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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS2009

Old Faithful Model for Radiolytic Gas-Driven Cryovolcanism at Enceladus

A new model is presented on how chemically driven cryovolcanism might contribute to episodic outgassing at the icy moon Enceladus and potentially elsewhere including Europa and Kuiper Belt Objects. Exposed water ices can become oxidized from radiolytic chemical alteration of near-surface water ice by space environment irradiation. In contact with primordially abundant reductants such as NH3, CH4, and other hydrocarbons, the product oxidants can react exothermically to produce volatile gases driving cryovolcanism via gas-piston forces on any subsurface liquid reservoirs. Radiolytic oxidants such as H2O2 and O2 can continuously accumulate deep in icy regoliths and be conveyed by rheological flows to subsurface chemical reaction zones over million-year time scales indicated by cratering ages for active regions of Enceladus and Europa. Surface blanketing with cryovolcanic plume ejecta would further accelerate regolith burial of radiolytic oxidants. Episodic heating from transient gravitational tides, radioisotope decay, impacts, or other geologic events might occasionally accelerate chemical reaction rates and ignite the exothermic release of cumulative radiolytic oxidant energy. The time history for the suggested "Old Faithful" model of radiolytic gas-driven cryovolcanism at Enceladus and elsewhere therefore consists of long periods of chemical energy accumulation punctuated by much briefer episodes of cryovolcanic activity. The most probable sequence for detection of activity in the current epoch is a long evolutionary phase of slow but continuous oxidant accumulation over billions of years followed by continuous but variable high activity over the past 10(exp 7)-10(exp 8) years. Detectable cryovolcanic activity could then later decline due to near-total oxidation of the rheologically accessible ice crust and depletion the accessible reductant abundances, as may have already occurred for Europa in the more intense radiation environment of Jupiter's magnetosphere. Astrobiological potential of Enceladus could correspondingly be higher than at Europa due to a less extreme state of oxidation and greater residual abundance of organics.

Cooper, John F.↗
NASA NTRS2011

The Transitional Protoplanetary Disk Frequency as a Function of Age: Disk Evolution in the Coronet Cluster, Taurus, and Other 1--8 Myr-old Regions

We present Spitzer 3.6-24 micron photometry and spectroscopy for stars in the 1-3 Myr-old Coronet Cluster, expanding upon the survey of Sicilia-Aguilar et al. (2008). Using sophisticated radiative transfer models, we analyze these new data and those from Sicilia-Aguilar et al. (2008) to identify disks with evidence for substantial dust evolution consistent with disk clearing: transitional disks. We then analyze data in Taurus and others young clusters - IC 348, NGC 2362, and eta Cha -- to constrain the transitional disk frequency as a function of time. Our analysis confirms previous results finding evidence for two types of transitional disks -- those with inner holes and those that are homologously depleted. The percentage of disks in the transitional phase increases from approx.15-20% at 1-2 Myr to > 50% at 5-8 Myr; the mean transitional disk lifetime is closer to approx. 1 Myr than 0.1-0.5 Myr, consistent with previous studies by Currie et al. (2009) and Sicilia-Aguilar et al. (2009). In the Coronet Cluster and IC 348, transitional disks are more numerous for very low-mass M3--M6 stars than for more massive K5-M2 stars, while Taurus lacks a strong spectral type-dependent frequency. Assuming standard values for the gas-to-dust ratio and other disk properties, the lower limit for the masses of optically-thick primordial disks is Mdisk approx. 0.001-0.003 M*. We find that single color-color diagrams do not by themselves uniquely identify transitional disks or primordial disks. Full SED modeling is required to accurately assess disk evolution for individual sources and inform statistical estimates of the transitional disk population in large samples using mid-IR colors.

Currie, Thayne↗
NASA NTRS2012

Evidence from Olivine-Hosted Melt Inclusions that the Martian Mantle has a Chondritic D/H Ratio and that Some Young Basalts have Assimilated Old Crust

