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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Peridynamic modeling of cementitious materials for nuclear waste management

Radioactive and hazardous waste generated from fuel processing plants, nuclear reactors, and hospitals, requires effective management strategies. Cementitious materials are widely applied for these needs, serving as structural materials, reactive barriers, or waste forms. In these applications cracking poses a significant risk to performance, driven by inconsistent shrinkage of the components and the varying strength and permeability of their interfaces. Traditional modeling approaches face challenges in representing the complex fracture behavior of cementitious materials due to the reliance on spatial derivatives and difficulties with mesh generation. Here, to overcome these limitations, we employ peridynamics, a novel continuum mechanics formulation that uses integrals to describe mechanical equilibrium, avoiding discontinuities associated with traditional methods. Through incorporation of a bi-linear softening model and quasistatics, an experimentally validated model for Portland cement concrete samples was created. Mechanical parameters, including compressive strength and elastic modulus were validated and variation due to aggregate packing was evaluated. Additionally, sensitivity analysis of the peridynamic parameters to the bulk material properties was established. The results lay the groundwork for evaluating the impact of unique conditions of cementitious waste forms that can be assessed to improve the reliability of waste management strategies.

Aggregates↗
DOE OSTI2018

Rheological Investigation on the Microstructure of Fuel Cell Catalyst Inks

We present a rheological investigation of fuel cell catalyst inks. The effects of ink parameters, which include carbon black-support structure, Pt presence on carbon support (Pt-carbon), and ionomer (Nafion) concentration, on the ink microstructure of catalyst inks were studied using rheometry in combination with ultrasmall-angle X-ray scattering (USAXS) and dynamic light scattering (DLS). Dispersions of a high-surface-area carbon (HSC), or Ketjen black type, demonstrated a higher viscosity than Vulcan XC-72 carbon due to both a higher internal porosity and a more agglomerated structure that increased the effective particle volume fraction of the inks. The presence of Pt catalyst on both the carbon supports reduced the viscosity through electrostatic stabilization. For carbon-only dispersions (without Pt), the addition of ionomer up to a critical concentration decreased the viscosity due to electrosteric stabilization of carbon agglomerates. However, with Pt-carbon dispersions, the addition of ionomer showed contrasting behavior between Vulcan and HSC supports. In the Pt-Vulcan dispersions, the effect of ionomer addition on the rheology was qualitatively similar to Vulcan dispersions without Pt. The Pt-HSC dispersions showed an increased viscosity with ionomer addition and a strong shear-thinning nature, indicating that Nafion likely flocculated the Pt-HSC aggregates. These results were verified using DLS and USAXS. Further, the observations of the effect of ionomer:carbon ratio and a comparison between carbons of different surface areas provided insights on the microstructure of the catalyst ink corresponding to the optimized I/C ratio for fuel cell performance reported in the literature.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods

Mononuclear Fe ions ligated by nitrogen (FeN x ) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O 2 reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure–reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeN x active centers. In the present study, we develop a kinetic probe reaction method that uses the aerobic oxidation of a model hydroquinone substrate to quantify the density of FeN x centers in Fe- N-C catalysts. The kinetic method is compared with low-temperature Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical reductive stripping of NO derived from NO 2 – on a suite of Fe-N-C catalysts prepared by diverse routes and featuring either the exclusive presence of Fe as FeN x sites or the coexistence of aggregated Fe species in addition to FeN x . The FeN x site densities derived from the kinetic method correlate well with those obtained from CO pulse chemisorption and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification approach. Furthermore, the kinetic method developed here does not require pretreatments that may alter active-site distributions nor specialized equipment beyond reaction vessels and analytical instrumentation (e.g., NMR).

