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At least 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Au 3 -to-Ag 3 coordinate-covalent bonding and other supramolecular interactions with covalent bonding strength

An efficient strategy for designing charge-transfer complexes using coinage metal cyclic trinuclear complexes (CTCs) is described herein. Due to opposite quadrupolar electrostatic contributions from metal ions and ligand substituents, [Au(m-Pz-(i-C 3 H7) 2 )] 3 ∙[Ag(m-Tz-(n-C 3 F 7 ) 2 )] 3 (Pz = pyrazolate, Tz = triazolate) has been obtained and its structure verified by single crystal X-ray diffraction – representing the 1st crystallographically-verified M 3 @M' 3 stacked adduct of monovalent coinage metal CTCs. Abundant supramolecular interactions with aggregate covalent bonding strength arise from a combination of M–M' (Au / Ag), metal–π, π–π interactions and hydrogen bonding in this charge-transfer complex, according to density functional theory analyses, yielding a computed binding energy of 66 kcal mol -1 between the two trimer moieties – a large value for intermolecular interactions between adjacent d 10 centres (nearly doubling the value for a recently claimed Au(I) / Cu(I) polar-covalent bond: Proc. Natl. Acad. Sci. U.S.A., 2017, 114, E5042) – which becomes 87 kcal mol -1 with benzene stacking. Surprisingly, DFT analysis suggests that: (a) some other literature precedents should have attained a stacked M 3 @M' 3 product akin to the one herein, with similar or even higher binding energy; and (b) a high overall intertrimer bonding energy by inferior electrostatic assistance, underscoring genuine orbital overlap between M and M' frontier molecular orbitals in such polar-covalent M–M' bonds in this family of molecules. The Au / Ag bonding is reminiscent of classical Werner-type coordinate-covalent bonds such as H 3 N: → Ag in [Ag(NH 3 ) 2 ] + , as demonstrated herein quantitatively. Solidstate and molecular modeling illustrate electron flow from the p-basic gold trimer to the p-acidic silver trimer with augmented contributions from ligand-to-ligand’ (LL'CT) and metal-to-ligand (MLCT) charge transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Molecular interactions in short-chain perfluoroalkyl carboxylic acids and aqueous solutions

The presence of short-chain per- and polyfluoroalkyl substances in water poses a major health and environmental challenge. Here, we have performed high-energy small- and wide-angle X-ray scattering measurements on CF 3 [CF 2 ] n COOH (where n = 1, 2, 3 represents the chain length) and their aqueous solutions at 10% mole concentrations to characterize their molecular interactions at the atomic and nanometer length scales. The experimental wide-angle structure factors have been modelled using Empirical Potential Structural Refinement. The oxygen–oxygen partial X-ray pair distribution functions show that the coordination number between the hydroxyl oxygen on the acid and surrounding oxygen water molecules increases significantly with acid chain length, rising from 3.2 for n = 1 to 4.1 for n = 3. The small-angle scattering is dominated by a sharp, high-intensity peak at Q 1 ~ 0.2 Å -1 and a smaller peak at Q 2 = 1.2 Å -1 for n = 3, both of which decrease with decreasing chain length. The Q 2 peak is attributed to groups of adjacent non-bonded acid molecules, and Q 1 has contributions from both correlations between acid molecules and water–water interactions. In all cases, the models show nanoscale aggregation occurs in the form of denser channels of winding hydrogen-bonded chains, approximately 20 water molecules in length, surrounding clusters of acid molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Anion-dependent phase behavior of methylimidazolium-based ionic liquids mixed with water: Correlation between local molecular structure and mesoscale behaviors