Magmatic degassing of volatile elements affects the climate and near-surface environment of Mars. Telescopic and meteorite studies have revealed that the Martian atmosphere and near-surface materials have D/H ratios ~5-6 times terrestrial values [e.g., 1, 2]. Such high D/H ratios are interpreted to result from the preferential loss of H relative to heavier D from the Martian atmosphere, assuming that the original Martian water inventory had a D/H ratio similar to terrestrial values and to H in primitive meteorites [e.g., 1, 3]. However, the primordial Martian D/H ratio has, until now, not been well constrained. The uncertainty over the Martian primordial D/H ratio has arisen both from the scarcity of primitive Martian meteorites and as a result of contamination by terrestrial and, perhaps, Martian surface waters that obscure the signature of the Martian mantle. This study reports a comprehensive dataset of magmatic volatiles and D/H ratios in Martian primary magmas based on low-contamination, in situ ion microprobe analyses of olivine-hosted melt inclusions from both depleted [Yamato 980459 (Y98)] and enriched [Larkman Nunatak 06319 (LAR06)] Martian basaltic meteorites. Analyses of these primitive melts provide definitive evidence that the Martian mantle has retained a primordial D/H ratio and that young Martian basalts have assimilated old Martian crust.

Usui, Tomohiro↗
NASA NTRS2012

Searching for Organics Preserved in 4.5 Billion Year Old Salt

Our understanding of early solar system fluids took a dramatic turn a decade ago with the discovery of fluid inclusion-bearing halite (NaCl) crystals in the matrix of two freshly fallen brecciated H chondrite falls, Monahans and Zag. Both meteorites are regolith breccias, and contain xenolithic halite (and minor admixed sylvite -- KCl, crystals in their regolith lithologies. The halites are purple to dark blue, due to the presence of color centers (electrons in anion vacancies) which slowly accumulated as 40K (in sylvite) decayed over billions of years. The halites were dated by K-Ar, Rb-Sr and I-Xe systematics to be 4.5 billion years old. The "blue" halites were a fantastic discovery for the following reasons: (1) Halite+sylvite can be dated (K is in sylvite and will substitute for Na in halite, Rb substitutes in halite for Na, and I substitutes for Cl). (2) The blue color is lost if the halite dissolves on Earth and reprecipitates (because the newly-formed halite has no color centers), so the color serves as a "freshness" or pristinity indicator. (3) Halite frequently contains aqueous fluid inclusions. (4) Halite contains no structural oxygen, carbon or hydrogen, making them ideal materials to measure these isotopic systems in any fluid inclusions. (5) It is possible to directly measure fluid inclusion formation temperatures, and thus directly measure the temperature of the mineralizing aqueous fluid. In addition to these two ordinary chondrites halite grains have been reliably reported in several ureilites, an additional ordinary chondrite (Jilin), and in the carbonaceous chondrite (Murchison), although these reports were unfortunately not taken seriously. We have lately found additional fluid inclusions in carbonates in several additional carbonaceous chondrites. Meteoritic aqueous fluid inclusions are apparently relatively widespread in meteorites, though very small and thus difficult to analyze.

Zolensky, Michael E.↗
NASA NTRS2006

Comparison of the Chromium Distribution in New Super Koropon Primer to 30 Year Old Super Koropon Using Focused Ion Beam/Scanning Electron Microscopy

Super Koropon primer (MB0125-055) plays a significant role in the corrosion protection of areas throughout the Orbiter. Because the Shuttle Program relies so heavily upon the performance of the Koropon primer, it is necessary to fully understand all aspects of the behavior of the coating. One area where little understanding of the Koropon primer still exists is the level of risk associated with age related degradation. Recently, efforts were undertaken to better understand the age life of the Koropon primer and to gain some insight into the aging process of this coating. In that study, an aluminum access panel from the Orbiter Enterprise was used to investigate the performance of the old Koropon film. A control panel was also used to study the performance of new Koropon coating. Preliminary investigations into the performance of aged Super Koropon primer indicated a significant decrease in corrosion protection. This investigation serves as an example of how Focused Ion Beam/Scanning Microscopy can be used to characterize the changes that occur as coatings age.

Lomness, Janice K.↗
NASA NTRS2013

ALMA Observations of the Molecular Gas in the Debris Disk of the 30 Myr Old Star HD 21997

