlorine species (RCS) defense mechanisms are important for bacterial fitness in diverse environments. In addition to the anthropogenic use of RCS in the form of bleach, these compounds are also produced naturally through photochemical reactions of natural organic matter and in vivo by the mammalian immune system in response to invading microorganisms. To gain insight into bacterial RCS defense mechanisms, we investigated Azospira suillum strain PS, which produces periplasmic RCS as an intermediate of perchlorate respiration. Our studies identified an RCS response involving an RCS stress-sensing sigma/anti-sigma factor system (SigF/NrsF), a soluble hypochlorite-scavenging methionine-rich periplasmic protein (MrpX), and a putative periplasmic methionine sulfoxide reductase (YedY1). We investigated the underlying mechanism by phenotypic characterization of appropriate gene deletions, chemogenomic profiling of barcoded transposon pools, transcriptome sequencing, and biochemical assessment of methionine oxidation. Our results demonstrated that SigF was specifically activated by RCS and initiated the transcription of a small regulon centering around yedY1 and mrpX. A yedY1 paralog ( yedY2 ) was found to have a similar fitness to yedY1 despite not being regulated by SigF. Markerless deletions of yedY2 confirmed its synergy with the SigF regulon. MrpX was strongly induced and rapidly oxidized by RCS, especially hypochlorite. Our results suggest a mechanism involving hypochlorite scavenging by sacrificial oxidation of the MrpX in the periplasm. Reduced MrpX is regenerated by the YedY methionine sulfoxide reductase activity. The phylogenomic distribution of this system revealed conservation in several Proteobacteria of clinical importance, including uropathogenic Escherichia coli and Brucella spp., implying a putative role in immune response evasion in vivo . In addition, bacteria are often stressed in the environment by reactive chlorine species (RCS) of either anthropogenic or natural origin, but little is known of the defense mechanisms they have evolved. Using a microorganism that generates RCS internally as part of its respiratory process allowed us to uncover a novel defense mechanism based on RCS scavenging by reductive reaction with a sacrificial methionine-rich peptide and redox recycling through a methionine sulfoxide reductase. As a result, this system is conserved in a broad diversity of organisms, including some of clinical importance, invoking a possible important role in innate immune system evasion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lowering the Impedance of Lanthanum Strontium Manganite-Based Electrodes with Lanthanum Oxychloride and Lanthanum Scavenging Chloride Salts

The impact of infiltrating chloride salts on the electrochemical behavior of lanthanum strontium manganite-yttria stabilized zirconia (LSM-YSZ) cathodes was investigated under solid oxide fuel cell operation. Infiltrating a lanthanum chloride solution resulted in the formation of a lanthanum oxychloride (LaOCl) phase. A LaOCl phase also formed by infiltrating an ammonium chloride solution; however, lanthanum was scavenged from the LSM phase to form LaOCl. The third infiltrating solution, a combination of zirconium chloride and yttrium nitrate, formed LaOCl by scavenging lanthanum from LSM and produced YSZ nanoparticles. Electrochemical impedance spectroscopy results suggest that LaOCl improves oxygen adsorption kinetics compared to a baseline LSM-YSZ cathode, reducing the low frequency impedance by 30%. In addition, scavenging lanthanum from LSM improved oxygen ion diffusion polarization as indicated by the observed 40% reduction in high frequency impedance and improved serial ohmic resistance by 19%. Finally, YSZ nanoparticles further reduced the high frequency impedance and ohmic resistance by 45% and 23%, respectively. The findings reveal new strategies for lowering the impedance of LSM-YSZ cathodes.

Taylor, Thomas H.↗

Direct observation of both contact and remote oxygen scavenging of GeO{sub 2} in a metal-oxide-semiconductor stack

In the path to incorporating Ge based metal-oxide-semiconductor into modern nano-electronics, one of the main issues is the oxide-semiconductor interface quality. Here, the reactivity of Ti on Ge stacks and the scavenging effect of Ti were studied using synchrotron X-ray photoelectron spectroscopy measurements, with an in-situ metal deposition and high resolution transmission electron microscopy imaging. Oxygen removal from the Ge surface was observed both in direct contact as well as remotely through an Al{sub 2}O{sub 3} layer. The scavenging effect was studied in situ at room temperature and after annealing. We find that the reactivity of Ti can be utilized for improved scaling of Ge based devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electron-Scavenging Chemistry of Benzoquinone on TiO2(110)

