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At least 397 records · Page 22

A Quantitative Molecular Atlas for Interactions Between Lignin and Cellulose

Lignin and cellulose are two of the most abundant polymers on Earth, and are found in close proximity within plant cell walls. Despite their ubiquity, relatively little is known quantitatively about their interactions within plants, and by extension how their interaction may affect industrial biomass utilization. Given the inherent heterogeneity of the lignin polymer and the structural complexity of cellulose, quantitative relationships between given cellulose faces and specific lignin chemistries have been challenging to ascertain experimentally. In this study, we use molecular simulation to examine individual combinations of cellulose binding face and lignin chemistry to build a quantitative lignin-cellulose interaction atlas, including contributions from both specific hydrogen bonds observed in simulation and nonspecific interactions between lignin and cellulose driven by solvent considerations. Over all monomeric and dimeric lignin chemistries tested, the hydrophobic 100 face is the preferred cellulose interaction site. Among the hydrophilic crystalline faces, binding of these molecules is strongest to the 110 cellulose face. The chemical composition of lignin monomers and dimers is also found to modulate the binding affinity, with additional methoxy groups increasing the contact area to the cellulose surface, which we hypothesize may protect native cellulose from degradation. Additional methoxylation and monomer linkages that facilitate planar aromatic ring orientations increase the binding affinity between small lignin-related molecules and cellulose, with the planar linkages between guaiacyl-type monomers leading to higher binding affinities. These trends can be extended to larger lignin polymers, where we quantify the relationships between lignin polymer size and binding affinity through replica exchange umbrella sampling simulations. Rather than molecular weight, the binding surface area between the lignin polymer and the cellulose surface dictates the interaction strength. As a result, based on the findings here, we expect there to be abundant and durable interaction between cellulose and lignin, particularly on the hydrophobic face of cellulose where cellulase enzymes typically bind.

09 BIOMASS FUELS↗

Fission yeast Duf89 and Duf8901 are cobalt/nickel-dependent phosphatase–pyrophosphatases that act via a covalent aspartyl–phosphate intermediate

Domain of Unknown Function 89 (DUF89) proteins are metal-dependent phosphohydrolases. Exemplary DUF89 enzymes differ in their metal and phosphosubstrate preferences. Here, we interrogated the activities and structures of two DUF89 paralogs from fission yeast—Duf89 and Duf8901. We find that Duf89 and Duf8901 are cobalt/nickel-dependent phosphohydrolases adept at hydrolyzing p-nitrophenylphosphate and PP i . Crystal structures of metal-free Duf89 and Co 2+ -bound Duf8901 disclosed two enzyme conformations that differed with respect to the position of a three-helix module, which is either oriented away from the active site in Duf89 or forms a lid over the active site in Duf8901. Lid closure results in a 16 Å movement of Duf8901 Asp195, vis-à-vis Asp199 in Duf89, that brings Asp195 into contact with an octahedrally coordinated cobalt. Reaction of Duf8901 with BeCl 2 and NaF in the presence of divalent cations Co 2+ , Ni 2+ , or Zn 2+ generated covalent Duf8901-(Asp248)–beryllium trifluoride (BeF 3 )•Co 2+ , Duf8901-(Asp248)–BeF 3 •Ni 2+ , or Duf8901-(Asp248)–BeF 3 •Zn 2+ adducts, the structures of which suggest a two-step catalytic mechanism via formation and hydrolysis of an enzyme-(aspartyl)–phosphate intermediate. Alanine mutations of Duf8901 Asp248, Asn249, Lys401, Asp286, and Asp195 that interact with BeF 3 •Co 2+ squelched p-nitrophenylphosphatase activity. A 1.8 Å structure of a Duf8901-(Asp248)–AlF 4 –OH 2 •Co 2+ transition-state mimetic suggests an associative mechanism in which Asp195 and Asp363 orient and activate the water nucleophile. Whereas deletion of the duf89 gene elicited a phenotype in which expression of phosphate homeostasis gene pho1 was derepressed, deleting duf8901 did not, thereby hinting that the DUF89 paralogs have distinct functional repertoires in vivo.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic and optical properties of Zn-doped β-Ga 2 O 3 Czochralski single crystals

