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

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All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

Mobility power flow analysis of an L-shaped plate structure subjected to distributed loading

An analytical investigation based in the Mobility Power Flow (MPF) method is presented for the determination of the vibrational response and power flow for two coupled flat plate structures in an L-shaped configuration, subjected to distributed excitation. The principle of the MPF method consists of dividing the global structure into a series of subsystems coupled together using mobility functions. Each separate subsystem is analyzed independently to determine the structural mobility functions for the junction and excitation locations. The mobility functions, together with the characteristics of the junction between the subsystems, are then used to determine the response of the global structure and the MPF. In the considered coupled plate structure, MPF expressions are derived for distributed mechanical excitation which is independent of the structure response. However using a similar approach with some modifications excitation by an acoustic plane wave can be considered. Some modifications are required to deal with the latter case are necessary because the forces (acoustic pressure) acting on the structure are dependent on the response of the structure due to the presence of the scattered pressure.

Cuschieri, J. M.↗
DOE OSTI2019

Charge-Lattice Coupling in Hole-Doped LuFe 2 O 4 + δ : The Origin of Second-Order Modulation

Understanding singularities in ordered structures, such as dislocations in lattice modulation and solitons in charge ordering, offers great opportunities to disentangle the interactions between the electronic degrees of freedom and the lattice. Specifically, a modulated structure has traditionally been expressed in the form of a discrete Fourier series with a constant phase and amplitude for each component. We report atomic scale observation and analysis of a new modulation wave in hole-doped ${\mathrm{LuFe}}_{2}{\mathrm{O}}_{4+{\delta}}$ that requires significant modifications to the conventional modeling of ordered structures. This new modulation with an unusual quasiperiodic singularity can be accurately described only by introducing a well-defined secondary modulation vector in both the phase and amplitude parameter spaces. Correlated with density-functional-theory (DFT) calculations, our results reveal that those singularities originate from the discontinuity of lattice displacement induced by interstitial oxygen in the system. The approach of our work is applicable to a wide range of ordered systems, advancing our understanding of the nature of singularity and modulation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Damping and mode shape modification for additively manufactured walls with captured powder

Here, this paper describes the fabrication, modeling, and dynamic testing of laser powder bed fusion stainless steel walls with captured powder cores. The purpose of the study is to determine the increased structural damping, or energy dissipation, and mode shape modification caused by the inclusion of the unmelted powder core within the solid walls. It is shown experimentally that the damping increases with larger powder core width and that the damping addition is mode dependent. Damping increases over the solid wall values by factors of 2.9–225 are reported depending on the mode number and core width. It is also seen that the mode shapes are distorted relative to the solid wall results as the core width is increased and wall thickness is decreased. Comparisons with finite element models confirm this trend.

42 ENGINEERING↗
DOE OSTI2020

Hydration and reaction mechanisms on sodium silicate glass surfaces from molecular dynamics simulations with reactive force fields

Recent development of reactive force fields have enabled molecular dynamics simulations of interactions between silicate glasses and water at the atomistic scale. While multicomponent silicate glasses encompass a wide variety of compositions and properties, one common structural feature in these glasses is the combination of the network structure that is made up of silica tetrahedra linked through corner sharing interspersed with network modifiers like alkali and alkaline-earth ions that break up the Si–O–Si linkages by forming nonbridging oxygen. In reactions with water, ion exchange between alkali ions in the glass and proton or hydronium in the solution, as well as hydrolysis reaction of the Si–O–Si linkages and subsequent silanol formation, is observed and well documented. Furthermore, we have used a set of recently developed reactive force field to investigate the reactions between water and the surfaces of silica and sodium silicate glasses of different compositions for reactions up to 8 nanoseconds. Our results indicate sodium leaching into water and diffusion of water molecules up to 25 Å into the glass surface. We examined the structural and compositional changes inside the glass and around the diffused ions and use these to explain the rates of silanol formation at the surface. We also observed proton transport in the glass which has an indirect influence on the silanol formation rates. While the surface of the glass was rough to start with, it undergoes further modification into a hydrated gel-like structure in the glass for up to 5 Å in the higher alkali containing glasses. It was found that the leached sodium ions remain close to the interface and that fragments of silicate network from the surface is capable of dislodging from the bulk glass and enter the aqueous solution. These simulations thus provide insights into the formation and structure of an alteration layers commonly observed in multicomponent silicate glasses corroded in aqueous solutions.