The mesoscopic phase behavior of decylmethylimidazolium (C 10 mim) ionic liquids (ILs) bearing three monovalent anions—thiocyanate (SCN − ), nitrate (NO 3 − ), and chloride (Cl − )—mixed with water at relatively high IL contents (50–95 wt%) was investigated. Small-angle and wide-angle X-ray scattering (SAXS/WAXS) were employed to follow the evolution of both local and mesoscale structures across this composition range. In the absence of water, C 10 mimSCN and C 10 mimCl behaved as disordered liquids, whereas C 10 mimNO 3 spontaneously formed a hexagonally ordered cylindrical mesophase and displayed a sticky-solid macroscopic appearance. Upon addition of water, C 10 mimSCN remained a viscous liquid and only weakly ordered lamellar domains were observed. This limited ordering is attributed to the lack of hydrogen bonding and weak interaction energy between SCN − anions and C 10 mim + cations. In contrast, the trigonal-planar NO 3 − and point-like Cl − anions promoted the formation of well-defined hexagonal mesophases up to 35–45 wt% water. The formation of hydrogen bonding of the two anions with imidazolium ring protons likely enabled the creation of compact ion clusters that effectively exclude water molecules from the immediate vicinity of the IL aggregates. These findings demonstrate that the interaction energy between ion pairs dictate IL-water interactions and therefore control the transition from disordered liquids to ordered mesophases in IL/water mixtures with high IL contents. In conclusion, the combined SAXS/WAXS analysis reveals a correlation between local intermolecular structure and the emergence of mesoscopic order, providing a systematic framework for tailoring mesoscale structures in alkylimidazolium-based IL/water systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Tuning the Mechanical Properties of a Polymer Semiconductor by Modulating Hydrogen Bonding Interactions

Conjugation breakers (CBs) with different H-bonding chemistry and linker flexibility are designed and incorporated into a Diketopyrrolopyrrole (DPP)-based conjugated polymer backbone. The effects of H-bonding interactions on polymer semiconductor morphology, mechanical properties and electrical performance are systematically investigated. We observe that CBs with H-bonding self-association constant >0.7 or denser packing tendency are able to induce higher polymer chain aggregation and crystallinity in as-casted thin film, resulting in higher modulus and crack on-set strain. Additionally, the rDoC (relative degree of crystallinity) of the stretched thin film with the highest crack on-set strain only suffers a small decrease, suggesting the main energy dissipation mechanism is the breakage of H-bonding interactions. By contrast, other less stretchable polymer films dissipate strain energy through the breakage of crystalline domains, indicated by drastic decrease in rDoC. Furthermore, we evaluate their electrical performance under mechanical strain in fully stretchable field-effect transistors. The polymer with the highest crack on-set strain has the least degradation in mobility as a function of strain. Overall, these observations suggest that we can aptly tune the mechanical properties in polymer semiconductors by modulating intermolecular interactions, such as H-bonding chemistry and linker flexibility. Such understanding provides molecular design guidelines for future stretchable semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Protein model quality assessment using rotation–equivariant transformations on point clouds

Machine learning research concerning protein structure has seen a surge in popularity over the last years with promising advances for basic science and drug discovery. Working with macromolecular structure in a machine learning context requires an adequate numerical representation, and researchers have extensively studied representations such as graphs, discretized 3D grids, and distance maps. As part of CASP14, we explored a new and conceptually simple representation in a blind experiment: atoms as points in 3D, each with associated features. These features—initially just the basic element type of each atom—are updated through a series of neural network layers featuring rotation-equivariant convolutions. Starting from all atoms, we further aggregate information at the level of alpha carbons before making a prediction at the level of the entire protein structure. We find that this approach yields competitive results in protein model quality assessment despite its simplicity and despite the fact that it incorporates minimal prior information and is trained on relatively little data. As a result, its performance and generality are particularly noteworthy in an era where highly complex, customized machine learning methods such as AlphaFold 2 have come to dominate protein structure prediction.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Noncoordinating Secondary Sphere Ion Modulates Supramolecular Clustering of Lanthanides

