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At least 595 records · Page 33

Ground Testing of the MISSE-16 Materials

The harsh space environment imposes very stringent requirements upon spacecraft materials, especially those located on exterior surfaces of space objects in low Earth orbit (LEO). As humankind moves from space exploration to space commercialization, these materials may have to last for 15–20 years without considerable degradation of their optical, electrical, mechanical, and thermal properties. Operational requirements dictate that these materials continue to function according to expectations. Hence, we must understand the effects of the space environment on materials currently in use as well as on untested materials. For the years, the Materials International Space Station Experiment Flight Facility (MISSE-FF) have flown many different materials to investigate the effect of LEO space weather exposure on the performance and durability of materials and devices. The MISSE-16 scientific team members plan to launch fifteen different novel and well-characterized spacecraft-relevant materials to the LEO environment for a duration of six months during the MISSE-16 mission. Changes in spectral reflectivity will be measured throughout the mission as the samples are exposed to the space environment. The same chemical damage the produces changes in optical reflectance also causes changes in numerous other physical properties such as electrical conductivity, mechanical strength, and chemical reactivity. Correlation of the changes in each of these properties as a function of radiation type, flux, and fluence allows various material properties to be inferred from one experimentally tractable measurement: color change. Flying identical test fixtures on the ram, zenith, and wake positions of the MISSE-FF, collecting spectrally resolved images of the materials, and concomitantly measuring the ambient space environment allows deconvolution of the material effects which occur as a result of exposure to neutral atomic oxygen (AO), unfiltered solar ultraviolet (UV) radiation, and electrons. The flight experiment will function as a ground truth reference for our team’s ongoing laboratory-based space weather-material interactions experiments. Comparison of the MISSE-16 data with extensive testing of “flight-duplicate” samples under simulated space weather conditions will enable development of chemical models for prediction of material degradation. This paper discusses preliminary results from the ground test campaign including measurements of UV/VIS/IR reflectance spectra, bidirectional reflectance distribution function (BRDF), surface potential decay, and surface morphology under electron and AO exposure.

Elena A. Plis↗

Liquid Metering Centrifuge Sticks (LMCS): A Centrifugal Approach to Metering Known Sample Volumes for Colorimetric Solid Phase Extraction (C-SPE)

Phase separation is one of the most significant obstacles encountered during the development of analytical methods for water quality monitoring in spacecraft environments. Removing air bubbles from water samples prior to analysis is a routine task on earth; however, in the absence of gravity, this routine task becomes extremely difficult. This paper details the development and initial ground testing of liquid metering centrifuge sticks (LMCS), devices designed to collect and meter a known volume of bubble-free water in microgravity. The LMCS uses centrifugal force to eliminate entrapped air and reproducibly meter liquid sample volumes for analysis with Colorimetric Solid Phase Extraction (C-SPE). C-SPE is a sorption-spectrophotometric platform that is being developed as a potential spacecraft water quality monitoring system. C-SPE utilizes solid phase extraction membranes impregnated with analyte-specific colorimetric reagents to concentrate and complex target analytes in spacecraft water samples. The mass of analyte extracted from the water sample is determined using diffuse reflectance (DR) data collected from the membrane surface and an analyte-specific calibration curve. The analyte concentration can then be calculated from the mass of extracted analyte and the volume of the sample analyzed. Previous flight experiments conducted in microgravity conditions aboard the NASA KC-135 aircraft demonstrated that the inability to collect and meter a known volume of water using a syringe was a limiting factor in the accuracy of C-SPE measurements. Herein, results obtained from ground based C-SPE experiments using ionic silver as a test analyte and either the LMCS or syringes for sample metering are compared to evaluate the performance of the LMCS. These results indicate very good agreement between the two sample metering methods and clearly illustrate the potential of utilizing centrifugal forces to achieve phase separation and metering of water samples in microgravity.

Gazda, Daniel B.↗

Effects of long term exposure on optical substrates and coatings (SOO50-2)

Kodak included 12 substrate and coating samples on the Long Duration Exposure Facility (LDEF) structure. There were 3 fused silica and 3 ultra low expansion (ULE(tm)) uncoated glass samples, 2 ULE(tm) samples with a high reflectance silver coating, 2 fused silica samples with an antireflectance coating, and 2 fused silica samples with a solar rejection coating. The sample dimensions were 32 mm diameter by 1 mm thick. A set of duplicate control samples was also manufactured and stored in a controlled environment for comparison purposes. A preliminary evaluation of the flight samples for effects from the 5 year mission showed that a contaminant was deposited on the samples, a micrometeroid impact occurred on one of the samples, and the radiation darkening which was expected for the glass did not occur. The results are presented in more detail.