The 30 Myr old A3-type star HD 21997 is one of the two known debris dust disks having a measurable amount of cold molecular gas. With the goal of understanding the physical state, origin, and evolution of the gas in young debris disks, we obtained CO line observations with the Atacama Large Millimeter/submillimeter Array (ALMA). Here, we report on the detection of (12)CO and (13)CO in the J = 2-1 and J = 3-2 transitions and C(18)O in the J = 2-1 line. The gas exhibits a Keplerian velocity curve, one of the few direct measurements of Keplerian rotation in young debris disks. The measured CO brightness distribution could be reproduced by a simple star+disk system, whose parameters are r(sub in) < 26 AU, r(sub out) = 138 +/- 20 AU, Stellar M = 1.8 +0.5/−0.2 Solar M, and i = 32. Deg. 6 +/- 3 deg..1. The total CO mass, as calculated from the optically thin C(18)O line, is about (4-8) ×10(exp −2 ) Solar M, while the CO line ratios suggest a radiation temperature on the order of 6-9 K. Comparing our results with those obtained for the dust component of the HD 21997 disk from ALMA continuum observations by Moor et al., we conclude that comparable amounts of CO gas and dust are present in the disk. Interestingly, the gas and dust in the HD 21997 system are not colocated, indicating a dust-free inner gas disk within 55 AU of the star. We explore two possible scenarios for the origin of the gas. A secondary origin, which involves gas production from colliding or active planetesimals, would require unreasonably high gas production rates and would not explain why the gas and dust are not colocated. We propose that HD 21997 is a hybrid system where secondary debris dust and primordial gas coexist. HD 21997, whose age exceeds both the model predictions for disk clearing and the ages of the oldest T Tauri-like or transitional gas disks in the literature, may be a key object linking the primordial and the debris phases of disk evolution.

molecular gas↗
NASA NTRS2019

Craters, Boulders and Regolith of (101955) Bennu Indicative of an Old and Dynamic Surface

Small, kilometre-sized near-Earth asteroids are expected to have young and frequently refreshed surfaces for two reasons: collisional disruptions are frequent in the main asteroid belt where they originate, and thermal or tidal processes act on them once they become near-Earth asteroids. Here we present early measurements of numerous large candidate impact craters on near-Earth asteroid (101955) Bennu by the OSIRIS-REx (Origins, Spectral Interpretation, Resource Identification, and Security- Regolith Explorer) mission, which indicate a surface that is between 100 million and 1 billion years old, predating Bennu's expected duration as a near-Earth asteroid. We also observe many fractured boulders, the morphology of which suggests an influence of impact or thermal processes over a considerable amount of time since the boulders were exposed at the surface. However, the surface also shows signs of more recent mass movement: clusters of boulders at topographic lows, a deficiency of small craters and infill of large craters. The oldest features likely record events from Bennu's time in the main asteroid belt.

near-Earth asteroids; Bennu; OSIRIS-REx↗
NASA NTRS2018

Organic Matter Preserved in 3-Billion-Year-Old Mudstones at Gale Crater, Mars

Establishing the presence and state of organic matter, including its possible biosignatures, in martian materials has been an elusive quest, despite limited reports of the existence of organic matter on Mars. We report the in situ detection of organic matter preserved in lacustrine mudstones at the base of the ~3.5-billion-year-old Murray formation at Pahrump Hills, Gale crater, by the Sample Analysis at Mars instrument suite onboard the Curiosity rover. Diverse pyrolysis products, including thiophenic, aromatic, and aliphatic compounds released at high temperatures (500° to 820°C), were directly detected by evolved gas analysis. Thiophenes were also observed by gas chromatography–mass spectrometry. Their presence suggests that sulfurization aided organic matter preservation. At least 50 nanomoles of organic carbon persists, probably as macromolecules containing 5% carbon as organic sulfur molecules.

Eigenbrode, Jennifer L.↗
NASA NTRS2019

Craters, Boulders and Regolith of (101955) Bennu Indicative of an Old and Dynamic Surface

Small, kilometre-sized near-Earth asteroids are expected to have young and frequently refreshed surfaces for two reasons: collisional disruptions are frequent in the main asteroid belt where they originate, and thermal or tidal processes act on them once they become near-Earth asteroids. Here we present early measurements of numerous large candidate impact craters on near-Earth asteroid (101955) Bennu by the OSIRIS-REx (Origins, Spectral Interpretation, Resource Identification, and Security-Regolith Explorer) mission, which indicate a surface that is between 100 million and 1 billion years old, predating BennuaCTMs expected duration as a near-Earth asteroid. We also observe many fractured boulders, the morphology of which suggests an influence of impact or thermal processes over a considerable amount of time since the boulders were exposed at the surface. However, the surface also shows signs of more recent mass movement: clusters of boulders at topographic lows, a deficiency of small craters and infill of large craters. The oldest features likely record events from Bennua time in the main asteroid belt.