36 MATERIALS SCIENCE↗
NASA NTRS2020

A Composite Analysis of Snowfall Modes from Four Winter Seasons in Marquette, Michigan

Presented are four winter seasons of data from an enhanced precipitation instrument suite based at the National Weather Service (NWS) Office in Marquette (MQT), Michigan (250–500 cm of annual snow accumulation). In 2014 the site was augmented with a Micro Rain Radar (MRR) and a Precipitation Imaging Package (PIP). MRR observations are utilized to partition large-scale synoptically driven (deep)and surface-forced (shallow) snow events. Coincident PIP and NWS MQT meteorological surface observations illustrate different characteristics with respect to snow event category. Shallow snow events are often extremely shallow, with MRR-indicated precipitation heights of less than 1500 m above ground level. Large vertical reflectivity gradients indicate efficient particle growth, and increased boundary layer turbulence inferred from observations of spectral width implies increased aggregation in shallow snow events. Shallow snow events occur 2 times as often as deep events; however, both categories contribute approximately equally to estimated annual accumulation. PIP measurements reveal distinct regime-dependent snow microphysical differences, with shallow snow events having broader particle size distributions and comparatively fewer small particles and deep snow events having narrower particle size distributions and comparatively more small particles. In addition, coincident surface meteorological measurements indicate that most shallow snow events are associated with surface winds originating from the northwest (over Lake Superior), cold temperatures, and relatively high surface pressures, which are characteristics that are consistent with cold-air outbreaks. Deep snow events have meteorologically distinct conditions that are accordant with midlatitude cyclones and frontal structures, with mostly southwest surface winds, warmer temperatures approaching freezing, and lower surface pressures.

Claire Pettersen↗
NASA NTRS1998

A Conceptual Approach to Assimilating Remote Sensing Data to Improve Soil Moisture Profile Estimates in a Surface Flux/Hydrology Model: Overview - Part 1

Knowledge of the amount of water in the soil is of great importance to many earth science disciplines. Soil moisture is a key variable in controlling the exchange of water and energy between the land surface and the atmosphere. Thus, soil moisture information is valuable in a wide range of applications including weather and climate, runoff potential and flood control, early warning of droughts, irrigation, crop yield forecasting, soil erosion, reservoir management, geotechnical engineering, and water quality. Despite the importance of soil moisture information, widespread and continuous measurements of soil moisture are not possible today. Although many earth surface conditions can be measured from satellites, we still cannot adequately measure soil moisture from space. Research in soil moisture remote sensing began in the mid 1970s shortly after the surge in satellite development. Recent advances in remote sensing have shown that soil moisture can be measured, at least qualitatively, by several methods. Quantitative measurements of moisture in the soil surface layer have been most successful using both passive and active microwave remote sensing, although complications arise from surface roughness and vegetation type and density. Early attempts to measure soil moisture from space-borne microwave instruments were hindered by what is now considered sub-optimal wavelengths (shorter than 5 cm) and the coarse spatial resolution of the measurements. L-band frequencies between 1 and 3 GHz (10-30 cm) have been deemed optimal for detection of soil moisture in the upper few centimeters of soil. The Electronically Steered Thinned Array Radiometer (ESTAR), an aircraft-based instrument operating a 1,4 GHz, has shown great promise for soil moisture determination. Initiatives are underway to develop a similar instrument for space. Existing space-borne synthetic aperture radars (SARS) operating at C- and L-band have also shown some potential to detect surface wetness. The advantage of radar is its much higher resolution than passive microwave systems, but it is currently hampered by surface roughness effects and the lack of a good algorithm based on a single frequency and single polarization. In addition, its repeat frequency is generally low (about 40 days). In the meantime, two new radiometers offer some hope for remote sensing of soil moisture from space. The Tropical Rainfall Measuring Mission (TRMM) Microwave Imager (TMI), launched in November 1997, possesses a 10.65 GHz channel and the Advanced Microwave Scanning Radiometer (AMSR) on both the ADEOS-11 and Earth Observing System AM-1 platforms to be launched in 1999 possesses a 6.9 GHz channel. Aside from issues about interference from vegetation, the coarse resolution of these data will provide considerable challenges pertaining to their application. The resolution of TMI is about 45 km and that of AMSR is about 70 km. These resolutions are grossly inconsistent with the scale of soil moisture processes and the spatial variability of factors that control soil moisture. Scale disparities such as these are forcing us to rethink how we assimilate data of various scales in hydrologic models. Of particular interest is how to assimilate soil moisture data by reconciling the scale disparity between what we can expect from present and future remote sensing measurements of soil moisture and modeling soil moisture processes. It is because of this disparity between the resolution of space-based sensors and the scale of data needed for capturing the spatial variability of soil moisture and related properties that remote sensing of soil moisture has not met with more widespread success. Within a single footprint of current sensors at the wavelengths optimal for this application, in most cases there is enormous heterogeneity in soil moisture created by differences in landcover, soils and topography, as well as variability in antecedent precipitation. It is difficult to interpret the meaning of 'mean' soil moisture under such conditions and even more difficult to apply such a value. Because of the non-linear relationships between near-surface soil moisture and other variables of interest, such as surface energy fluxes and runoff, mean soil moisture has little applicability at such large scales. It is for these reasons that the use of remote sensing in conjunction with a hydrologic model appears to be of benefit in capturing the complete spatial and temporal structure of soil moisture. This paper is Part I of a four-part series describing a method for intermittently assimilating remotely-sensed soil moisture information to improve performance of a distributed land surface hydrology model. The method, summarized in section II, involves the following components, each of which is detailed in the indicated section of the paper or subsequent papers in this series: Forward radiative transfer model methods (section II and Part IV); Use of a Kalman filter to assimilate remotely-sensed soil moisture estimates with the model profile (section II and Part IV); Application of a soil hydrology model to capture the continuous evolution of the soil moisture profile within and below the root zone (section III); Statistical aggregation techniques (section IV and Part II); Disaggregation techniques using a neural network approach (section IV and Part III); and Maximum likelihood and Bayesian algorithms for inversely solving for the soil moisture profile in the upper few cm (Part IV).