36 MATERIALS SCIENCE↗
NASA NTRS2014

CEO Sites Mission Management System (SMMS)

Late in fiscal year 2011, the Crew Earth Observations (CEO) team was tasked to upgrade its science site database management tool, which at the time was integrated with the Automated Mission Planning System (AMPS) originally developed for Earth Observations mission planning in the 1980s. Although AMPS had been adapted and was reliably used by CEO for International Space Station (ISS) payload operations support, the database structure was dated, and the compiler required for modifications would not be supported in the Windows 7 64-bit operating system scheduled for implementation the following year. The Sites Mission Management System (SMMS) is now the tool used by CEO to manage a heritage Structured Query Language (SQL) database of more than 2,000 records for Earth science sites. SMMS is a carefully designed and crafted in-house software package with complete and detailed help files available for the user and meticulous internal documentation for future modifications. It was delivered in February 2012 for test and evaluation. Following acceptance, it was implemented for CEO mission operations support in April 2012. The database spans the period from the earliest systematic requests for astronaut photography during the shuttle era to current ISS mission support of the CEO science payload. Besides logging basic image information (site names, locations, broad application categories, and mission requests), the upgraded database management tool now tracks dates of creation, modification, and activation; imagery acquired in response to requests; the status and location of ancillary site information; and affiliations with studies, their sponsors, and collaborators. SMMS was designed to facilitate overall mission planning in terms of site selection and activation and provide the necessary site parameters for the Satellite Tool Kit (STK) Integrated Message Production List Editor (SIMPLE), which is used by CEO operations to perform daily ISS mission planning. The CEO team uses the SMMS for three general functions - database queries of content and status, individual site creation and updates, and mission planning. The CEO administrator of the science site database is able to create or modify the content of sites and activate or deactivate them based on the requirements of the sponsors. The administrator supports and implements ISS mission planning by assembling, reporting, and activating mission-specific site selections for management; deactivating sites as requirements are met; and creating new sites, such as International Charter sites for disasters, as circumstances warrant. In addition to the above CEO internal uses, when site planning for a specific ISS mission is complete and approved, the SMMS can produce and export those essential site database elements for the mission into XML format for use by onboard Earth-location systems, such as Worldmap. The design, development, and implementation of the SMMS resulted in a superior database management system for CEO science sites by focusing on the functions and applications of the database alone instead of integrating the database with the multipurpose configuration of the AMPS. Unlike the AMPS, it can function and be modified within the existing Windows 7 environment. The functions and applications of the SMMS were expanded to accommodate more database elements, report products, and a streamlined interface for data entry and review. A particularly elegant enhancement in data entry was the integration of the Google Earth application for the visual display and definition of site coordinates for site areas defined by multiple coordinates. Transfer between the SMMS and Google Earth is accomplished with a Keyhole Markup Language (KML) expression of geographic data (see figures 3 and 4). Site coordinates may be entered into the SMMS panel directly for display in Google Earth, or the coordinates may be defined on the Google Earth display as a mouse-controlled polygonal definition and transferred back into the SMMS as KML input. This significantly reduces the possibility of errors in coordinate entries and provides visualization of the scale of the site being defined. CEO now has a powerful tool for managing and defining sites on the Earth's surface for both targets of astronaut photography or other onboard remote sensing systems. It can also record and track results by sponsor, collaborator, or type of study.

Trenchard, Mike↗
NASA NTRS1973

Attitude control of a large flexible spacecraft using three-axis mass expulsion control.

A study of the elastic effects of large area solar arrays on attitude control of a spacecraft was conducted. It is demonstrated for sufficiently low structural frequencies that excitation of certain modes can induce instability in the pitch axis. Stiffening the arrays can eliminate the instability. However, a severe weight penalty is associated with such modification. A more efficient means of minimizing the structural interaction effects is to change the shape of the array. For stable configurations, another problem may be encountered. This is the imposition of high rates on the spacecraft bus by oscillation of the solar arrays. Since low rates are required to obtain accurate science experiment results, it is imperative that the high rate problem be resolved. This also is possible by changing the solar array configuration.