The chemistry of benzoquinone (BQ) on TiO2(110) was examined using temperature programmed desorption (TPD), electron energy loss spectroscopy (EELS) and Auger electron spectroscopy (AES). BQ adsorbs mostly molecularly on the clean surface, although EELS demonstrates that electrons from surface Ti3+ sites at oxygen vacancy sites (VO) are readily oxidized by the high electron scavenging ability of the molecule. In contrast, when the surface is covered with water, subsequently adsorbed BQ molecules that scavenge surface electrons also abstract H from surface OHbr groups to form hydroquinone (HQ), which desorbs at ~450 K. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. The research was performed using the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural basis of heme scavenging by the ChtA and HtaA hemophores in Corynebacterium diphtheriae

Corynebacterium diphtheriae causes diphtheria, a potentially fatal infectious disease that damages tissues in the upper respiratory tract. In order to proliferate, this pathogen acquires the essential nutrient iron from heme (iron-protoporphyrin IX) primarily found in human hemoglobin (Hb). C. diphtheriae secretes ChtA and HtaA hemophore proteins that bind ferric heme (hemin) via conserved region (CR) domains. Here, we demonstrate that their CR domains scavenge hemin after it is spontaneously released from Hb, and define the structural basis of hemin binding to ChtA and the N-terminal CR domain from HtaA by determining X-ray crystal structures of their protein-hemin complexes. Resonance Raman and electron paramagnetic resonance experiments demonstrate that the CR domains from ChtA and HtaA engage in pentacoordinate hemin binding through a conserved iron-tyrosyl linkage, though variations in their hemin pockets alter the way they stabilize the axial tyrosine and mask hemin’s metal. The importance of these interactions is probed using isothermal titration calorimetry experiments, which represent the first quantitative assessment of CR-hemin affinity and reveal that ChtA binds hemin via an enthalpically driven process. Hemin partitioning experiments using native mass spectrometry demonstrate that the cohort of CR domains within C. diphtheriae ’s hemin-uptake system have dissociation constants for hemin between 0.8 and 22 nM, raising the possibility that affinity differences contribute to the directional flow of hemin into the cell. Collectively, the results of this work provide insight into how C. diphtheriae and other pathogenic and commensal corynebacterium species utilize CR domains to scavenge iron rich hemin from their environment.

Corynebacterium diphtheriae↗

Porous Ti-MOF-74 Framework as a Strong-Binding Nitric Oxide Scavenger

Combining synthesis, infrared spectroscopy, and ab initio modeling we show that the titanium-based porous framework Ti-MOF-74 has potential as an environmental nitric oxide (NO) scavenger, exhibiting an extraordinarily strong binding affinity and selectivity over other flue-gas components. The robustness upon exposure to water vapor and high flue-gas stack temperatures suggests that this material can perform well in an industrial environment. In-depth analysis of the Ti-NO bond indicates that the NO forms a strong covalent bond with the Ti. The process of this NO bond formation involves a reaction with the OH- capping groups of the Ti to form NO x groups, after which the excess NO binds to the open Ti metal sites. Ti-MOF-74 thus becomes, to the best of our knowledge, the first known porous framework that binds NO significantly stronger than water, providing novel avenues for environmental and physiological scavenging applications.

36 MATERIALS SCIENCE↗

Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability

Doped ceria compounds demonstrate excellent radical scavenging abilities and are promising additives to improve the chemical durability of polymer electrolyte membrane (PEM) fuel cells. Here in this paper, Ce 0.85 Zr 0.15 O 2 (CZO) nanoparticles were incorporated into the cathode catalyst layers (CLs) of PEM fuel cells (based on Nafion XL membranes containing 6.0 μg cm -2 ion-exchanged Ce) at loadings of 10 and 55 μg cm -2 . When compared to a CZO-free baseline, CZO-containing membrane electrode assemblies (MEAs) demonstrated extended lifetimes during PEM chemical stability accelerated stress tests (ASTs), exhibiting reduced electrochemical gas crossover, open circuit voltage decay, and fluoride emission rates. The MEA with high CZO loading (55 μg cm -2 ) demonstrated performance losses, which are attributed to Ce poisoning of the PEM and CL ionomer regions, which is supported by X-ray fluorescence (XRF) analysis. In the MEA with the low CZO loading (10 μg cm -2 ), both the beginning of life (BOL) performance and the performance after 500 hours of ASTs were nearly identical to the BOL performance of the CZO-free baseline MEA. XRF analysis of the MEA with low CZO loading reveals that the BOL PEM Ce concentrations are preserved after 1408 hours of ASTs and that Ce contents in the cathode CL are not significant enough to reduce performance. Therefore, employing a highly effective radical scavenger such as CZO, at a loading of 10 μg cm -2 in the cathode CL, dramatically mitigates degradation effects, which improves MEA chemical durability and minimizes performance losses.