K. J. Walsh↗
NASA NTRSDate not supplied

4.32 Billion Year Old Impact Melts at Apollo 14: Dating the Procellarum Basin?

Introduction: Recent work has improved our understanding of lunar crustal structure and basin evolution on the Moon, but its early impact history and implications for solar system dynamics remain poorly established [1,2]. In particular, there is a derth of absolute ages, especially for the period >4.0 Ga, that could be related to basin-forming events. Here we present U-Pb isotopic data for Zr-rich minerals found in impact-melt fragments from Apollo 14 soil sample 14163 that, when combined with previously published data, dates an impact event at 4324±15 Ma. The compositions and ages of these impact-melt fragments provide unique information about the timing of early impact events and the composition of the lunar crust. Results: Fourteen rocklets ranging in size from 1 to 3 mm were extracted from soil 14163. Most are impactmelt rocks with 10-30% clasts of mostly pyroxene and plagioclase (100 to 500 μm) in a crystalline matrix. Textures of the matrix vary from subophitic, formed by intergrowths of 10-20 μm plagioclase and pyroxene crystals, to poikilitic, with plagioclase and pyroxene reaching 20-50 μm size. Some fragments that contain no visible clasts have similar textures are also interpreted as impact-melt rocks. All fragments contain notably large proportions of euhedral to subhedral ilmenite, zircon, apatite/merrillite and less abundant zirconolite and baddeleyite in the melt matrices. These grains often form intricate intergrowths with each other and rock-forming minerals, indicating their crystallization from the melt (Fig. 1). However, some slightly larger (~50 μm) zircon and phosphate grains can be interpreted as relict clasts based on their granular textures and relationships with the surrounding phases (Fig. 1). This implies that zircon and phosphate minerals were present in the target rocks. Some of these grains were profoundly remelted during the impact, which resulted in an oversaturation of the melt in Zr and P and crystallization of new grains of Zrrich minerals and phosphates during melt solidification. The presence of zircon and phosphates indicates that the melts were significantly enriched in KREEP components and ties their provenance to the Procellarum- KREEP Terrane (PKT) [3]. Combined U-Pb zircon data obtained for all fragments form two main clusters on a concordia diagram (Fig. 2), between about 4.3 and 3.9 Ga. Phosphate data mostly concentrate on the younger end of this age range but some analyses are almost as old as the older zircon grains (Fig. 2). Figure 1: Zircon (Zr) and phosphate (Apt; Mer) grains in impact melt fragments from Apollo 14 soil 14161. A-zircon grains crystallized from impact melt; B-phosphate grain inherited from the target; C- granular zircon grains Our interpretation of these data is that all U-rich minerals experienced variable resetting of the U-Pb system, with phosphate, where closure temperature is significantly lower than that in zircon, affected more profoundly by Pb loss than zircon. Our best estimate of the time of formation of zircon and phosphate is based on statistically valid analysis of grains interpreted texturally as grown from the impact melt (Fig. 2). Ten of these analyses define an age of 4324±15 Ma (MSWD=3.0, probability of fit P=0.002). Our best estimate for the time of resetting is obtained by combining data from phosphates that are statistically indistinguishable from 3.9 Ga within the analytical uncertainties. This group is represented by 18 analyses of 15 phosphate grains from different fragments (Fig. 2) and defines an age of 3922±6 Ma (MSWD=1.2, P=0.23). Conversely, a minimum age of the target lithologies, remelted in the impact that produced the rocklets studied here (Fig. 2), can be determined from the five oldest analyses of zircon clasts at 4338±13 Ma (MSWD=1.5, P=0.2), which is indistinguishable from the age of the impact melt within the uncertainties. The obtained ages, combined with textural evidence, imply that the impact melt was formed at 4324±15 Ma, and that it occurred in a zircon-rich target with a minimum age of 4338±13 Ma. Further reworking occurred during a second impact event at 3922±6 Ma. Discussion: The younger age of 3922±6 Ma can be interpreted as the time of the Imbrium impact. The older age of 4324±15 Ma would then be the time of formation of the impact melt, which was then caught in the Imbrium ejecta either at the Apollo 14 landing site or within the target rocks of the Imbrium impact. The presence of abundant accessory phases such as zircons and phosphates is consistent with a substantial KREEP component in the analyzed particles. The current distribution of KREEP on the lunar surface appears to be strongly influenced by Imbrum ejecta [4] so interpretation of the 4.32 Ga age depends in part on assumed structure of the pre-impact crust and distribution of KREEP within the crust. If KREEP was present only in the deep crust at 4.32 Ga, then a basin-scale impact possibly analogous to Imbrium or larger may be necessary to excavate a KREEPy impact melt at this time. However, if KREEPy materials were present closer to the surface perhaps due to redistribution related to Mg-suite magmatism, then smaller impacts might be able to rework KREEPy compositions at shallower depths. The coherence of the data on the particles analysed here suggests a large volume of melt that has been preserved since 4.32 Ga, consistent with a large impact event. Relict zircons and mineral clasts suggests that the igneous crust in the vicinity of this impact was well developed by at least 4.34 Ga, similar to the model age of KREEP and older than the isochron ages of many Mg-suite cumulates [5]. A problem that confronts all lunar sample studies using the current collection is that the pre-Imbrium geology of the PKT (the source of these 4.32 Ga impact melts) is not well constrained. The South Pole-Aitken basin contains regions that are moderately enriched in Th, but its ejecta is Th-poor [6]; therefore these A14 fragments are probably not SPA ejecta. Alternatively, these fragments may represent formation of a hypothesized Procellarum basin [7] although the lack of a clearly defined basin ejecta signature is a potential problem with that interpretation. In any case, they provide a younger limit on the age of lunar differentiation and formation of KREEP within the lunar crust. Figure 2: U-Pb data for zircon and phosphate grains from impact melt fragments. A-all data; B-data used for age calculations. References: [1] Orgel C., Michael G., Fassett C. I., van der Bogert C. H., Riedel C., Kneissl T., and Hiesinger H. (2018) J. Geophys. Res. Planets 123, 748- 762. [2] Evans A. J., Andrews-Hanna J. C., Head J. W., Soderblom J. M., Solomon S. C., and Zuber M. T. (2018) J. Geophys. Planets. 123, 1596-1617. [3] Jolliff, B.L., Gillis, J.J., Haskin, L.A., Korotev, R.L. and Wieczorek, M.A. (2000) J. Geophys. Res: Planets 105, 4197-4216. [4] Haskin L. A. (1998) J. Geophys. Res. Planets 103, 1679-1689. [5] Borg L.E., Gaffney A.M., and Shearer C.K. (2015) MAPS 50, 715-732. [6] Moriarty, D.P., Watkins, R.N., Valencia, S.N., Kendall, J.D., Evans, A.J., Dygert, N. and Petro, N.E. (2021) J. Geophys. Res. Planets 126. [7] Zhu, M.H., Wünnemann, K., Potter, R.W., Kleine, T. and Morbidelli, A. (2019) J. Geophys. Res: Planets 124, 2117-2140