Marsh, E. L.↗
NASA NTRS2013

Monte Carlo Bayesian Inference on a Statistical Model of Sub-gridcolumn Moisture Variability Using High-resolution Cloud Observations : Sensitivity Tests and Results - Part II

Part I presented a Monte Carlo Bayesian method for constraining a complex statistical model of GCM sub-gridcolumn moisture variability using high-resolution MODIS cloud data, thereby permitting large-scale model parameter estimation and cloud data assimilation. This part performs some basic testing of this new approach, verifying that it does indeed significantly reduce mean and standard deviation biases with respect to the assimilated MODIS cloud optical depth, brightness temperature and cloud top pressure, and that it also improves the simulated rotational-Ramman scattering cloud optical centroid pressure (OCP) against independent (non-assimilated) retrievals from the OMI instrument. Of particular interest, the Monte Carlo method does show skill in the especially difficult case where the background state is clear but cloudy observations exist. In traditional linearized data assimilation methods, a subsaturated background cannot produce clouds via any infinitesimal equilibrium perturbation, but the Monte Carlo approach allows finite jumps into regions of non-zero cloud probability. In the example provided, the method is able to restore marine stratocumulus near the Californian coast where the background state has a clear swath. This paper also examines a number of algorithmic and physical sensitivities of the new method and provides guidance for its cost-effective implementation. One obvious difficulty for the method, and other cloud data assimilation methods as well, is the lack of information content in the cloud observables on cloud vertical structure, beyond cloud top pressure and optical thickness, thus necessitating strong dependence on the background vertical moisture structure. It is found that a simple flow-dependent correlation modification due to Riishojgaard (1998) provides some help in this respect, by better honoring inversion structures in the background state.

Monte Carlo Bayesian inference↗
NASA NTRS2004

A Stigmergic Cooperative Multi-Robot Control Architecture

In nature, there are numerous examples of complex architectures constructed by relatively simple insects, such as termites and wasps, which cooperatively assemble their nests. A prototype cooperative multi-robot control architecture which may be suitable for the eventual construction of large space structures has been developed which emulates this biological model. Actions of each of the autonomous robotic construction agents are only indirectly coordinated, thus mimicking the distributed construction processes of various social insects. The robotic construction agents perform their primary duties stigmergically, i.e., without direct inter-agent communication and without a preprogrammed global blueprint of the final design. Communication and coordination between individual agents occurs indirectly through the sensed modifications that each agent makes to the structure. The global stigmergic building algorithm prototyped during the initial research assumes that the robotic builders only perceive the current state of the structure under construction. Simulation studies have established that an idealized form of the proposed architecture was indeed capable of producing representative large space structures with autonomous robots. This paper will explore the construction simulations in order to illustrate the multi-robot control architecture.

Howsman, Thomas G.↗
NASA NTRS1974

Apollo experience report: Spacecraft structure subsystem

The flightworthiness of the Apollo spacecraft structure was verified primarily through a rigorous, vehicle level, ground test program and flight tests. The failures and anomalies encountered during this testing were the major factors considered in determining necessary modifications to the basic design of the spacecraft structure. In this report, these failures, their causes, and their resolutions are discussed. A description of the spacecraft structure and discussions of the ground and flight test programs are presented.

Smith, P. D.↗
NASA NTRS1995

Modification of Experimental Protocols for a Space Shuttle Flight and Applications for the Analysis of Cytoskeletal Structures During Fertilization, Cell Division , and Development in Sea Urchin Embryos

To explore the role of microgravity on cytoskeletal organization and skeletal calcium deposition during fertilization, cell division, and early development, the sea urchin was chosen as a model developmental system. Methods were developed to employ light, immunofluorescence, and electron microscopy on cultures being prepared for flight on the Space Shuttle. For analysis of microfilaments, microtubules, centrosomes, and calcium-requiring events, our standard laboratory protocols had to be modified substantially for experimentation on the Space Shuttle. All manipulations were carried out in a closed culture chamber containing 35 ml artificial sea water as a culture fluid. Unfertilized eggs stored for 24 hours in these chambers were fertilized with sperm diluted in sea water and fixed with concentrated fixatives for final fixation in formaldehyde, taxol, EGTA, and MgCl2(exp -6)H2O for 1 cell to 16 cell stages to preserve cytoskeletal structures for simultaneous analysis with light, immunofluorescence, and electron microscopy, and 1.5 percent glutaraldehyde and 0.4 percent formaldehyde for blastula and plueus stages. The fixed samples wre maintained in chambers without degradation for up to two weeks after which the specimens were processed and analyzed with routine methods. Since complex manipulations are not possible in the closed chambers, the fertilization coat was removed from fixation using 0.5 percent freshly prepared sodium thioglycolate solution at pH 10.0 which provided reliable immunofluorescence staining for microtubules. Sperm/egg fusion, mitosis, cytokinesis, and calcium deposition during spicule formatin in early embryogenesis were found to be without artificial alterations when compared to cells fixed fresh and processed with conventional methods.