The role of counterions in molecular recognition of lanthanides is underexplored, especially when they exhibit weak interactions with the metal cations. Here, we report a complementary and comprehensive investigation integrating theoretical calculations with X-ray absorption fine structure spectroscopy, dynamic light scattering, and small-angle X-ray scattering to reveal atomic-scale structural features beyond the immediate coordination sphere of a system used for rare-earth element separations. Here, our results indicate the formation of an unusual T-shaped outer-sphere lanthanide complex, containing two ligands and two nitrate ions in the first coordination sphere, whereas the third nitrate is weakly coordinated and resides in the second shell. This unique structural arrangement causes inhomogeneous charge distribution, leading to self-assembly of the complexes into larger nanoclusters through sterically directed electrostatic interactions in the nonpolar medium. Our findings point to the importance of "noncoordinating" anions in defining the degree of supramolecular aggregation and ion cluster assembly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

STARDUST and Interplanetary Dust Particles - Big Science from Small Samples

Comets are primitive bodies that are widely believed to be a reservoir of preserved interstellar and circumstellar grains, and molecular cloud materials (organics). Direct samples of cometary dust along with interstellar grains will be returned by the STARDUST Mission in 2006. Analyses of interplanetary dust particles (IDPs) and analogue materials in the laboratory provide constraints and serve as "ground truth" for evaluating various hypotheses on the nature of comets and interstellar grains. Anhydrous IDPs are the most primitive remnants of the primordial Solar System, and are our only known samples of comets. These cometary lDPs are rich in preserved interstellar organic compounds II]. In addition, abundant interstellar silicates have recently been discovered in cluster lDPs [2]. In some of these IDPs, the presolar silicate abundance reaches 1 wt %, exceeding the total presolar grain abundance in meteorites by three orders of magnitude, where presolar silicates are still notably absent. The results to date support the idea that comets are rich in presolar materials, but are at odds with the common perception that they are 'pristine aggregates of interstellar grains'. These results underscore the scientific importance of sample return missions to comets. The technology for the analysis of micrometer-sized samples is well advanced. The newest generation of ion probe instruments allow for isotopic analyses at the submicrometer level. The nature of the organic matter is analyzed using Infrared and soft X-ray spectroscopy techniques on synchrotron-based instruments, also at the micrometer-scale and smaller. Electron microscopy and spectroscopy provide details on the mineralogy and chemistry of constituent grains in !DPs at nearly the atomic scale. Novel sample preparation techniques have been developed such that all of these measurements can now be made on the same 10 micrometer diameter particle. Returned comet samples captured in aerogel will pose new challenges in sample analysis, but should provide a major leap in our understanding of the fundamental building blocks of our Solar System.

Keller, L. P.↗
DOE OSTI2020

Ring currents modulate optoelectronic properties of aromatic chromophores at 25 T

The properties of organic molecules can be influenced by magnetic fields, and these magnetic field effects are diverse. They range from inducing nuclear Zeeman splitting for structural determination in NMR spectroscopy to polaron Zeeman splitting organic spintronics and organic magnetoresistance. A pervasive magnetic field effect on an aromatic molecule is the aromatic ring current, which can be thought of as an induction of a circular current of π-electrons upon the application of a magnetic field perpendicular to the π-system of the molecule. While in NMR spectroscopy the effects of ring currents on the chemical shifts of nearby protons are relatively well understood, and even predictable, the consequences of these modified electronic states on the spectroscopy of molecules has remained unknown. In this work, we find that photophysical properties of model phthalocyanine compounds and their aggregates display clear magnetic field dependences up to 25 T, with the aggregates showing more drastic magnetic field sensitivities depending on the intermolecular interactions with the amplification of ring currents in stacked aggregates. These observations are consistent with ring currents measured in NMR spectroscopy and simulated in time-dependent density functional theory calculations of magnetic field-dependent phthalocyanine monomer and dimer absorption spectra. Here, we propose that ring currents in organic semiconductors, which commonly comprise aromatic moieties, may present new opportunities for the understanding and exploitation of combined optical, electronic, and magnetic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2018