John Vallimont↗

Developing Mass Spectrometry for Water Quantitation and Volatiles Analysis from In-Situ Regolith

With a revived focus to create a sustainable hu-man presence on the moon, and in preparation for future Mars exploration, it is imperative that all resources are utilized to their fullest potential [1]. In-Situ Resource Utilization (ISRU) will be critical for future mission success as it would enable in-dependent operation of missions while reducing the dependence on the complex supply chain created between the Earth, the moon and Mars. One of the most critical resources that has been identified for ISRU on the lunar surface is water [2]. Water is a versatile resource that can be used in various space operations, such as ra-diation shielding and conversion to oxygen (O2) for propellant [3,4]. One of the most water rich resources is thought to be within the regolith lo-cated in the permanently shadowed regions (PSR) of the Moon; several upcoming missions, such as PRIME-1 and VIPER, are already sched-uled to confirm this hypothesis [5,6]. However, there are currently no missions planned to quanti-fy the abudance of water at these regions. The quantity of water contained in the ice will inform and help the development of future ISRU plants and operation. Water and other volatile gases can be detect-ed upon controlled heating of icy lunar regolith for an accurate quantification of water. This method is similar to thermogravimetric analysis, which was used to analyze Apollo lunar regolith sam-ples. However, losses via sublimation/evaporation or contamination may have occurred with the samples due to the transit and exposure to the terrestrial environment. Furthermore, water would not be expected for these samples since they were not collected from a PSR. Thus, for more accurate results, icy lunar regolith should be ana-lyzed in situ to provide the most representative composition of both water and other volatile gas-es. The Light Water Analysis and Volatile Extract (LightWAVE) project aims to address this knowledge gap. A system has been developed to collect, heat and analyze evolved gases from lu-nar regolith on the lunar surface. The gases will be analyzed by a modified commercial off the shelf (COTS) residual gas analyzer (RGA) quad-rupole mass spectrometer. Evolved gases from heated regolith samples can be identified by the observed mass-to-charge (m/z) ratios, and the peak intensities correlate to the abundances of the observed gases for quantitation. Therefore, our group is developing a calibration methodology utilizing a COTS RGA to quantitate water from in-situ regolith samples on the lunar surface. The partial pressure of water and ideal gas law will be used to quantify the total water evolved from a regolith sample. Here we present our methodol-ogy for the design and calibration for water quan-titation using a COTS RGA.

Nilab Azim↗

Measurement of PuO 2 film thickness by electron probe microanalysis (EPMA) calibration curve method

Plutonium (Pu) surfaces are highly reactive toward oxygen containing species and, therefore, invariably covered with oxides (e.g. PuO 2 ) during transport and handling. The actual thickness of the surface oxide may dictate if a plutonium part is suitable for a certain application. As a result, a cost-effective, quick, non-destructive, yet reliable means to measure the oxide layer thickness formed on Pu samples is desirable. In this study, the cross-sections of a series of room temperature grown oxides on Pu samples were trenched by focus ion beam (FIB) then observed by scanning electron microscopy (SEM) to measure the surface oxide thicknesses, which were then combined with the corresponding oxygen k-ratios provided by electron probe microanalysis (EPMA) to form calibration curves. Oxide thickness measurements for the calibration curves were made on samples within the typical SEM observable range for PuO 2 (35–400 nm). The portion of the calibration curve in the thinner oxide region (<35 nm) were approximated via Pouchou and Pichoir’s Φ(ρz) theory. Two specimens with micrometer-thick PuO 2 standards (one formed at room temperature and the other at higher temperature with a higher level of crystallinity) were made for the k-ratios in this study, allowing EPMA users to choose the standard that best suits their needs. If the surface corrosion is known to be PuO 2 (from the environment in which the Pu sample is stored) or if the stoichiometry of the surface oxide is confirmed by a preliminary/compliment technique, these calibration curves allow EPMA users to quickly and efficiently determine PuO 2 thicknesses from the measured oxygen k-ratios of their samples. The methodology presented in this study can also be used as a template for creating calibration curves for oxides grown on other actinides.

36 MATERIALS SCIENCE↗

Cleanroom Robotics: Appropriate Technology for a Sample Receiving Facility?