Crosson, William L.↗
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 OSTI2023

Impact of fluorination on Li + solvation and dynamics in ionic liquid-hydrofluoroether locally concentrated electrolytes

The thermal, physical, structural, and transport properties of ionic liquid (IL) electrolytes based on n-methyl-n-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide [PYR14][TFSI] and Li-salts of lithium (nonafluorobutane)(trifluoromethanesulfonyl)imide [Li][IM14] and [Li][TFSI] (0 ≤ x Li ≤ 0.3), with addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) (0 ≤ x TTE ≤ 0.45) were studied. While [IM14] increases glass transition, TTE improves conductivity over a wider liquidus range. Li + is solvated primarily by [TFSI] with some contribution by [IM14]. However, both 7 Li- 19 F HOESY NMR and spatial distribution functions (SDFs) derived from molecular dynamics (MD) indicate short contacts between the fluorines of TTE and Li + . This is a result of tighter anion-solvated Li + without aggregation of the Li + solvates, consistent with Raman measurements, thus confirming the existence of fluorous domains in the bulk which leads to improved fluidity and a Li + diffusivity of 1.26 x 10 –12 m 2 /s at 0 °C (x Li = 0.20) with a Li + transference of 0.16. Improved transport properties translated to a higher capacity of the TTE/IL electrolyte in a Li||LiFePO 4 half-cell with 95mAh/g at 0.1C, compared to the IL electrolyte without TTE (60 mAh/g). Furthermore, this study demonstrates the tunability of solvation and transport properties in IL electrolytes by asymmetric fluorinated anions and hydrofluoroether co-solvents for low temperature Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Grazing-incidence diffraction reveals cellulose and pectin organization in hydrated plant primary cell wall

Abstract The primary cell wall is highly hydrated in its native state, yet many structural studies have been conducted on dried samples. Here, we use grazing-incidence wide-angle X-ray scattering (GIWAXS) with a humidity chamber, which enhances scattering and the signal-to-noise ratio while keeping outer onion epidermal peels hydrated, to examine cell wall properties. GIWAXS of hydrated and dried onion reveals that the cellulose ( $$110/1\overline{1}0$$ 110 / 1 1 ¯ 0 ) lattice spacing decreases slightly upon drying, while the (200) lattice parameters are unchanged. Additionally, the ( $$110/1\overline{1}0$$ 110 / 1 1 ¯ 0 ) diffraction intensity increases relative to (200). Density functional theory models of hydrated and dry cellulose microfibrils corroborate changes in crystalline properties upon drying. GIWAXS also reveals a peak that we attribute to pectin chain aggregation. We speculate that dehydration perturbs the hydrogen bonding network within cellulose crystals and collapses the pectin network without affecting the lateral distribution of pectin chain aggregates.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2001