Molecular Dynamics Simulations of Liquid and Polymer Electrolytes for Energy Storage Devices

Advancing beyond current lithium-ion technology is necessary in order to enable energy storage devices for electric airplanes. Electrolyte stability is a key limiting factor, yet the design of improved electrolytes remains a formidable challenge. Molecular dynamics (MD) simulations are a powerful tool for studying electrolytes, since they can be used to evaluate structural, thermodynamic, and transport properties, and can provide molecular-level detail often inaccessible to experimental techniques. Our computational materials groups at the NASA Ames Research Center has developed models and methods to accurately simulate both liquid and polymer electrolytes.We report the results from atomistic MD simulations of several electrolyte materials, with lithium salts dissolved in ionic liquids, dimethoxyethane (DME), and polyethylene oxide (PEO). For improved accuracy, we employ polarizable models, where each atom is given an environment-dependent atomic dipole. The simulations accurately predict bulk transport properties, including viscosity, diffusion, and ionic conductivity, in quantitative agreement with available experimental data. Moreover, the simulations provide important insights into the solvation structure of the lithium ions.We also report the results from coarse-grained MD simulations of polyanion electrolytes. In order to more efficiently capture the longer length- and time-scales of these systems, we employ a generic bead-spring model. These simulations provide important insight into how the polymer chain architecture and ionic interaction strengths affect the ionic aggregation behavior and cation dynamics. Despite the simplicity of the model, the simulations yield qualitative agreement with experimental data for similar systems.

Abbott, Lauren J.↗
NASA NTRS2010

Chemical Evolution of Presolar Organics in Astromaterials

Sub-micron, hollow organic globules reported from several carbonaceous chondrites, interplanetary dust particles, and comet Wild-2 samples returned by NASA?s Stardust mission are enriched in N-15/N-14 and D/H compared with terrestrial materials and the parent materials [1-4]. These anomalies are ascribed to the preservation of presolar cold molecular cloud material from where H, C, and N isotopic constraints point to chemical fractionation near 10 K [5]. An origin well beyond the planet forming region and their survival in meteorites suggests submicrometer organic globules were once prevalent throughout the solar nebula. The survival of the membrane structures indicates primitive meteorites and cometary dust particles would have delivered these organic precursors to the early Earth as well as other planets and satellites. The physical, chemical, and isotopic properties of the organic globules varies to its meteorite types and its lithologies. For example, organic globules in the Tagish Lake meteorite are always embedded in fined grained (poorly crystallized) saponite, and hardly encapsulated in coarse grained serpentine, even though saponite and serpentine are both main components of phyllosilicate matrix of the Tagish Lake meteorite. The organic globules are commonly observed in the carbonate-poor lithology but not in the carbonate-rich one. In Tagish Lake, isolated single globules are common, but in the Bells (CM2) meteorite, globules are mostly aggregated. We will review the evolutions of the organic globules from its birth to alteration in the parent bodies in terms of its own physical and chemical properties as well as its associated minerals.

Nakamura-Messenger, K.↗
DOE OSTI2025

Detection of non‐native species formed during fibrillization of the myocilin olfactomedin domain

