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High-Capacity Enzymatic Degradation of Postconsumer Poly(ethylene terephthalate): Modeling and Experimental Investigations

Enzymatic degradation is considered as one of the key steps for biorecycling of polyethylene terephthalate (PET), a widely used plastic. Recently, we have developed an optimized leaf-branch compost cutinase PelB-LCC ICCG and demonstrated ∼80% degradation of 200 g L −1 recycled PET (RPET) within two days in bioreactors. In this study, continued research efforts were made to achieve a complete degradation of up to 300 g L −1 RPET in bioreactors. First, low-capacity reaction conditions with ≤5 g L −1 PET were examined to identify the key variables for PET degradation with PelB-LCC ICCG , including temperature, enzyme loading, and product inhibition. To better understand and further optimize the enzymatic degradation process, a mechanism-based model was established to describe the kinetics of PET degradation and formation of the main product terephthalic acid (TPA) and byproducts MHET and BHET in high-capacity bioreactors. Model simulation suggested that a minimal enzyme loading of ∼1.4 mg PelB-LCC ICCG g −1 RPET is required to achieve a nearly complete degradation of RPET within 48 h, which was used to guide more high-capacity experiments with 100−300 g L −1 RPET in fully controlled 1 L bioreactors. A higher temperature (≥65 °C) was found not only to enable rapid degradation in the beginning but also to induce a gradual increase in RPET’s crystallinity and significantly slow down the degradation after 48 h. A high loading of RPET solids and the accumulation of the produced insoluble TPA pose a big challenge on mixing and mass transfer in the stirred bioreactor, which can be addressed by increasing the stirring speed. The results pave the way toward biorecycling of PET at a large scale.

enzymatic degradation

Exploring Natural and Social Drivers of Forest Degradation in Post-Soviet Georgia

The Caucasus Mountains harbor high concentrations of endemic species and provide an abundance of ecosystem services yet are significantly understudied compared to other ecosystems in Eurasia. In the country of Georgia, at the heart of the Caucasus region, forest degradation has been the largest land change process over the last thirty years. The prevailing narrative is that legal and illegal cutting of trees for fuelwood is primarily responsible for this process. Yet, since independence from the Soviet Union in 1991, the country has undergone rapid socioeconomic and institutional changes which have not been explored as drivers of forest change. We combine newly available land-cover change estimates, Georgian statistical data, and historical institutional change data to examine socioeconomic drivers of forest degradation. Our analysis controls for concurrent changes in climate that would affect degradation and examines variation at the regional (state) level from 2011 to 2019, as well as at the national level from 1987 to 2019. We find that higher winter temperature and drought are associated with higher degradation at the regional scale, while major institutional changes and drought are associated with higher forest degradation at the national level. Access to natural gas, the major energy alternative to fuelwood, had no significant association with degradation. Our results challenge the narrative that poverty and a lack of alternative energy infrastructure drive forest degradation and suggest that government policies banning household fuelwood cutting, including the new Forest Code of 2020, may not reduce forest degradation. Given these results, improved data on wood harvesting and more research on the commercial drivers of degradation and their links to economic and political reforms is needed to better inform forest policy in the region, especially given ongoing risks from climate change.

Institutions

On-line Inductively Coupled Plasma Mass Spectrometry Reveals Material Degradation Dynamics of Au and Cu Catalysts during Electrochemical CO 2 Reduction