Chakrabarti, Amitabha↗
DOE OSTI2022

In-plane and through-plane dielectric properties of graphene oxide membrane: Effect of Al 3 + modification

A graphene oxide (GO) membrane can be used in structural dielectric capacitors and planar micro-supercapacitors as a dielectric separator material due to its excellent through-plane and in-plane dielectric properties. The ability to tailor the dielectric properties of the GO membrane is crucial for dielectric applications. We believe this to be the first demonstration describing how Al 3+ ions impact the dielectric properties of the GO membrane through cation to oxygenated functional groups interactions. In this work, the Al 3+ -modification to the GO membrane was realized through a facile pre-coordination method followed by layer-by-layer assembling. The influence of Al 3+ on the GO membranes’ through-plane and in-plane dielectric properties (dielectric constant and dielectric loss) was investigated in the frequency range from 0.01 Hz to 10 5 Hz. Plane-to-plane and edge-to-edge Al 3+ coordination with the functional group on the basal plane or edge of the GO sheets was proposed to understand the metal ion's impact on the dielectric properties. The results demonstrated that the Al 3+ modification was an effective strategy to tailoring the GO membranes’ dielectric properties in a low frequency regime and further suggested the possibility of designing dielectric GO membranes with controllable dielectric performance. At a low frequency range (0.01–1 Hz), the addition of Al 3+ increased the through-plane dielectric constant and decreased the in-plane dielectric constant. In terms of dielectric loss, unmodified GO membranes exhibited a higher in-plane dielectric loss than the through-plane dielectric loss. Al 3+ -modified GO membranes exhibited increased through-plane dielectric loss and decreased in-plane dielectric loss compared to the unmodified GO membranes.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Exploring the impact of Cr-doping on the crystallographic and magnetic structure of Mn 5 Si 3 antiferromagnetic alloy

Here, the role of Cr-doping on the structural and magnetic ground states of Mn 5 Si 3 alloy has been investigated through temperature-dependent neutron powder diffraction (NPD) and X-ray absorption fine structure (XAFS) techniques. All the Cr-doped alloys of nominal composition Mn 5-x Cr x Si 3 (for x = 0.05, 0.1, and 0.2) undergo two first-order magneto-structural phase transitions from hexagonal (space group: P6 3 /mcm) paramagnetic → orthorhombic (space group: Ccmm) collinear antiferromagnetic → orthorhombic (space group: Cc2m) non-collinear antiferromagnetic phase on cooling from room temperature. NPD studies at different constant temperatures indicate that both anti ferromagnetic phases are commensurate in nature and can be represented by q = (0,1,0) magnetic propagation vector for all the Cr-doped alloys. Such doping at the Mn-site results in a significant modification of the non-collinear antiferromagnetic structure (both moment size and orientation) and hence affects the unusual magnetic properties, like inverted hysteresis loop, thermomagnetic irreversibility, etc. The XAFS measurements were performed to interpret the local environment of doped Cr atoms in detail, which is critical for a microscopic understanding of the unusual properties of this class of Cr-doped Mn 5 Si 3 alloys. The analysis confirms the elemental state of Cr in the doped alloys and indicates a high degree of preservation of local crystallographic structure with varying Cr concentration and sample temperature. Doping induces intriguing changes in XAFS patterns, elucidated through different types of scattering mechanisms associated with the central absorbing Cr atom.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Predicting the chemical space of fungal polyketides by phylogeny-based bioinformatics analysis of polyketide synthase-nonribosomal peptide synthetase and its modification enzymes

Fungal polyketide synthase (PKS)–nonribosomal peptide synthetase (NRPS) hybrids are key enzymes for synthesizing structurally diverse hybrid natural products (NPs) with characteristic biological activities. Predicting their chemical space is of particular importance in the field of natural product chemistry. However, the unexplored programming rule of the PKS module has prevented prediction of its chemical structure based on amino acid sequences. Here, we conducted a phylogenetic analysis of 884 PKS–NRPS hybrids and a modification enzyme analysis of the corresponding biosynthetic gene cluster, revealing a hidden relationship between its genealogy and core structures. This unexpected result allowed us to predict 18 biosynthetic gene cluster (BGC) groups producing known carbon skeletons (number of BGCs; 489) and 11 uncharacterized BGC groups (171). The limited number of carbon skeletons suggests that fungi tend to select PK skeletons for survival during their evolution. The possible involvement of a horizontal gene transfer event leading to the diverse distribution of PKS–NRPS genes among fungal species is also proposed. This study provides insight into the chemical space of fungal PKs and the distribution of their biosynthetic gene clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Tours of High-containment and Pristine Facilities in Support of Mars Sample Return (MSR) Sample Receiving Facility (SRF) Definition Studies