β-Ga 2 O 3 has several soluble deep acceptors that impart insulating behavior. In this study, we investigate Zn doping (0.25at.%) in bulk Czochralski and vertical gradient freeze β-Ga 2 O 3 . Representative crystals were assessed for orientation (electron backscatter diffraction and Raman spectroscopy), purity (glow discharge mass spectrometry and secondary ion mass spectrometry), optical properties (ultraviolet to near infrared absorption), and electrical properties (resistivity and current–voltage). Purity measurements indicate that Zn evaporation is insufficient to inhibit doping of Zn into β-Ga 2 O 3 . Hybrid functional calculations show Zn substitutes nearly equally on tetrahedral and octahedral sites, with less than ~0.1eV preference for the octahedral (Ga II ) site. Furthermore, calculations show that Zn Ga acts as a deep acceptor with trapping levels ~1.3 and ~0.9eV above the valence band for one and two holes, respectively. The solubility and electronic behavior of Zn dopants are consistent with measured concentrations >1×10 18 atoms/cm 3 and electrical measurements that show resistivity 10 11 –10 13 Ωcm, with no p-type conduction.

36 MATERIALS SCIENCE↗

Algorithm Plans Collision-Free Path for Robotic Manipulator

An algorithm has been developed to enable a computer aboard a robot to autonomously plan the path of the manipulator arm of the robot to avoid collisions between the arm and any obstacle, which could be another part of the robot or an external object in the vicinity of the robot. In simplified terms, the algorithm generates trial path segments and tests each segment for potential collisions in an iterative process that ends when a sequence of collision-free segments reaches from the starting point to the destination. The main advantage of this algorithm, relative to prior such algorithms, is computational efficiency: the algorithm is designed to make minimal demands upon the limited computational resources available aboard a robot. This path-planning algorithm utilizes a modified version of the collision-detection method described in "Improved Collision-Detection Method for Robotic Manipulator" (NPO-30356), NASA Tech Briefs, Vol. 27, No. 3 (June 2003), page 72. The method involves utilization of mathematical models of the robot constructed prior to operation and similar models of external objects constructed automatically from sensory data acquired during operation. This method incorporates a previously developed method, known in the art as the method of oriented bounding boxes (OBBs), in which an object is represented approximately, for computational purposes, by a box that encloses its outer boundary. Because many parts of a robotic manipulator are cylindrical, the OBB method has been extended in this method to enable the approximate representation of cylindrical parts by use of octagonal or other multiple-OBB assemblies denoted oriented bounding prisms (OBPs). A multiresolution OBB/OBP representation of the robot and its manipulator arm and a multiresolution OBB representation of external objects (including terrain) are constructed and used in a process in which collisions at successively finer resolutions are detected through computational detection of overlaps between the corresponding OBB and OBP models. For computational efficiency, the process is started at the coarsest resolution and stopped as soon as possible, preferably before reaching the finest resolution. At the coarsest resolution, there is a single OBB enclosing all relevant external objects and a single OBB enclosing the entire robot. At the next finer level of resolution, the coarsest-resolution OBB is divided into two OBBs, and so forth. If no collision is detected at the coarsest resolution, then there is no need for further computation to detect collisions. If a collision is detected at the coarsest resolution, then tests for collisions are performed at the next finer level of resolution. This process is continued to successively finer resolutions until either no more collisions are detected or the finest resolution is reached.

Backes, Paul↗

X-ray Polarization Detection of Cassiopeia A with IXPE

We report on a ∼5σ detection of polarized 3–6 keV X-ray emission from the supernova remnant Cassiopeia A (Cas A) with the Imaging X-ray Polarimetry Explorer (IXPE). The overall polarization degree of 1.8% ± 0.3% is detected by summing over a large region, assuming circular symmetry for the polarization vectors. The measurements imply an average polarization degree for the synchrotron component of ∼2.5%, and close to 5% for the X-ray synchrotron-dominated forward shock region. These numbers are based on an assessment of the thermal and nonthermal radiation contributions, for which we used a detailed spatial-spectral model based on Chandra X-ray data. A pixel-by-pixel search for polarization provides a few tentative detections from discrete regions at the ∼ 3σ confidence level. Given the number of pixels, the significance is insufficient to claim a detection for individual pixels, but implies considerable turbulence on scales smaller than the angular resolution. Cas A's X-ray continuum emission is dominated by synchrotron radiation from regions within ≲1017 cm of the forward and reverse shocks. We find that (i) the measured polarization angle corresponds to a radially oriented magnetic field, similar to what has been inferred from radio observations; (ii) the X-ray polarization degree is lower than in the radio band (∼5%). Since shock compression should impose a tangential magnetic-field structure, the IXPE results imply that magnetic fields are reoriented within ∼1017 cm of the shock. If the magnetic-field alignment is due to locally enhanced acceleration near quasi-parallel shocks, the preferred X-ray polarization angle suggests a size of 3 × 1016 cm for cells with radial magnetic fields.