Abstract Glaucoma is a group of neurodegenerative diseases that together are the leading cause of irreversible blindness worldwide. Myocilin‐associated glaucoma is an inherited form of this disease, caused by intracellular aggregation of misfolded mutant myocilin. In vitro, the myocilin C‐terminal olfactomedin domain (OLF), the relevant domain for glaucoma pathogenesis, can be driven to form amyloid‐like fibrils under mild conditions. Here we characterize a species present during in vitro fibrillization. Purified OLF was subjected to fibrillization at concentrations required for downstream electron microscopy imaging and NMR spectroscopy. Additional biophysical techniques, including analytical ultracentrifugation and X‐ray crystallography, were employed to further characterize the multicomponent mixture. Negative stain transmission electron microscopy (TEM) shows a non‐native species reminiscent of known prefibrillar oligomers from other amyloid systems, NMR indicates a minor population of partially misfolded species is present in solution, and cryo‐EM imaging shows two‐dimensional protein arrays. The predominant soluble species remaining in solution after the fibril reaction is natively folded, as evidenced by X‐ray crystallography. In summary, after incubating OLF under fibrillization‐promoting conditions, there is a heterogeneous mixture consisting of soluble folded protein, mature amyloid‐like fibrils, and partially misfolded intermediate species that at present belie additional molecular detail. The characterization of OLF fibrillar species illustrates the challenges associated with developing a comprehensive understanding of the fibrillization process for large, non‐model amyloidogenic proteins.

Scelsi, Hailee F. [School of Chemistry and Biochem↗
DOE OSTI2022

Atomic structure of the Leishmania spp. Hsp100 N-domain

We report Hsp100 is an ATP-dependent unfoldase that promotes protein disaggregation or facilitates the unfolding of aggregation-prone polypeptides marked for degradation. Recently, new Hsp100 functions are emerging. In Plasmodium, an Hsp100 drives malaria protein export, presenting a novel drug target. Whether Hsp100 has a similar function in other protists is unknown. We present the 1.06 angstrom resolution crystal structure of the Hsp100 N-domain from Leishmania spp., the causative agent of leishmaniasis in humans. Our structure reveals a network of methionines and aromatic amino acids that define the putative substrate-binding site and likely evolved to protect Hsp100 from oxidative damage in host immune cells.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1998

Fabrication and Atomic Force Microscopy Characterization of Molecular Composites of Fullerenes in Aerogel Matrix for Optical Limiting

An optical limiter is a device which exhibits a decrease in the transmittance in a material with an increase in intensity of light. Sol-gel techniques offer many advantages in the fabrication of materials. These materials possess many desirable properties for nonlinear optical (NLO) device applications which include transparency, high thermal and chemical stabilities, very low refractive index and dielectric constants. C60 shows a higher excited state absorption cross section than the ground state absorption cross section over the complete visible spectrum, and the spectrum of the excited state absorption of C60 has the same general shape as the ground state absorption. This fact suggests that fullerenes are ideal optical limiting materials. Aerogels are fabricated by sol-gel processing. One of the key issues is the dispersion of fullerenes into small and uniform pores of silica aerogel host matrices. The aerogel network was characterized by Raman spectroscopy. Atomic force microscopy is a technique with many advantages to characterize the aerogel materials. The morphology of the cleaved surface for a C60/aerogel sample shows that there are long paralleled shaped stripes with 20-30 nm in width and about 500 nm in length on the cleaved surface. The cleaved surface also was etched by 5% HF solution for one minutes, and it became smoother after HF etching. The main feature in on the surface is the spherical particles with the size of few nanometers, and no aggregated fullerenes appear. The fullerenes are well dispersed in the aerogel matrices.

Lu, W. J .↗
NASA NTRS2020

An evolutionary system of mineralogy. Part II: Interstellar and solar nebula primary condensation mineralogy (>4.565 Ga)