Soot Formation in Laminar Acetylene/Air Diffusion Flames at Atmospheric Pressure

The flame structure and soot-formation (soot nucleation and growth) properties of axisymmetric laminar coflowing jet diffusion flames were studied experimentally. Test conditions involved acetylene-nitrogen jets burning in coflowing air at atmospheric pressure. Measurements were limited to the axes of the flames and included soot concentrations, soot temperatures, soot structure, major gas species concentrations, radical species (H, OH, and O) concentrations, and gas velocities. The results show that as distance increases along the axes of the flames, detectable soot formation begins when significant H concentrations are present, and ends when acetylene concentrations become small. Species potentially associated with soot oxidation--O2, CO2, H2O, O, and OH-are present throughout the soot-formation region so that soot formation and oxidation proceed at the same time. Strong rates of soot growth compared to soot nucleation early in the soot-formation process, combined with increased rates of soot nucleation and oxidation as soot formation proceeds, causes primary soot particle diameters to reach a maximum relatively early in the soot-formation process. Aggregation of primary soot particles proceeds, however, until the final stages of soot oxidation. Present measurements of soot growth (corrected for soot oxidation) in laminar diffusion flames were consistent with earlier measurements of soot growth in laminar premixed flames and exhibited encouraging agreement with existing hydrogen-abstraction/carbon-addition (HACA) soot growth mechanisms in the literature that were developed based on measurements within laminar premixed flames. Measured primary soot particle nucleation rates in the present laminar diffusion flames also were consistent with corresponding rates measured in laminar premixed flames and yielded a crude correlation in terms of acetylene and H concentrations and the temperature.

Xu, F.↗
NASA NTRS2012

An Icy Kuiper Belt Around the Young Solar-type Star HD 181327

Context. HD 181327 is a young main sequence F5/F6 V star belonging to the Beta Pictoris moving group (age approx.. 12 Myr). It harbors an optically thin belt of circumstellar material at radius approx.. 90 AU, presumed to result from collisions in a population of unseen planetesimals. Aims. We aim to study the dust properties in the belt in details, and to constrain the gas-to-dust ratio. Methods. We obtained far-infrared photometric observations of HD 181327 with the PACS instrument onboard the Herschel Space Observatory, complemented by new 3.2 mm observations carried with the ATCA array. The geometry of the belt is constrained with newly reduced HST/NICMOS scattered light images that allow the degeneracy between the disk geometry and the dust properties to be broken. We then use the radiative transfer code GRaTeR to compute a large grid of models, and we identify the grain models that best reproduce the spectral energy distribution (SED) through a Bayesian analysis. We attempt to detect the oxygen and ionized carbon fine-structure lines with Herschel/PACS spectroscopy, providing observables to our photochemical code ProDiMo. Results. The HST observations confirm that the dust is confined in a narrow belt. The continuum is detected with Herschel/PACS completing nicely the SED in the far-infrared. The disk is marginally resolved with both PACS and ATCA. A medium integration of the gas spectral lines only provides upper limits on the [OI] and [CII] line fluxes.We show that the HD 181327 dust disk consists of micron-sized grains of porous amorphous silicates and carbonaceous material surrounded by an important layer of ice, for a total dust mass of approx.. 0.05 Solar Mass (in grains up to 1 mm). We discuss evidences that the grains consists of fluffy aggregates. The upper limits on the gas atomic lines do not provide unambiguous constraints: only if the PAH abundance is high, the gas mass must be lower than approx. 17 Solar Mass. Conclusions. Despite the weak constraints on the gas disk, the age of HD 181327 and the properties of the dust disk suggest that it has passed the stage of gaseous planets formation. The dust reveals a population of icy planetesimals, similar to the primitive Edgeworth-Kuiper belt, that may be a source for the future delivery of water and volatiles onto forming terrestrial planets.