Polarimetry↗

Preferred orbit planes in the gravitational field of a tumbling spheroidal galaxy

An analytic method is described by means of which the preferred planes into which gas will settle by dissipative differential precession in a slightly nonspherical, nonstatic potential can be determined. Attention is given to the analysis of circular orbit precession in the external potential of a slightly prolate spheroidal mass that is tumbling about a short axis, providing a crude model for barred spiral galaxies as well as for prolate elliptical ones. The results obtained agree with previous work on the existence, orientation, and stability of periodic orbits in triaxial potentials. Depending on the source and injection geometry of the gas and on the nature of dissipation in the gas, the orbital dynamics presented could lead to enhanced, or even catastrophic, radial inflow and to steady state warped structures.

Durisen, R. H.↗

Energy based fracture initiation criterion for strain-crystallizing rubber-like materials with pre-existing cracks

Fracture prediction is indispensable for polymers, like rubbers, which have a broad range of applications mainly due to their high extensibility. The phenomenon known as strain-induced crystallization further contributes to the fracture toughness of certain rubbers. Here in this study, a criterion based on internal bond energy, incorporating the effects of crystallization, is proposed to predict fracture initiation in rubber-like materials with pre-existing cracks. First, a multi-scale mechanical model is developed for characterizing the behavior of rubber when subjected to both uniaxial and biaxial deformation states. At the microscale, both the amorphous and crystalline chain segments are modeled as elastic in order to consider the energy contribution by the molecular bond distortions. This internal energy is considered along with the entropic and crystalline free energy for each chain. In the chain model, the effects of loading condition and the relative orientation of a chain on its crystallinity are taken into account. At the macroscopic scale, an existing crystallinity distribution function is adapted and a mixed finite element formulation with an augmented Lagrangian multiplier is utilized to impose the incompressibility constraint. A non-affine maximal advance path constraint based homogenization model is utilized for bridging the two scales. Its potential to account for anisotropy in the stretched network compels the model to be preferable due to its physical significance, for the purpose of fracture modeling. The rigidity of the crystallites is accounted for by proposing a crystallite distortion energy in addition to the critical bond dissociation energy, for fracture initiation to occur. The model is validated by comparison with existing experimental results for both crystallizing and non-crystallizing rubbers. In addition to its potential to predict the material behavior when subjected to uniaxial and biaxial loading, the capability of the model to quantitatively estimate the effect of crystallization on fracture initiation is also verified.

36 MATERIALS SCIENCE↗

Creating and Perpetuating Social Memory across the Ancient Cost Rican Landscape

For most of the time that Native Americans lived in ancient Costa Rica, their travel across the landscape was task-oriented and thus sufficiently randomized to leave no detectable trace. That changed about 500 BC in the Arenal area when people separated their cemeteries from their villages, and travel between them was ritually mediated by travel along the same path, in single file, in as straight a line as possible. The inadvertent erosion over centuries of use entrenched paths 2 or more meters deep, and we believe the cultural standard developed that the preferred way of entering a special place was by an entrenched path. People created and perpetuated social memory across their landscapes with generation after generation of use. The construction of meaning developed as the paths entrenched, ultimately embedding that meaning deep in people s belief systems as well as literally embedding it in the landscape. the Arenal area, a series of chiefdoms did develop east of the area at about AD 1000. To satisfy their need for monumentality, we suggest here that chiefs chose the proper entrenched entryway as exemplified in the Arenal area, for elaboration. On the rocky slopes of the volcanoes monumental entryways were built of stone, and on the fine alluvial plains they were of earthen construction. For instance, the radiating entrenched roads entering Cutris are about 4 km long and as wide as 50 meters, and many meters deep.