The evolutionary system of mineralogy relies on varied physical and chemical attributes, including trace elements, isotopes, solid and fluid inclusions, and other information-rich characteristics, to understand processes of mineral formation and to place natural condensed phases in the deep-time context of planetary evolution. Part I of this system reviewed the earliest refractory phases that condense at T > 1000 K within the turbulent expanding and cooling atmospheres of highly evolved stars. Part II considers the subsequent formation of primary crystalline and amorphous phases by condensation in three distinct mineral-forming environments, each of which increased mineralogical diversity and distribution prior to the accretion of planetesimals >4.5 billion years ago. (1) Interstellar molecular solids: Varied crystalline and amorphous molecular solids containing primarily H, C, O, and N are observed to condense in cold, dense molecular clouds in the interstellar medium (10 < T < 20 K; P < 10−13 atm). With the possible exception of some nanoscale organic condensates preserved in carbonaceous meteorites, the existence of these phases is documented primarily by telescopic observations of absorption and emission spectra of interstellar molecules in radio, microwave, or infrared wavelengths. (2) Nebular and circumstellar ice: Evidence from infrared observations and laboratory experiments suggest that cubic H2O (“cubic ice”) condenses as thin crystalline mantles on oxide and silicate dust grains in cool, distant nebular and circumstellar regions where T ~100 K. (3) Primary condensed phases of the inner solar nebula: The earliest phase of nebular mineralogy saw the formation of primary refractory minerals that solidified through high-temperature condensation (1100 < T < 1800 K; 10−6 < P < 10−2 atm) in the solar nebula more than 4.565 billion years ago. These earliest mineral phases originating in our solar system formed prior to the accretion of planetesimals and are preserved in calcium-aluminum-rich inclusions, ultra-refractory inclusions, and amoeboid olivine aggregates.

Shaunna M. Morrison↗
DOE OSTI2024

Defect Self-Elimination in Nanocube Superlattices Through the Interplay of Brownian, van der Waals, and Ligand-Based Forces and Torques

Understanding defect healing is necessary for realizing devices based on nanoparticle-superlattices with controlled electronic and optoelectronic performance. However, key questions remain regarding nanoparticle interactions and resulting assembly dynamics and defect self-elimination. In particular, for anisotropic particles, additional degrees of freedom beyond those of spherical particles, such as rotational dynamics and toques, significantly impact phenomena. Here, in this work, we investigate nanocube (NC) superlattices by employing liquid phase transmission electron microscopy, continuum theories and molecular dynamics simulations. Analyzing interparticle forces and torques due to van der Waals, Brownian, and ligand interactions, we find that the latter dominates and that the anisotropic NC morphology introduces significant torques. In imperfect regions, unbalanced forces and torques induce NC translations and rotations that are transmitted to neighboring NCs, prompting “chain interactions” in a 2D network, which lead to defect self-elimination. This fundamental understanding will further enable design and fabrication of defect-free superlattices, as well as those with tailored defects, via assembly of anisotropic particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2013

Dust in the Solar System - Properties and Origins

Interplanetary dust pervades the inner Solar System, giving rise to a prominent glow above the horizon at sunrise and sunset known as the zodiacal light. This dust derives from the disintegration of comets as they approach the Sun and from collisions among main-belt asteroids. The Earth accretes roughly 4x10(exp 6) kg/year of 1 - 1,000 micron dust particles as they spiral into the Sun under the influence of Poynting-Robertson drag and solar wind drag. Samples of these grains have been collected from deep sea sediments, Antarctic ice and by high-altitude aircraft and balloon flights. Interplanetary dust particles (IDPs) collected in the stratosphere have been classified by their IR spectra into olivine, pyroxene, and hydrated silicate-dominated classes. Most IDPs have bulk major and minor element abundances that are similar to carbonaceous chondrite meteorites. Hydrated silicate-rich IDPs are thought to derive from asteroids based on their mineralogy and low atmospheric entry velocities estimated from peak temperatures reached during atmospheric entry. Anhydrous IDPs are typically aggregates of 0.1 - approx. 1 micron Mg-rich olivine and pyroxene, amorphous silicates (GEMS), Fe, Nisulfides and rare spinel and oxides bound together by carbonaceous material. These IDPs are often argued to derive from comets based on compositional similarities and high atmospheric entry velocities that imply high eccentricity orbits. Infrared spectra obtained from anhydrous IDPs closely match remote IR spectra obtained from comets. The most primitive (anhydrous) IDPs appear to have escaped the parent-body thermal and aqueous alteration that has affected meteorites. These samples thus consist entirely of grains that formed in the ancient solar nebula and pre-solar interstellar and circumstellar environments. Isotopic studies of IDPs have identified silicate stardust grains that formed in the outflows of red giant and asymptotic giant branch stars and supernovae]. These stardust grains include both amorphous and crystalline silicates. The organic matter in these samples also exhibits highly anomalous H, C, and N isotopic compositions that are consistent with formation in low temperature environments at the outermost regions of the solar nebula or presolar cold molecular cloud. The scientific frontiers for these samples include working toward a better understanding of the origins of the solar system amorphous and crystalline grains in IDPs and the very challenging task of determining the chemical composition of sub-micron organic grains. Laboratory studies of ancient and present-day dust in the Solar System thus reveal in exquisite detail the chemistry, mineralogy and isotopic properties of materials that derive from a range of astrophysical environments. These studies are an important complement to astronomical observations that help to place the laboratory observations into broader context.