HD 181327↗
DOE OSTI2021

Discussion on molecular dynamics (MD) simulations of the asphalt materials

The application of asphalt materials in pavement engineering has been increasingly widespread and sophisticated over the past several decades. Variations in the properties of asphalt binder during mixing, transportation, and paving can affect the performance of asphalt pavement. However, the asphalt material is a non-homogeneous and complex organic substance, consisting of various molecules with widely various molecular weights, elemental compositions, and structures. This complexity leads to difficulties for researchers to clearly and immediately understand the properties of asphalt materials and their variations. The multi-scale research approach combines macroscopic experimental data and microscopic simulation results from a practical engineering perspective. It helps to improve the understanding of asphalt materials. The molecular dynamics (MD) simulation proposes a corresponding molecular model of asphalt material based on experimental data, and the simulation algorithm is able to derive properties similar to those of real asphalt. Here, this paper provides a comprehensive review of the current studies on MD simulation of asphalt materials, including modeling, properties, and multi-scale analysis. As a key part of the computational simulation, this paper discusses the typical asphalt binder and asphalt-aggregate interface models constructed by different groups, and also presents their differences from real samples and their feasibility based on fundamental properties. After the introduction of molecular models, the extensive work made by researchers based on molecular models is categorically reviewed and discussed. The strengths and weaknesses of MD simulation methods in the study of asphalt materials are also summarized in order to provide the reader with a more comprehensive understanding of the relevant contents and to guide subsequent research.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Digital image processing of nanometer-size metal particles on amorphous substrates

The task of differentiating very small metal aggregates supported on amorphous films from the phase contrast image features inherently stemming from the support is extremely difficult in the nanometer particle size range. Digital image processing was employed to overcome some of the ambiguities in evaluating such micrographs. It was demonstrated that such processing allowed positive particle detection and a limited degree of statistical size analysis even for micrographs where by bare eye examination the distribution between particles and erroneous substrate features would seem highly ambiguous. The smallest size class detected for Pd/C samples peaks at 0.8 nm. This size class was found in various samples prepared under different evaporation conditions and it is concluded that these particles consist of 'a magic number' of 13 atoms and have cubooctahedral or icosahedral crystal structure.

Soria, F.↗
NASA NTRS2000

Soot Formation in Laminar Acetylene/Air Diffusion Flames at Atmospheric Pressure

The flame structure and soot-formation (soot nucleation and growth) properties of axisymmetric laminar coflowing jet diffusion flames were studied experimentally. Test conditions involved acetylene-nitrogen jets burning in coflowing air at atmospheric pressure. Measurements were limited to the axes of the flames and included soot concentrations, soot temperatures, soot structure, major gas species concentrations, radical species (H, OH, and O) concentrations, and gas velocities. The results show that as distance increases along the axes of the flames, detectable soot formation begins when significant H concentrations are present, and ends when acetylene concentrations become small. Species potentially associated with soot oxidation-O2, CO2, H2O, O, and OH-are present throughout the soot-formation region so that soot formation and oxidation proceed at the same time. Strong rates of soot growth compared to soot nucleation early in the soot-formation process, combined with increased rates of soot nucleation and oxidation as soot formation proceeds, causes primary soot particle diameters to reach a maximum relatively early in the soot-formation process. Aggregation of primary soot particles proceeds, however, until the final stages of soot oxidation. Present measurements of soot growth (corrected for soot oxidation) in laminar diffusion flames were consistent with earlier measurements of soot growth in laminar premixed flames and exhibited encouraging agreement with existing hydrogen-abstraction/carbon-addition (HACA) soot growth mechanisms in the literature that were developed based on measurements within laminar premixed flames. Measured primary soot particle nucleation rates in the present laminar diffusion flames also were consistent with corresponding rates measured in laminar premixed flames and yielded a crude correlation in terms of acetylene and H concentrations and the temperature.

Xu, F.↗
NASA NTRS2001

Soot Formation in Laminar Acetylene/Air Diffusion Flames at Atmospheric Pressure

The flame structure and soot-formation (soot nucleation and growth) properties of axisymmetric laminar coflowing jet diffusion flames were studied experimentally. Test conditions involved acetylene-nitrogen jets burning in coflowing air at atmospheric pressure. Measurements were limited to the axes of the flames and included soot concentrations, soot temperatures, soot structure, major gas species concentrations, radical species (H, OH, and O) concentrations, and gas velocities. The results show that as distance increases along the axes of the flames, detectable soot formation begins when significant H concentrations are present, and ends when acetylene concentrations become small. Species potentially associated with soot oxidation-O2, CO2, H2O, O, and OH-are present throughout the soot-formation region so that soot formation and oxidation proceed at the same time. Strong rates of soot growth compared to soot nucleation early in the soot-formation process, combined with increased rates of soot nucleation and oxidation as soot formation proceeds, causes primary soot particle diameters to reach a maximum relatively early in the soot-formation process. Aggregation of primary soot particles proceeds, however, until the final stages of soot oxidation. Present measurements of soot growth (corrected for soot oxidation) in laminar diffusion flames were consistent with earlier measurements of soot growth in laminar premixed flames and exhibited encouraging agreement with existing hydrogen-abstraction/carbon-addition (HACA) soot growth mechanisms in the literature that were developed based on measurements within laminar premixed flames. Measured primary soot particle nucleation rates in the present laminar diffusion flames also were consistent with corresponding rates measured in laminar premixed flames and yielded a crude correlation in terms of acetylene and H concentrations and the temperature.