NASA is currently pursuing a vigorous program that will collect samples from a variety of solar system environments. The Mars Exploration Program is expected to launch spacecraft that are designed to collect samples of martian soil, rocks, and atmosphere and return them to Earth, perhaps as early as 2016. International treaty obligations mandate that NASA conduct such a program in a manner that avoids cross-contamination both Earth and Mars. Because of this requirement, Mars sample curation will require a high degree biosafety, combined with extremely low levels inorganic, organic, and biological contamination.

Bell, M. S.↗

Mars Science Laboratory Drill

This drill (see Figure 1) is the primary sample acquisition element of the Mars Science Laboratory (MSL) that collects powdered samples from various types of rock (from clays to massive basalts) at depths up to 50 mm below the surface. A rotary-percussive sample acquisition device was developed with an emphasis on toughness and robustness to handle the harsh environment on Mars. It is the first rover-based sample acquisition device to be flight-qualified (see Figure 2). This drill features an autonomous tool change-out on a mobile robot, and novel voice-coil-based percussion. The drill comprises seven subelements. Starting at the end of the drill, there is a bit assembly that cuts the rock and collects the sample. Supporting the bit is a subassembly comprising a chuck mechanism to engage and release the new and worn bits, respectively, and a spindle mechanism to rotate the bit. Just aft of that is a percussion mechanism, which generates hammer blows to break the rock and create the dynamic environment used to flow the powdered sample. These components are mounted to a translation mechanism, which provides linear motion and senses weight-on-bit with a force sensor. There is a passive-contact sensor/stabilizer mechanism that secures the drill fs position on the rock surface, and flex harness management hardware to provide the power and signals to the translating components. The drill housing serves as the primary structure of the turret, to which the additional tools and instruments are attached. The drill bit assembly (DBA) is a passive device that is rotated and hammered in order to cut rock (i.e. science targets) and collect the cuttings (powder) in a sample chamber until ready for transfer to the CHIMRA (Collection and Handling for Interior Martian Rock Analysis). The DBA consists of a 5/8-in. (.1.6- cm) commercial hammer drill bit whose shank has been turned down and machined with deep flutes designed for aggressive cutting removal. Surrounding the shank of the bit is a thick-walled maraging steel collection tube allowing the powdered sample to be augured up the hole into the sample chamber. For robustness, the wall thickness of the DBA was maximized while still ensuring effective sample collection. There are four recesses in the bit tube that are used to retain the fresh bits in their bit box. The rotating bit is supported by a back-to-back duplex bearing pair within a housing that is connected to the outer DBA housing by two titanium diaphragms. The only bearings on the drill in the sample flow are protected by a spring-energized seal, and an integrated shield that diverts the ingested powdered sample from the moving interface. The DBA diaphragms provide radial constraint of the rotating bit and form the sample chambers. Between the diaphragms there is a sample exit tube from which the sample is transferred to the CHIMRA. To ensure that the entire collected sample is retained, no matter the orientation of the drill with respect to gravity during sampling, the pass-through from the forward to the aft chamber resides opposite to the exit tube.

Okon, Avi B.↗

Fuzzy learning under and about an unfamiliar fuzzy teacher

This study addresses the problem of optimal parametric learning in unfamiliar fuzzy environments. Prior studies in the domain of unfamiliar environments, which employed either crisp or fuzzy approaches to model the uncertainty or imperfectness of the learning environment, assumed that the training sample labels provided by the unfamiliar teacher were crisp, even if not perfect. Here, the more realistic problem of fuzzy learning under an unfamiliar teacher who provides only fuzzy (instead of crisp) labels, is tackled by expanding the previously defined fuzzy membership concepts to include an additional component representative of the fuzziness of the teacher. The previously studied scenarios, namely, crisp and fuzzy learning under (crisp) unfamiliar teacher, can be looked upon as special cases of this new methodology. As under the earlier studies, the estimated membership functions can then be deployed during the ensuing classification decision phase to judiciously take into account the imperfectness of the learning environment. The study also offers some insight into the properties of several of these fuzzy membership function estimators by examining their behavior under certain specific scenarios.