During 2019 and 2020, the NASA Tiger Team RAMA (acronym of the authors) toured several high-containment biosafety laboratories and pristine space-mission facilities worldwide to better understand their practices, capabilities, and lessons-learned to aid in planning a Sample Receiving Facility (SRF) in support of Mars Sample Return (MSR). The team also included tours of a manufacturer of mobile and modular high-containment facilities as well as manufacturers of isolators and gloveboxes. In addition, the team visited the European Space Agency (ESA)ultraclean and sterile ISO 3 / airborne molecular contamination -9 (AMC-9) isolator line to clean and assemble the most critical hardware for ESA’s ExoMars Mars Lander System, and researchers developing a novel double-walled isolator (DWI) and robotic handling techniques in support of an MSR SRF. The RAMA team visits covered several construction modalities for an MSR SRF: (1) a new traditional fixed facility; (2) use of an existing fixed Biosafety Level 4(BSL-4) facility; (3) a novel modular BSL-4 approach; and (4) a hybrid combination of fixed, modular, and existing facilities. A new fixed facility approach can be tailored to MSR’s needs and is the approach used by all U.S. BSL-4 laboratories constructed to date. However, this approach could be the most expensive modality, take the longest to implement (8-12 years), and have significant programmatic risk of delay. The utilization of an existing BSL-4 facility may be possible depending on the final contamination control and science requirements for the MSR SRF. Due to the internal dimensions of the labs visited and facility structural requirements, it is unlikely that any modification can be made to the facility to meet cleanliness requirements. Furthermore, due to possible construction delays, possible capacity issues, and potential cross contamination vectors from in-house select agents, there may also be significant programmatic risks for sharing an existing facility. Another approach is building a contemporary modular facility. This is a novel approach that has recently been used for a BSL-3/3Ag facilities. The modular elements would be installed in a traditional building or shell structure. A modular facility has many advantages over a traditional fixed facility with lower costs, shorter design/construction/ commissioning schedule, and flexibility for easier retrofits and future expansion. Lastly, a hybrid approach of combining the use of either: (1) a modular facility inside a new fixed facility or (2) a modular and/or fixed BSL-4 annex in conjunction with an existing BSL-4 space should be considered. The advantage of a hybrid approach is that the facility could leverage the strengths of other approaches. Beyond facility construction approaches, the RAMA team investigated technologies and techniques for isolating and handling Martian samples in pristine environments. For example, ESA has been studying and developing a DWI breadboard along with other sample-handling technologies. The research and development investment for clean, remote manipulation and robotics at the start of the facility design phase would be beneficial to the SRF. Additionally, under-standing the lessons learned from Thales Alenia Space during the construction and operation of the most advanced state-of-the-art precision cleaning, sterilization, and assembly glovebox isolators ever developed for spacecraft hardware are also critical for the SRF. The RAMA team lays out a summary of the 18 facilities toured, and includes 43 observations,18 findings, and 22 areas of possible follow-up that the RAMA team and others could pursue to enable further findings. The observations and findings illustrate that constructing an MSR SRF would combine the complexity of both high-containment and pristine facilities, and merging these technologies would be challenging, but achievable.

Mars Sample Return↗
DOE OSTI2025

Tuning Interface Electronic Properties via Chiral Two‐Dimensional Metal‐Organic Frameworks

Control over structural symmetries in nanomaterials offers a powerful approach to engineer electronic properties. For instance, breaking of mirror symmetries in two-dimensional (2D) materials with a hexagonal lattice can lead to nontrivial electronic topologies and correlated-electron phenomena. Yet, the impact of structural chirality on the electronic properties of 2D materials and interfaces remains underexplored. Here, how chiral phases of a 2D metal-organic framework (MOF) with a hexagonal lattice—consisting of hexaazatriphenylene molecules coordinated to Cu atoms—scatter, confine, and perturb the Shockley surface state (SS) electrons of an underlying Ag(111) substrate is investigated. Via low-temperature scanning tunneling microscopy and spectroscopy, noncontact atomic force microscopy, and numerical calculations based on an electronic plane-wave expansion method, modifications of the Ag(111) SS band structure are shown and quantified, including gap openings and lifts of band degeneracies, driven exclusively by the structural chirality of the 2D MOF phases. These findings highlight how structural symmetries, in particular chirality, affect electronic states at material interfaces, expanding on the toolkit for designing 2D materials with tailored electronic properties.