36 MATERIALS SCIENCE↗

Transient electron scavengers modulate carrier density at a polar/nonpolar perovskite oxide heterojunction

Here, we show how transient electron scavengers can be utilized to control the carrier concentration at polar/non-polar perovskite interfaces. By combining quantitative synchrotron x-ray-based interface structure determination with ab initio modeling, we demonstrate that Nd vacancy formation and the resulting formation of Nd adatoms, stabilized by oxygen scavengers at the growth front, can quantitatively account for the decreased carrier concentration at the SrTiO 3 /n NdTiO 3 /SrTiO 3 (001) heterojunction for n = 1 unit cell. This study yields new insights into growth mechanisms and the effect of transient species and defects on the electronic properties of oxide heterojunctions.

36 MATERIALS SCIENCE↗

Grain boundary scavenging through reactive sintering of strontium and iron in samarium doped ceria electrolyte for ITSOFC applications

Highlights: • Addition of iron and strontium to Samarium doped ceria by combustion method and sintered at 1000 °C, 1200 °C, 1300 °C. • Viscous phase sintering of iron at 1200 °C modified to reactive sintering of iron and strontium at 1300 °C. • Grain boundary activation energy lowered without compensating the grain activation energy. • The highest scavenging factor of 10.52 with the lowest activation energy of 1.02eV was achieved. - Abstract: Lowering the operational temperature of ceria based electrolytes is important for commercialization of solid oxide fuel cells. Here, we report the effect of iron, strontium and iron/strontium co-addition in samarium (20 mol %) doped ceria (SDC) with respect to sintering, microstructural modifications and ionic conductivity. The nanoparticle synthesized through glycine-nitrate combustion method was sintered at 1000, 1200 and 1300 °C. An increase in density was observed in iron doped SDC due to viscous flow sintering while co-addition of strontium and iron lead to the reactive sintering at 1300 °C by forming a eutectic liquid phase which resulted in the density of 99%. The presence of iron and strontium generated a compensatory tensile strain in the lattice and an enhancement in oxygen vacancy concentration which resulted in higher ionic conductivity. Co-addition of strontium and iron in SDC, not only increases the density but also reduces the activation energy for grain boundary conductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Performance Leap of Lithium Metal Batteries in LiPF 6 Carbonate Electrolyte by a Phosphorus Pentoxide Acid Scavenger

Phosphorus pentoxide (P 2 O 5 ) is investigated as an acid scavenger to remove the acidic impurities in a commercial lithium hexafluorophosphate (LiPF 6 ) carbonate electrolyte to improve the electrochemical properties of Li metal batteries. Nuclear magnetic resonance (NMR) measurements reveal the detailed reaction mechanisms of P 2 O 5 with the LiPF 6 electrolyte and its impurities, which removes hydrogen fluoride (HF) and difluor-ophosphoric acid (HPO 2 F 2 ) and produces phosphorus oxyfluoride (POF 3 ), OF 2 P-O-PF 5 - anions, and ethyl difluorophosphate (C 2 H 5 OPOF 2 ) as new electrolyte species. The P 2 O 5 -modified LiPF 6 electrolyte is chemically compatible with a Li metal anode and LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) cathode, generating a PO x F y -rich solid electrolyte interphase (SEI) that leads to highly reversible Li electrodeposition, while eliminating transition metal dissolution and cathode particle cracking. The excellent electrochemical properties of the P 2 O 5 -modified LiPF6 electrolytes are demonstrated on Li||NMC622 pouch cells with 0.4 Ah capacity, 50 mu m Li anode, 3 mAh cm -2 NMC622 cathode, and 3 g Ah -1 electrolyte/capacity ratio. The pouch cells can be galvanostatically cycled at C/3 for 230 cycles with 87.7% retention.

25 ENERGY STORAGE↗

Identification of the Active Species in Photochemical Hole Scavenging Reactions of Methanol on TiO2

Molecular and dissociative methanol adsorption species were prepared on rutile TiO2(110) surfaces to study photocatalytic oxidation of methanol in ultrahigh vacuum (UHV) using temperature-programmed desorption (TPD). Adsorbed methoxy groups (CH3O-) were found to be the photoactive form of adsorbed methanol converted to adsorbed formaldehyde and a surface OH group by hole-mediated C-H bond cleavage. These results suggest that adsorbed methoxy is the effective hole scavenger in photochemical reactions involving methanol.

10 SYNTHETIC FUELS↗