Dasarathy, Belur V.↗

NASA's Aerosol Sampling Experiment Summary

In a spacecraft cabin environment, the size range of indoor aerosols is much larger and they persist longer than on Earth because they are not removed by gravitational settling. A previous aerosol experiment in 1991 documented that over 90 of the mass concentration of particles in the NASA Space Shuttle air were between 10 m and 100 m based on measurements with a multi-stage virtual impactor and a nephelometer (Liu et al. 1991). While the now-retired Space Shuttle had short duration missions (less than two weeks), the International Space Station (ISS) has been continually inhabited by astronauts for over a decade. High concentrations of inhalable particles on ISS are potentially responsible for crew complaints of respiratory and eye irritation and comments about 'dusty' air. Air filtration is the current control strategy for airborne particles on the ISS, and filtration modeling, performed for engineering and design validation of the air revitalization system in ISS, predicted that PM requirements would be met. However, aerosol monitoring has never been performed on the ISS to verify PM levels. A flight experiment is in preparation which will provide data on particulate matter in ISS ambient air. Particles will be collected with a thermophoretic sampler as well as with passive samplers which will extend the particle size range of sampling. Samples will be returned to Earth for chemical and microscopic analyses, providing the first aerosol data for ISS ambient air.

Thermophoretic sampler↗

Summary of ADTT Website Functionality and Features

This report summarizes development of the ADTT web-based design environment by the ELORET team in 2000. The Advanced Design Technology Testbed had been in development for several years, with demonstration applications restricted to aerodynamic analyses of subsonic aircraft. The key changes achieved this year were improvements in Web-based accessibility, evaluation of collaborative visualization, remote invocation of geometry updates and performance analysis, and application to aerospace system analysis. Significant effort was also devoted to post-processing of data, chiefly through comparison of similar data for alternative vehicle concepts. Such comparison is an essential requirement for designers to make informed choices between alternatives. The next section of this report provides more discussion of the goals for ADTT development. Section 3 provides screen shots from a sample session in the ADTT environment, including Login and navigation to the project of interest, data inspection, analysis execution and output evaluation. The following section provides discussion of implementation details and recommendations for future development of the software and information technologies that provide the key functionality of the ADTT system. Section 5 discusses the integration architecture for the system, which links machines running different operating systems and provides unified access to data stored in distributed locations. Security is a significant issue for this system, especially for remote access to NAS machines, so Section 6 discusses several architectural considerations with respect to security. Additional details of some aspects of ADTT development are included in Appendices.

Hawke, Veronica↗

Penetrator Coring Apparatus for Cometary Surfaces

Touch and go impact coring is an attractive technique for sampling cometary nuclei and asteroidal surface on account of the uncertain strength properties and low surface gravities of these objects. Initial coring experiments in low temperature (approx. 153K polycrystalline ice) and porous rock demonstrate that simultaneous with impact coring, measurements of both the penetration strength and constraints on the frictional properties of surface materials can be obtained upon core penetration and core sample extraction. The method of sampling an asteroid, to be deployed, on the now launched MUSES-C mission, employs a small gun device that fires into the asteroid and the resulted impact ejecta is collected for return to Earth. This technique is well suited for initial sampling in a very low gravity environment and deployment depends little on asteroid surface mechanical properties. Since both asteroids and comets are believed to have altered surface properties a simple sampling apparatus that preserves stratigraphic information, such as impact coring is an attractive alternate to impact ejecta collection.

Braun, David F.↗

Automated Miniaturized Instrument for Space Biology Applications and the Monitoring of the Astronauts Health Onboard the ISS

Human space travelers experience a unique environment that affects homeostasis and physiologic adaptation. The spacecraft environment subjects the traveler to noise, chemical and microbiological contaminants, increased radiation, and variable gravity forces. As humans prepare for long-duration missions to the International Space Station (ISS) and beyond, effective measures must be developed, verified and implemented to ensure mission success. Limited biomedical quantitative capabilities are currently available onboard the ISS. Therefore, the development of versatile instruments to perform space biological analysis and to monitor astronauts' health is needed. We are developing a fully automated, miniaturized system for measuring gene expression on small spacecraft in order to better understand the influence of the space environment on biological systems. This low-cost, low-power, multi-purpose instrument represents a major scientific and technological advancement by providing data on cellular metabolism and regulation. The current system will support growth of microorganisms, extract and purify the RNA, hybridize it to the array, read the expression levels of a large number of genes by microarray analysis, and transmit the measurements to Earth. The system will help discover how bacteria develop resistance to antibiotics and how pathogenic bacteria sometimes increase their virulence in space, facilitating the development of adequate countermeasures to decrease risks associated with human spaceflight. The current stand-alone technology could be used as an integrated platform onboard the ISS to perform similar genetic analyses on any biological systems from the tree of life. Additionally, with some modification the system could be implemented to perform real-time in-situ microbial monitoring of the ISS environment (air, surface and water samples) and the astronaut's microbiome using 16SrRNA microarray technology. Furthermore, the current system can be enhanced substantially by combining it with other technologies for automated, miniaturized, high-throughput biological measurements, such as fast sequencing, protein identification (proteomics) and metabolite profiling (metabolomics). Thus, the system can be integrated with other biomedical instruments in order to support and enhance telemedicine capability onboard ISS. NASA's mission includes sustained investment in critical research leading to effective countermeasures to minimize the risks associated with human spaceflight, and the use of appropriate technology to sustain space exploration at reasonable cost. Our integrated microarray technology is expected to fulfill these two critical requirements and to enable the scientific community to better understand and monitor the effects of the space environment on microorganisms and on the astronaut, in the process leveraging current capabilities and overcoming present limitations.