M D Norman↗
DOE OSTI2024

Getting allometry right at the Oak Ridge free‐air CO 2 enrichment experiment: Old problems and new opportunities for global change experiments

Societal Impact Statement Free‐air CO 2 enrichment (FACE) experiments provide essential data on forest responses to increasing atmospheric CO 2 for evaluations of climate change impacts on humanity. Understanding and reducing the uncertainty in the experimental results is critical to ensure scientific and public confidence in the models and policy initiatives that derive therefrom. One source of uncertainty is the estimation of tree biomass using mathematical relationships between biomass and easily obtained and non‐destructive measurements (allometry). We evaluated the robustness of the allometric relationships established at the beginning of a FACE experiment and discuss the challenges and opportunities for the new generation of FACE experiments. Summary Long‐term field experiments to elucidate forest responses to rising atmospheric CO 2 concentration require allometric equations to estimate tree biomass from non‐destructive measurements of tree size. We analyzed whether the allometric equations established at the beginning of a free‐air CO 2 enrichment (FACE) experiment in a Liquidambar styraciflua plantation were still valid at the end of the 12 year experiment. Aboveground woody biomass was initially predicted by an equation that included bole diameter, taper, and height, assuming that including taper and height as predictors would accommodate changes in tree structure that might occur over time and in response to elevated CO 2 . At the conclusion of the FACE experiment, we harvested 23 trees, measured dimensions and dry mass of boles and branches, and extracted and measured the woody root mass of 10 trees. Although 10 of the harvested trees were larger than the trees used to establish the allometric relationship, measured aboveground woody biomass was well predicted by the original allometry. The initial linear equation between bole basal area and woody root biomass underestimated final root biomass by 28%, but root biomass was just 21% of total wood mass, and errors in aboveground and belowground estimates were offsetting. The allometry established at the beginning of the experiment provided valid predictions of tree biomass throughout the experiment. New allometric approaches using terrestrial laser scanning should reduce an important source of uncertainty in decade‐long forest experiments and in assessments of centuries‐long forest biomass accretion used in evaluating carbon offsets and climate mitigation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Influence of plateau, slope, and valley on soil hydrology during the dry season in a Central Amazon old‐growth forest