Sheets, Payson↗

Multi-scale computer-aided design and photo-controlled macromolecular synthesis boosting uranium harvesting from seawater

By integrating multi-scale computational simulation with photo-regulated macromolecular synthesis, this study presents a new paradigm for smart design while customizing polymeric adsorbents for uranium harvesting from seawater. A dissipative particle dynamics (DPD) approach, combined with a molecular dynamics (MD) study, is performed to simulate the conformational dynamics and adsorption process of a model uranium grabber, i.e., PAO m -b-PPEGMA n , suggesting that the maximum adsorption capacity with atomic economy can be achieved with a preferred block ratio of 0.18. The designed polymers are synthesized using the PET-RAFT polymerization in a microfluidic platform, exhibiting a record high adsorption capacity of uranium (11.4 ± 1.2 mg/g) in real seawater within 28 days. This study offers an integrated perspective to quantitatively assess adsorption phenomena of polymers, bridging metal-ligand interactions at the molecular level with their spatial conformations at the mesoscopic level. The established protocol is generally adaptable for target-oriented development of more advanced polymers for broadened applications.

97 MATHEMATICS AND COMPUTING↗

A Comparison of Structurally Connected and Multiple Spacecraft Interferometers

Structurally connected and multiple spacecraft interferometers are compared in an attempt to establish the maximum baseline (referred to as the "cross-over baseline") for which it is preferable to operate a single-structure interferometer in space rather than an interferometer composed of numerous, smaller spacecraft. This comparison is made using the total launched mass of each configuration as the comparison metric. A framework of study within which structurally connected and multiple spacecraft interferometers can be compared is presented in block diagram form. This methodology is then applied to twenty-two different combinations of trade space parameters to investigate the effects of different orbits, orientations, truss materials, propellants, attitude control actuators, onboard disturbance sources, and performance requirements on the cross-over baseline. Rotating interferometers and the potential advantages of adding active structural control to the connected truss of the structurally connected interferometer are also examined. The minimum mass design of the structurally connected interferometer that meets all performance-requirements and satisfies all imposed constraints is determined as a function of baseline. This minimum mass design is then compared to the design of the multiple spacecraft interferometer. It is discovered that the design of the minimum mass structurally connected interferometer that meets all performance requirements and constraints in solar orbit is limited by the minimum allowable aspect ratio, areal density, and gage of the struts. In the formulation of the problem used in this study, there is no advantage to adding active structural control to the truss for interferometers in solar orbit. The cross-over baseline for missions of practical duration (ranging from one week to thirty years) in solar orbit is approximately 400 m for non-rotating interferometers and 650 m for rotating interferometers.

Surka, Derek M.↗

Preferential Attraction of Oviposition-Ready Oriental Fruit Flies to Host Fruit Odor over Protein Food Odor

Olfaction plays a key role in the location of food and oviposition resources by tephritid fruit flies. Adult females, including oriental fruit fly, Bactrocera dorsalis, can sustain egg production throughout their lives provided they obtain sufficient protein. Thus, preferential attraction to food or oviposition sites (host fruit) will depend on a fly’s particular physiological state. In this study, laboratory bioassays were conducted with mature, mated B. dorsalis (provisioned protein and sugar ad libitum) to evaluate attraction to traps baited with torula yeast versus six host fruit sources (guava, guava juice, mango, orange, Surinam cherry, or white sapote). Females that preferred fruit laid a significant number of eggs around the trap entrance (average 405 eggs/fly), while almost no eggs were laid by females that preferred yeast (0.5 and 1.3 eggs/fly on two occasions). Similar results were observed in a bioassay using headspace extracts of guava juice and torula yeast, supporting olfactory-mediated responses. When individual females were allowed to oviposit in guava juice traps 0–24 h after a choice test, 45.8% of females that chose guava juice laid eggs (average 14.7 eggs/fly), compared with 27.5% that chose yeast (average 6.5 eggs/fly). Dissections indicated that females with a preference for guava juice had an egg load 2.4 times greater than females that preferred yeast. These results suggest there is an olfactory-based behavioral switch in preference from protein to host odors when female B. dorsalis are oviposition-ready. We discuss the implications of our findings for practical behavioral management and detection programs for B. dorsalis.