Human space travelers↗

Global patterns of diversity and metabolism of microbial communities in deep-sea hydrothermal vent deposits

When deep-sea hydrothermal fluids mix with cold oxygenated fluids, minerals precipitate out of solution and form hydrothermal deposits. These actively venting deep-sea hydrothermal deposits support a rich diversity of thermophilic microorganisms which are involved in a range of carbon, sulfur, nitrogen, and hydrogen metabolisms. Global patterns of thermophilic microbial diversity in deep-sea hydrothermal ecosystems have illustrated the strong connectivity between geological processes and microbial colonization, but little is known about the genomic diversity and physiological potential of these novel taxa. Here we explore this genomic diversity in 42 metagenomes from four deep-sea hydrothermal vent fields and a deep-sea volcano collected from 2004 to 2018 and document their potential implications in biogeochemical cycles. Our dataset represents 3635 metagenome-assembled genomes encompassing 511 novel and recently identified genera from deep-sea hydrothermal settings. Some of the novel bacterial (107) and archaeal genera (30) that were recently reported from the deep-sea Brothers volcano were also detected at the deep-sea hydrothermal vent fields, while 99 bacterial and 54 archaeal genera were endemic to the deep-sea Brothers volcano deposits. We report some of the first examples of medium- (≥ 50% complete, ≤ 10% contaminated) to high-quality (> 90% complete, < 5% contaminated) MAGs from phyla and families never previously identified, or poorly sampled, from deep-sea hydrothermal environments. We greatly expand the novel diversity of Thermoproteia, Patescibacteria (Candidate Phyla Radiation, CPR), and Chloroflexota found at deep-sea hydrothermal vents and identify a small sampling of two potentially novel phyla, designated JALSQH01 and JALWCF01. Metabolic pathway analysis of metagenomes provides insights into the prevalent carbon, nitrogen, sulfur, and hydrogen metabolic processes across all sites and illustrates sulfur and nitrogen metabolic “handoffs” in community interactions. We confirm that Campylobacteria and Gammaproteobacteria occupy similar ecological guilds but their prevalence in a particular site is driven by shifts in the geochemical environment. Our study of globally distributed hydrothermal vent deposits provides a significant expansion of microbial genomic diversity associated with hydrothermal vent deposits and highlights the metabolic adaptation of taxonomic guilds. Collectively, our results illustrate the importance of comparative biodiversity studies in establishing patterns of shared phylogenetic diversity and physiological ecology, while providing many targets for enrichment and cultivation of novel and endemic taxa.

59 BASIC BIOLOGICAL SCIENCES↗

Mineralogy Considerations for 2003 MER Site Selection and the Importance for Astrobiology

Much of the discussion of site selection on Mars is based on interesting images of the surface combined with safety issues. I argue that the two rovers should be sent to mineralogically distinct regions. Compositional information is still poorly constrained on Mars; however, the instruments on the 2003 Mars Exploration Rovers (MERs) will provide a unique opportunity for detailed characterization including mineral identification. There is strong motivation for sending one rover to a "typical" region on Mars to be used as a ground truth for the Thermal Emission Spectrometer (TES), while the other rover should be sent to a site where water and chemical alteration are likely to have occurred. Determining the mineralogy of the Martian surface material provides information about the past and present environments on Mars which are an integral aspect of whether or not Mars was suitable for the origin of life. Understanding the mineralogy of terrestrial samples from potentially Mars-like environments is essential to this effort.