Messenger, Scott↗
DOE OSTI2024

Getting to the root of the problem: Soil carbon and microbial responses to root inputs within a buried paleosol along an eroding hillslope in southwestern Nebraska, USA

Large quantities of soil carbon (C) can persist within paleosols for millennia due to burial and subsequent isolation from plant-derived inputs, atmospheric conditions, and microbial activity at the modern surface. Erosion exposes buried soils to modern root-derived C influx via root exudation and root turnover, thus stimulating microbial activity leading to SOC decomposition and accumulation through organo-mineral stabilization of modern C. With this study we aim to quantify how modern root-derived C inputs impact paleosol C decomposition and stabilization across varying degrees of isolation from modern surface conditions in southwestern Nebraska, USA, where hillslope erosion is bringing a buried Late-Pleistocene-early Holocene paleosol (the “Brady Soil”) closer to the modern surface. We collected Brady Soil samples from 0.2m, 0.4m, and 1.2m below the modern surface and conducted two lab-based incubations. Soils were amended with either (1) a lab-synthesized mixture of low molecular weight compounds (12 atom% 13 C), or (2) 13 C enriched root residues (92 atom% 13 C), in 30-day and 240-day incubation experiments, respectively. Here we determined microbial responses to synthetic root exudates and residues by partitioning the 13 C label from Brady Soil C, including measurements of total, root, and primed C respiration, microbial biomass C (MBC), microbial C use efficiency (CUE). To assess the capacity of isolated paleosols to accrue modern plant C, we used Nano-scale Secondary Ion Mass Spectrometry imaging. We found that: (1) adding root-derived C inputs primed Brady Soil C across all depths, and was mediated by depth and composition of root additions; (2) root-derived C inputs stimulated microbial biomass C (MBC) growth similarly across depths, but the magnitude of CUE and MBC varied by chemistry of root-derived additions; (3) new particulate organic matter was incorporated into mineral-associated pools over time; (4) material from the added root residues was found in association with bacterial cells and fungal hyphae as well as with soil aggregate and mineral surfaces. Our study shows that paleosols defy expectations of C content and reactivity with depth, and changes in land cover and climate will expose buried paleosols to modern surface conditions, increasing respired C. This work highlights the importance of evaluating the role resurfacing buried soils through landscape change plays in C cycle feedbacks to the climate system.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Ballistic Frenkel-exciton gate with a high on-off ratio

Here it is shown that the exciton interactions within organic dye aggregates, as modeled by the Frenkel Hamiltonian, enable the construction of an on/off switchable exciton gate. In this construction, a single exciton residing on a controlling gate molecule may pass or inhibit the ballistic propagation of an exciton in a proximal gate channel consisting of an array of dye molecules. High on-off ratios in excess of 102 can be achieved through the use of static difference dipole-dipole interactions between the gate and the gate channel which effectively creates a switchable Bragg grating. The gate channel and controlling gate molecule exhibit entanglement with the quantum mechanical superposition of the presence and absence of exciton occupation on the gate molecule.

74 ATOMIC AND MOLECULAR PHYSICS↗