A significant challenge in commercializing electrochemical CO 2 reduction (CO 2 R) is achieving catalyst durability. Here, in this study, online inductively coupled mass spectrometry (ICP–MS) was used to investigate catalyst degradation via nanoparticle detachment and/or dissolution into metal ions under CO 2 R operating conditions in 0.1 M KHCO 3 . We developed an experimental framework with ex situ characterization to validate the online ICP–MS method for in situ evaluation of degradation from metal foils. By varying the applied potential and microenvironment (CO 2 vs N 2 -saturated electrolyte), we gained insights into the degradation of Au and Cu foils under CO 2 R and hydrogen evolution reaction (HER) conditions. While both Au and Cu foils were observed to be stable to dissolution in these regimes, degradation via nanoparticle detachment from the foil surface at the femtogram scale was observed as a function of reaction conditions, providing new insights into material degradation mechanisms. When applying potential steps at −0.1 and −1.0 V vs the reversible hydrogen electrode (RHE), Au was found to degrade via nanoparticle detachment under CO 2 R operating conditions more than under HER conditions, while Cu was found to degrade via nanoparticle detachment in similar amounts during both reactions. Au lost ∼1.8× more mass and ∼7.5× more nanoparticles than Cu under CO 2 R operating conditions. This study demonstrates the use of online ICP–MS to gain insight into the degradation of Au and Cu, the importance of studying unconventional degradation mechanisms such as nanoparticle detachment, and that online ICP–MS can be further utilized to gain fundamental understanding of catalyst durability for a variety of reaction systems.

Yan, Katherine [Stanford Univ., CA (United States)

Sulfoquinovose is exclusively metabolized by the gut microbiota and degraded differently in mice and humans

Abstract Background Sulfoquinovose (SQ) is a green-diet-derived sulfonated glucose and a selective substrate for a limited number of human gut bacteria. Complete anaerobic SQ degradation via interspecies metabolite transfer to sulfonate-respiring bacteria produces hydrogen sulfide, which has dose- and context-dependent health effects. Here, we studied potential SQ degradation by the mammalian host and the impact of SQ supplementation on human and murine gut microbiota diversity and metabolism. Results 13 CO 2 breath tests with germ-free C57BL/6 mice gavaged with 13 C-SQ were negative. Also, SQ was not degraded by human intestinal cells in vitro, indicating that SQ is not directly metabolized by mice and humans. Addition of increasing SQ concentrations to human fecal microcosms revealed dose-dependent responses of the microbiota and corroborated the relevance ofAgathobacter rectalisandBilophila wadsworthiain cooperative degradation of SQ to hydrogen sulfide via interspecies transfer of 2,3-dihydroxy-1-propanesulfonate (DHPS). Similar to the human gut microbiome, the genetic capacity for SQ or DHPS degradation is sparsely distributed among bacterial species in the gut of conventional laboratory mice.Escherichia coliandEnterocloster clostridioformiswere identified as primary SQ degraders in the mouse gut. SQ and DHPS supplementation experiments with conventional laboratory mice and their intestinal contents showed that SQ was incompletely catabolized to DHPS. Although someE. clostridioformisgenomes encode an extended sulfoglycolytic pathway for both SQ and DHPS fermentation, SQ was only degraded to DHPS by a mouse-derivedE. clostridioformisstrain. Conclusions Our findings suggest that SQ is solely a nutrient for the gut microbiota and not for mice and humans, emphasizing its potential as a prebiotic. SQ degradation by the microbiota of conventional laboratory mice differs from the human gut microbiota by absence of DHPS degradation activity. Hence, the microbiota of conventional laboratory mice does not fully represent the SQ metabolism in humans, indicating the need for alternative model systems to assess the impact of SQ on human health. This study advances our understanding of how individual dietary compounds shape the microbial community structure and metabolism in the gut and thereby potentially influence host health.