Bishop, J. L.↗

Lunar laser ranging data processing in a Unix/X windows environment

In cooperation with the NASA Crustal Dynamics Project initiative placing workstation computers at each of its laser ranging stations to handle data filtering and normalpointing, MLRS personnel have developed a new generation of software to provide the same services for the lunar laser ranging data type. The Unix operating system and X windows/Motif provides an environment for both batch and interactive filtering and normalpointing as well as prediction calculations. The goal is to provide a transportable and maintainable data reduction environment. This software and some sample displays are presented. that the lunar (or satellite) datacould be processed on one computer while data was taken on the other. The reduction of the data was totally interactive and in no way automated. In addition, lunar predictions were produced on-site, another first in the effort to down-size historically mainframe-based applications. Extraction of earth rotation parameters was at one time attempted on site in near-realtime. In 1988, the Crustal Dynamics Project SLR Computer Panel mandated the installation of Hewlett-Packard 9000/360 Unix workstations at each NASA-operated laser ranging station to relieve the aging controller computers of much of their data and communications handling responsibility and to provide on-site data filtering and normal pointing for a growing list of artificial satellite targets. This was seen by MLRS staff as an opportunity to provide a better lunar data processing environment as well.

Ricklefs, Randall L.↗

Surface chemistry of neutron irradiated tungsten in a high-temperature multi-material environment

Deuterium retention was measured on neutron irradiated tungsten samples where one side of the samples had a visually clean metallic luster and the opposite side appeared to have a reacted surface film. Deuterium plasma exposure and subsequent thermal desorption from the reacted surface side produced spectra with larger total deuterium desorption at lower temperatures than from the clean surface side. For neutron irradiation, these W disk samples were installed in an irradiation capsule in such a way that one side of W sample was in contact with the surface of another W sample, and the opposite side was in contact with a SiC temperature monitor. The composition of the reacted surface was investigated using X-ray photoelectron spectroscopy and showed that SiC had interdiffused into the W samples. Neutron enhanced diffusion likely contributed to this as SiC and W are stable at temperatures exceeding the irradiation temperature. Results highlight the need to consider the surface chemistry of samples in drawing conclusions on hydrogen isotope retention of W materials and also illustrate the complexity of multi-material nuclear environments expected in fusion devices.

36 MATERIALS SCIENCE↗

Property changes induced by the space environment in composite materials on LDEF: Solar array materials passive LDEF experiment A0171 (SAMPLE)

Surface modifications to composite materials induced by long term exposure in low earth orbit (LEO) were dominated by atomic oxygen erosion and micrometeoroid and space debris impacts. As expected, calculated erosion rates were peculiar to material type and within the predicted order of magnitude. Generally, about one ply of the carbon fiber composites was eroded during the 70 month LDEF experiment. Matrix erosion was greater than fiber erosion and was more evident for a polysulfone matrix than for epoxy matrices. Micrometeoroid and space debris impacts resulted in small (less than 1mm) craters and splattered contaminants on all samples. Surfaces became more diffuse and darker with small increases in emissivity and absorption. Tensile strength decreased roughly with thickness loss, and epoxy matrices apparently became slightly embrittled, probably as a result of continued curing under UV and/or electron bombardment. However, changes in the ultimate yield stress of the carbon reinforced epoxy composites correlate neither with weave direction nor fiber type. Unexpected developments were the discovery of new synergistic effects of the space environment in the interaction of atomic oxygen and copious amounts of contamination and in the induced luminescence of many materials.

Source record↗

Molecular Insights Into the Ionic Assembly of Poly-Galacturonic Acid Oligomers - Impact of Charge, Ionic Radius, and Polymer Functionalization

Pectin, a major class of matrix polysaccharides present in plant cell walls (PCW), contains widespread anionic saccharides that cross-link in the presence of cations. It modulates important functions such as cell-cell adhesion and determines the PCW's biomechanical properties. It is known that mono-, di-, and tri-valent cations facilitate cross-linking; however, significant knowledge gaps remain in understanding the structure and mechanism of pectin cross-linking. In this study, replica-exchange molecular dynamics (REMD) simulations were employed to elucidate the role of ionic charge, ionic radii, and functional groups on the cross-linking of homogalacturonan (HG), the most abundant pectin molecule. Our enhanced sampling approach in fully solvated environments suggests more effective cross-linking with higher-valent and smaller ions, and that the "zipper" conformation is more favorable than the prevalent "egg-box" conformation. These findings advance our fundamental understanding of pectin matrix structure in PCWs and provide a solid foundation to probe structure-property relationships in pectic polysaccharides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