54 ENVIRONMENTAL SCIENCES↗

Endotaxial growth of CoSi2 within (111) oriented Si in a molecular beam epitaxy system

A new mode of growth is reported in which buried metallic layers can be fabricated within a single-crystal semiconductor through preferential subsurface growth on previously-grown 'seed' regions. The deposition of Co at 800 C at a rate of 0.01 nm/s on (111) Si substrates containing buried CoSi2 columns 40-100 nm below the Si surface results in the growth and coalescence of these subsurface columns. The formation of a CoSi2 layer on the Si surface is suppressed by this growth mode. It is proposed that the high diffusion rate of Co at 800 C, coupled with the high growth rate of CoSi2 at the subsurface columns, is responsible for this preferred 'endotaxial' growth mode. This growth technique was used to produce a continuous buried single-crystal layer of CoSi2 under a single-crystal Si capping layer.

George, T.↗

Comparison of excess free energy at an interface according to the applied interpolation scheme for elasticity: A phase-field method

Phase-field modeling is an effective simulation technique for modeling microstructure evolution of elastically anisotropic systems. To introduce the elastic energy contribution in a phase field model, an interpolation scheme is used to define the mechanical properties within the phases and across the continuous interface. Several existing interpolation schemes introduce a potential excess elastic energy at the interface, which undesirable effect on microstructure evolution needs to be evaluated. In this study, we focused on three interpolation schemes including Khachaturyan’ scheme (KHS), Voigt–Taylor’s scheme (VTS), and Steinbach–Apel’s scheme (SAS). Comparisons of these schemes’ performances were performed in three configuration types using the MOOSE (Multiphysics Object-Oriented Simulation Environment) framework: bi-crystal, isotropic particle-matrix and anisotropic particle-matrix. The contribution of excess elastic energy on the interface energy as a function of interface width and the computational time to steady-state were evaluated in these three configurations. SAS introduces the lowest excess elastic energy contribution and the VTS has the biggest contribution amongst the considered schemes. Moreover, when modeling precipitation in an anisotropic elastic material, the SAS approach seems to predict more physical convex shapes during growth, making it preferable to KHS and VTS. Finally, as currently implemented, SAS requires the largest computational time and KHS requires the smallest time to reach steady-state amongst the considered schemes.

36 MATERIALS SCIENCE↗

Microstructural Evolution of Steel During Magnetic Field-Assisted Processing

Advancing magnetic field-assisted processing, as an energy-efficient method for tailoring steel microstructures, requires a thorough understanding of how the high magnetic field impacts microstructural evolution, particularly its effect on prior austenite grain structures. The current investigation of a near-eutectoid composition, Fe-C alloy, uses electron backscatter diffraction to examine the morphology and orientation of martensite and pearlite microstructures, and to reconstruct the parent austenite microstructures present during equivalent heating under varied magnetic field strengths (0-T, 2-T, 5-T, and 9-T). It was observed that the magnetic field has a negligible effect on martensite lath/block width, slightly decreases prior austenite grain size, and increases the fraction of austenite grains with annealing twins. Additionally, the magnetic field increases the phase fraction of proeutectoid ferrite but has a negligible effect on pearlite block size and the distribution of boundary misorientation angles. No preferred texture was induced by the magnetic field, regardless of the applied field direction, in the proeutectoid ferrite phase or the martensite and prior austenite microstructures. Furthermore, the observed results contradict previous literature, and the differences are discussed.

Magnetic Materials↗

Anisotropic surface potentials induced by competitive ion adsorption enable the synthesis of branched cubic Pt mesocrystals

Creation of complex nanostructured materials through oriented attachment (OA) requires the manipulation of interparticle forces, including electrostatic repulsion, which depends strongly on surface potentials and can be modified through the effect of solution environment on interfacial chemistry. Here we show that time-dependent anisotropies in surface potential driven by competitive ion adsorption can alter facet-selectivity during OA. This phenomenon enables the synthesis of branched cubic Pt mesocrystals. Initially, Pt nanoparticles attach preferentially at their {100} facets to form a well-defined cubic core. Over time, changes in ion adsorption shift the attachment preference to the {111} facets, promoting branch formation. In both stages, anisotropic surface potentials generate electrostatic torques that align the particles prior to attachment. These findings demonstrate a generalizable strategy for directing the architecture of nanomaterials through time-resolved control of interfacial chemistry during OA, offering new pathways for the design of complex mesoscale structures.