Xu, F.↗
DOE OSTI2020

Assembly of Building Blocks by Double-End-Anchored Polymers in the Dilute Regime Mediated by Hydrophobic Interactions at Controlled Distances

Hierarchical assembly of building blocks via competing, orthogonal interactions is a hallmark of many of nature’s composite materials that do not require highly specific ligand-receptor interactions. To mimic this assembly mechanism requires the development of building blocks capable of tunable interactions. In the present work, we explored the interplay between repulsive (steric and electrostatic) and attractive hydrophobic forces. The designed building blocks allow hydrophobic forces to effectively act at controlled, large distances, to create and tune the assembly of membrane-based building blocks under dilute conditions and affect their interactions with cellular membranes via physical cross-bridges. Specifically, we employed double-end-anchored poly(ethylene glycol)s (DEA-PEGs)—hydrophilic PEG tethers with hydrophobic tails on both ends. Using differential-interference-contrast optical microscopy, synchrotron small angle X-ray scattering (SAXS), and cryogenic electron microscopy, we investigated the ability of DEA-PEGs to mediate assembly in the dilute regime on multiple length scales and on practical time scales. The PEG length, anchor hydrophobicity, and molar fraction of DEA-PEG molecules within a membrane strongly affect the assembly properties. Additional tuning of the intermembrane interactions can be achieved by adding repulsive interactions via PEG-lipids (steric) or cationic lipids to the DEA-PEG-mediated attractions. Further, while the optical and electron microscope imaging methods provided qualitative evidence of the ability of DEA-PEGs to assemble liposomes, the SAXS measurements and quantitative line-shape analysis in dilute preparations demonstrated that the ensemble average of loosely organized liposomal assemblies maintains DEA-PEG concentration-dependent tethering on defined nanometer length scales. For cationic liposome–DNA nanoparticles (CL–DNA NPs), aggregation induced by DEA-PEGs decreased internalization of NPs by cells, but tuning the DEA-PEG-induced attractions by adding repulsive steric interactions via PEG-lipids limited aggregation and increased NP uptake. However, confocal microscopy imaging together with colocalization studies with Rab11 and LysoTracker as markers of intracellular pathways showed that modifying CL–DNA NPs with DEA-PEGs alters their interactions with the plasma and endosomal membranes.

- x-ray scattering↗
DOE OSTI2018

Accessing crystal–crystal interaction forces with oriented nanocrystal atomic force microscopy probes

Biominerals serve as crucial structures of living systems and play an important role for biochemical processes. Understanding their crystallization mechanisms is therefore central to many areas of biology, biogeoscience and biochemistry. Some biominerals, such as bone and dentin, are hierarchical nanocomposite structures constructed by sequentially added individual oriented nanocrystals. The driving forces that enable this oriented assembly are still poorly understood, with advances in understanding limited in part by the availability of techniques that can precisely measure the delicate interactions between nanocrystals, as a function of their separation distance and mutual orientation. Here we provide a novel and comprehensive protocol for i.) fabricating oriented single nanocrystal atomic force microscopy (AFM) probes using focus ion beam (FIB) milling - probes that are capable of accessing the nanoscale forces between oriented single-crystal faces, and ii.) performing oriented nanocrystal interaction force measurements using dynamic force spectroscopy (DFS) and environmental transmission electron microscopy (ETEM)-AFM techniquqes. These methods have recently led to seminal breakthroughs in force quantification for understanding oriented aggregation at the nanoscale. First, we detail two FIB milling based methods to fabricate AFM nanocrystal probes. One method requires careful pre-coating with a protective layer to avoid FIB damage to the face of interest, which is later chemically removed, and the other entails removal of the FIB damage layer with in situ polishing. We illustrate how to fabricate oriented nanocrystal force probes using commercial bulk crystals or nano/micro-crystals of calcite, zinc oxide, and rutile; the methods are fully transferrable to the apatites comprising bone minerals. The typical protocol for fabricating one AFM crystal probe takes 2-3 h. Finally, we describe how to measure interaction forces between nanocrystals in solution conditions of interest by performing AFM based DFS, or in the controlled environment of ETEM, using the resulting oriented nanocrystal probes. In addition, we illustrate how to quantify the direction-specific interaction forces for a given pair of interacting oriented nanocrystal faces, and how to relate this information generally to understanding crystallization by particle attachment.