Soil moisture regulates plant water supply and drought sensitivity in tropical forests, yet its vertical and topographic variation remains poorly characterized. We combined high-frequency time-domain reflectometry measurements from 5 to 100 cm across plateau, slope, and valley landforms at the Zona Florestal 2 research site north of Manaus, Central Amazonia, to quantify how soil moisture memory, timing of responses to rainfall, dry-down rates (τ), and soil–water depletion vary across these contrasting landforms. Landform-specific soil moisture calibration curves ensured accurate volumetric water content estimates in these highly weathered soils. During the 2023 dry-to-wet transition (August–November), soil moisture memory showed strong topographic contrasts, with valley profiles increasing from ∼47 h at 5 cm to ∼154 h at 100 cm, while plateaus exhibited higher near-surface persistence (∼124 h at 5 cm) but weaker memory at depth. Dry-down behavior reinforced these differences as valley soils exhibited τ values exceeding ∼200 h, more than double the characteristic τ of plateau soils (∼90 h). Rainfall–soil moisture correlations indicated immediate responses at shallow depths in valleys and progressively longer lags with depth on plateaus and slopes. These hydrologic patterns were mirrored in depletion profiles, which declined sharply below 30 cm on plateaus but remained high and sustained throughout the upper meter in slopes and valleys. Together, these findings provide the first depth-resolved field measurements of soil moisture memory, rainfall coupling, dry-down constants, and depletion dynamics across major upland landforms in Central Amazonia and offer clear observational benchmarks for improving land-surface and ecosystem model representations of soil–water processes.

Hillslope↗
DOE OSTI2021

The coordination properties and ionic radius of actinium: A 120-year-old enigma

Actinium is an elusive element with untamed properties and represents a peculiar case in the periodic table, as its isotopes are all radioactive, the longest-lived one having only a 22-year half-life, and the availability of actinium isotopes remains very low (microgram level, at best), hindering research on its compounds. Despite being a natural element discovered more than 120 years ago, and despite an increasing interest in using one of its isotopes ( 225 Ac) for highly efficient cancer therapies, the chemistry of actinium is still largely unknown relative to other elements. Since Ac is the first element of the actinide series, it is accepted that its ion, Ac 3+ , is the most voluminous trivalent cation of the periodic table. However, the structural data available on Ac 3+ compounds are scarce and have mainly been collected in the 1940-1960's, when actinide chemistry was still in its infancy, and have not been put in perspective with the advances in the chemistry of other elements, making it difficult to accurately evaluate its actual size and coordination chemistry. Here, we review progress made on the chemistry of lanthanides and actinides and reevaluate the structural data published on Ac 3+ since the era of the Manhattan Project. The data are combined across different spectroscopic and characterization methods and presented in the context of periodic trends. When considering crystallographic data, solution chemistry results, and the nuclear properties of actinium isotopes, it appears that some structural parameters ascribed to the Ac 3+ ion may have been overestimated. This review can guide researchers interested in actinide sciences and those who are pursuing the development of actinium-based radiotherapies, from isotope production to clinical trials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

New-to-nature chemistry from old protein machinery: carbene and nitrene transferases

Hemoprotein-catalyzed carbene and nitrene transformations have emerged as powerful tools for constructing complex molecules; they also nicely illustrate how new protein catalysts can emerge, evolve and diversify. These laboratory-invented enzymes exploit the ability of proteins to tame highly reactive carbene and nitrene species and direct their fates with high selectivity. New-to-nature carbene and nitrene transferases catalyze many useful reactions, including some that have no precedent using chemical methods. Here we cover recent advances in this field, including alkyne cyclopropenation, arene cyclopropanation, carbene C–H insertion, intramolecular nitrene C–H insertion, alkene aminohydroxylation, and primary amination. For such transformations, biocatalysts have exceeded the performance of reported small-molecule catalysts in terms of selectivity and catalyst turnovers. Lastly, we offer our thoughts on using these new enzymatic reactions in chemical synthesis, integrating them into biological pathways and chemo-enzymatic cascades, and on their current limitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