Bae, Yuna [Pacific Northwest National Laboratory (↗

Single Crystals of Vanadium Oxides as a Lens for Understanding Structural and Electronic Phase Transformations, Ion Transport, Chemo-Mechanical Coupling, and Electrothermal Neuronal Emulation

Vanadium oxides cystallize in a diverse array of structures and compositions arising from the redox versatility of vanadium, variable covalency of V−O bonds, and myriad coordination geometries. Their open frameworks present abundant interstitial sites that enable insertion of guest-ions. In such compounds, V3d electron and spin localization and disorder couple strongly to structural preferences. The rich structural diversity manifests as a “rugged” free energy landscape with multiple interconvertible polymorphs. Such a landscape sets up structural, electronic, and magnetic transitions that underpin the promise of these materials as ion-insertion battery electrodes; compact primitives for brain-inspired computing, and heterogeneous catalysts. Here, we examine the structural and compositional diversity, electronic instabilities, defect dynamics, structure transformations, mechanical properties, and surface structure of vanadium oxides using single crystals as a distinctive lens. Single crystals enable the measurement of structure−function correlations without the ensemble and orientational averaging inevitable in polycrystalline materials. Their well-defined surfaces further enable examination of facet-dependent reactivity toward molecular adsorbates, ion fluxes, and lattice (mis)matched solids. We provide a comprehensive account of vanadium-oxide single-crystal studies, from delineation of common structural motifs to single-crystal growth techniques, topochemical modification strategies, mechanisms underpinning electronic instabilities, and implementation as electrothermal neurons and battery electrode materials.

Ponis, John [Texas A&M University, College Station↗

Strong evidence that the galactic bulge is shining in gamma rays

There is growing evidence that the Galactic Center Excess identified in the Fermi-LAT gamma-ray data arises from a population of faint astrophysical sources. We provide compelling supporting evidence by showing that the morphology of the excess traces the stellar over-density of the Galactic bulge. By adopting a template of the bulge stars obtained from a triaxial 3D fit to the diffuse near-infrared emission, we show that it is detected at high significance. The significance deteriorates when either the position or the orientation of the template is artificially shifted, supporting the correlation of the gamma-ray data with the Galactic bulge. In deriving these results, we have used more sophisticated templates at low-latitudes for the Fermi bubbles compared to previous work and the three-dimensional Inverse Compton (IC) maps recently released by the GALPROP team. Our results provide strong constraints on Millisecond Pulsar (MSP) formation scenarios proposed to explain the excess. We find that an admixture formation scenario, in which some of the relevant binaries are primordial and the rest are formed dynamically, is preferred over a primordial-only formation scenario at 7.6σ confidence level. Our detailed morphological analysis also disfavors models of the disrupted globular clusters scenario that predict a spherically symmetric distribution of MSPs in the Galactic bulge. For the first time, we report evidence of a high energy tail in the nuclear bulge spectrum that could be the result of IC emission from electrons and positrons injected by a population of MSPs and star formation activity from the same site.

79 ASTRONOMY AND ASTROPHYSICS↗

Space ultra-vacuum facility and method of operation

A wake shield facility providing an ultrahigh vacuum level for space processing is described. The facility is in the shape of a truncated, hollow hemispherical section, one side of the shield convex and the other concave. The shield surface is preferably made of material that has low out-gassing characteristics such as stainless steel. A material sample supporting fixture in the form of a carousel is disposed on the convex side of the shield at its apex. Movable arms, also on the convex side, are connected by the shield in proximity to the carousel, the arms supporting processing fixtures, and providing for movement of the fixtures to predetermined locations required for producing interations with material samples. For MBE processes a vapor jet projects a stream of vaporized material onto a sample surface. The fixtures are oriented to face the surface of the sample being processed when in their extended position, and when not in use they are retractable to a storage position. The concave side of the shield has a support structure including metal struts connected to the shield, extending radially inward. The struts are joined to an end plate disposed parallel to the outer edge of the shield. This system eliminates outgassing contamination.

Naumann, Robert J.↗