Zhang, Xin (ORCID:000000032000858X)↗
DOE OSTI2017

Development and Modeling of a Novel Self-Assembly Process for Polymer and Polymeric Composite Nanoparticles

Extensive computational simulations and experiments have been used to investigate the structure, dynamics and resulting photophysical properties of a number para-phenylenevinylene (PPV) based polymers and oligomers. These studies have shown how the morphology and structure are controlled to a large extent by the nature of the solute-solvent interactions in the initial solution phase preparation. A good solvent such as dichloromethane generates non-compact structures with more of a defect-extended chain like morphology while a bad solvent such as toluene leads to compact organized and folded structures with rod-like morphologies. Secondary structural organization is induced by using the solution phase structures to generate solvent-free single molecule nanoparticles. These nanoparticles are very compact and rod shaped, consisting of near-cofacial ordering of the conjugated PPV chain backbones between folds located at tetrahedral defects (sp3 C-C bonds). The resulting photophysical properties exhibit a significant enhancement in the photoluminescence quantum yield, lifetime, and stability. In addition, the single molecule nanoparticles have Gaussian-like emission spectra with discrete center frequencies that are correlated to a conjugation length, allowing the design of nanoparticles which luminesces at a particular frequency. We followed a similar approach and applied a comparable methodology in our recent work on polythiophenes in order to study the effect of polymer architecture on nanoscale assembly. Unlike linear chains of comparable size, we observed aggregation of the bottlebrush architecture of poly(norbornene)-g-poly(3-hexylthiophene) (PNB-g-P3HT) after the freeze-drying and dissolution processes. The behavior can be attributed to a significant enhancement in the number of π-π interactions between grafted P3HT side chains.

Sumpter, Bobby G.↗
NASA NTRS2016

Prospects of the ICESat-2 Laser Altimetry Mission for Savanna Ecosystem Structural Studies Based on Airborne Simulation Data

The next planned spaceborne lidar mission is the Ice, Cloud and land Elevation Satellite 2 (ICESat-2), which will use the Advanced Topographic Laser Altimeter System (ATLAS) sensor, a photon counting technique. To pre-validate the capability of this mission for studying three dimensional vegetation structure in savannas, we assessed the potential of the measurement approach to estimate canopy height in an oak savanna landscape. We used data from the Multiple Altimeter Beam Experimental Lidar (MABEL), an airborne photon counting lidar sensor developed by NASA's Goddard Space Flight Center. ATLAS-like data was generated using the MATLAS simulator, which adjusts MABEL data's detected number of signal and noise photons to that expected from the ATLAS instrument. Transects flown over the Tejon ranch conservancy in Kern County, California, USA were used for this work. For each transect we chose to use data from the near infrared channel that had the highest number of photons. We segmented each transect into 50 m, 25 m and 14 m long blocks and aggregated the photons in each block into a histogram based on their elevation values. We then used an automated algorithm to identify cut off points where the cumulative density of photons from the highest elevation indicates the presence of the canopy top and likewise where such cumulative density from the lowest elevation indicates the mean terrain elevation. MABEL derived height metrics were moderately correlated to discrete return lidar (DRL) derived height metrics r(sub 2) and RMSE values ranging from 0.60 to 0.73 and 2.9 m to 4.4 m respectively) but MATLAS simulation resulted in more modest correlations with DRL indices r(sub 2) ranging from 0.5 to 0.64 and RMSE from 3.6 m to 4.6 m). Simulations also indicated that the expected number of signal photons from ATLAS will be substantially lower, a situation that reduces canopy height estimation precision especially in areas of low density vegetation cover. On the basis of the simulated data, there is reason to believe that the ability of ICESat-2 to estimate height in savannas will be comparable to the original ICESat mission although the respective sensors have different measurement principles.

Gwenzi, David↗