band structure engineering↗
DOE OSTI2020

High-Strength Polylactic Acid (PLA) Biocomposites Reinforced by Epoxy-Modified Pine Fibers

The stiffness and tensile strength of biopolymers (e.g., polylactic acid (PLA)) are less than desirable for load-bearing applications in their neat form. The use of natural fibers as reinforcements for composites (for large-scale three-dimensional (3D) printing) has expanded rapidly, attributable to their low weight, low cost, high stiffness, and renewable nature. Silane and acid/alkali are typically used to modify the surface of natural fibers to improve the fiber/polymer interfacial adhesion. In this study, a simple method of impregnation was developed to modify pine fibers (loblolly, mesh size of 90–180 μm, 30 wt %) with a solvent-borne epoxy to reinforce PLA. As a benefit of the epoxy modification (0.5–10 wt %), the tensile strengths and Young’s moduli of the epoxy-modified pine/PLA composites increased by up to 20 and 82%, respectively, as compared to that of neat PLA. Furthermore, the epoxy-modified pine/PLA composites, with an optimum epoxy modification (1.0 wt %), had fewer voids on the fracture surface as compared with pine/PLA composites without the modification of pine fibers via epoxy. Finally, results confirmed that epoxy partially penetrated the pore/hollow inner structures of pine fibers and improved the fiber/matrix interfacial adhesion. Epoxy modification is found to be a simple and effective technique to improve the properties of biocomposites.

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

A Biologically Inspired Cooperative Multi-Robot Control Architecture

A prototype cooperative multi-robot control architecture suitable for the eventual construction of large space structures has been developed. In nature, there are numerous examples of complex architectures constructed by relatively simple insects, such as termites and wasps, which cooperatively assemble their nests. The prototype control architecture emulates this biological model. Actions of each of the autonomous robotic construction agents are only indirectly coordinated, thus mimicking the distributed construction processes of various social insects. The robotic construction agents perform their primary duties stigmergically i.e., without direct inter-agent communication and without a preprogrammed global blueprint of the final design. Communication and coordination between individual agents occurs indirectly through the sensed modifications that each agent makes to the structure. The global stigmergic building algorithm prototyped during the initial research assumes that the robotic builders only perceive the current state of the structure under construction. Simulation studies have established that an idealized form of the proposed architecture was indeed capable of producing representative large space structures with autonomous robots. This paper will explore the construction simulations in order to illustrate the multi-robot control architecture.

Howsman, Tom↗
DOE OSTI2025

Mass spectrometry structural analysis of intrinsically disordered phosphoproteins

Phosphorylation is a ubiquitous protein modification that is known to play important roles in many biological phenomena including cell signaling, the opening and closing of membrane protein channels, and even triggering of amyloid protein aggregation. Despite the effects phosphorylation has on protein function, the impact phosphorylation has on the structure of proteins is not well understood. Here, to determine how phosphorylation affects the structure of proteins, top-down mass spectrometry (TD-MS) and ion mobility-mass spectrometry (IM-MS) were performed on various phosphorylated proteins and their dephosphorylated proteoforms. TD-MS with collision- and electron-based fragmentation techniques was utilized to locate phosphorylation sites on the intrinsically disordered amyloid proteins β-casein and α-synuclein. TD-MS also provided evidence that alkaline phosphatase dephosphorylates β-casein from the N-terminus to the C-terminus. Furthermore, IM-MS of common phosphorylated proteins such as β-casein, α-casein, ovalbumin, and phosvitin indicates that phosphorylation promotes compaction of protein structure in denaturing as well as native conditions. Increases in abundance of more compact conformers are also observed when the disease related amyloid protein α-synuclein is phosphorylated at serine 129. We interpret the increased abundance of more compact conformers when proteins are phosphorylated as evidence that salt bridges form between negatively charged phosphates and positively charged residues, which alters protein structure. Salt bridge formation due to phosphorylation could be a mechanism for regulating protein function and be responsible for many of the phenomena observed in nature.

Amyloid proteins↗