Microbiology

2025 Status Report - Fiberboard Properties and Degradation Rates for Storage of 9975 Shipping Package in KAC

Fiberboard assemblies in the 9975 package were identified as susceptible to aging and degradation under long-term storage conditions. Thermal, mechanical, and physical properties have been measured on fiberboard samples aging for up to 20 years at accelerated conditions. The aging environments include elevated temperature up to 250 ºF (the maximum allowed service temperature for fiberboard in 9975 packages) and elevated humidity. Accelerated aging results have been analyzed and used to build aging models. Correlations relating several properties (thermal conductivity, energy absorption, weight, dimensions, and density) to their rate of change in potential storage environments have been developed. Combined with an estimate of the actual conditions the fiberboard experiences in K-Area Complex (KAC), these models allow development of service life predictions. KAC completed calculations that supported extending the service life of 9975 packages with 3013 containers in storage from 20 years to 40 years. These calculations addressed the potential for degraded fiberboard properties following 40 years in storage using degradation models. The 40 year storage evaluations assumed the degradation rates from initial values for density, dimensional, and thermal properties were 0.5% per year (i.e., after 40 years, the density, dimensional, and thermal properties of fiberboard were 80% of its initial values). The updated degradation models developed in this report were compared to the assumptions in those calculations, and the current results for fiberboard dimensions, density, axial and radial thermal conductivities, and energy absorption remain consistent with those calculations. Additional data will continue to be collected to permit future refinements to the models and assumptions. Some of the predicted degradation rates presented in this report are purposely high to accelerate aging. These rates relate to environments that do not exist within KAC or are postulated to only occur as upset conditions that are unlikely to persist for an extended period. For a typical package stored in KAC with approximately 10-12 watts internal heat load or less, and ambient temperatures below 90 ºF, the fiberboard assemblies experience storage conditions less severe than any of the aging environments (i.e., under 125 °F) used in this study. Fiberboard in conforming packages with lower internal heat loads should experience little or no degradation and is expected to provide a service life beyond the currently approved 40 year storage period. Packages with higher internal heat loads may not continue to perform their required safety functions beyond 40 years. Ultimately, service life will be determined by the cumulative effect of degradation from all the conditions these packages might encounter. The results and model predictions presented in this report are applicable to 9975 packages with cane or softwood fiberboard overpack assemblies. These degradation models do not address the effects of nonconforming conditions such as the presence of excess moisture and mold or beetle infestations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W

Measuring the Stress Factors for Photovoltaic (PV) Backsheet Degradation

Back sheet failure has resulted in power loss and large-scale recall of photovoltaic modules, resulting in billions of dollars in lost revenue. The light exposure on the backside of a photovoltaic module comes primarily from reflected light which alters the distribution of natural sunlight. Because of this, modelling the backside exposure and duplicating the exposure is much more difficult than modeling the frontside exposure. This project aims to study how various back sheets and junction box materials degrade under different conditions and to develop Python code to help model and predict degradation. The stress factors for back-sheet degradation must be quantified to extrapolate accelerated stress tests to the field. Test samples were placed in the A3, A4, and A5 conditions, as defined in IEC 62788-7-2, to assess the temperature and humidity dependence of ultraviolet (UV) induced degradation. We are utilizing a custom chamber with exposure from 0.5 UV-suns to 5 UV-suns to understand the dependence of degradation on light intensity. A group of samples put in the A3 condition had glass filters with 50% UV cut-offs of 320 nm, 335 nm, and 360 nm to assess the wavelength dependence of UV degradation. All this data is necessary to assess the impact of non-standard UV light exposure. The material evaluation tests include gloss measurements, attenuated total internal reflectance Fourier transform infrared spectroscopy (ATR-FTIR), UV-visible reflectance/transmittance utilizing a Cary Ci7000 spectrophotometer, and a nano-indenter for surface hardness and modulus measurements. Alongside the experimental work, there is a computational effort using raytracing and Python open-source tools in PVDeg , PVLib, and Bifacial_Radiance. This code will create specific exposure scenarios and enable the evaluation of chamber degradation relative to field degradation. Equation 1 is a strawman equation used to model degradation on the backside of a PV module. We will create simplified code, based on the results of ray-tracing calculations, which uses a view factor approach to provide fast calculations for the most common exposure scenarios.

14 SOLAR ENERGY

Antimisting kerosene: Low temperature degradation and blending

The inline filtration characteristics of freshly blended and degraded antimisting fuels (AMK) at low temperature are examined. A needle valve degrader was modified to include partial recirculation of degraded fuel and heat addition in the bypass loop. A pressure drop across the needle valve of up to 4,000 psi was used. The pressure drop across a 325 mesh filter screen placed inline with the degrader and directly downstream of the needle valve was measured as a function of time for different values of pressure drop across the needle valve. A volume flux of 1 gpm/sq in was employed based on the frontal area of the screen. It was found that, at ambient temperatures, freshly blended AMK fuel could be degraded using a single pass degradation at 4,000 psi pressure drop across the needle valve to give acceptable filterability performance. At fuel temperatures below -20 C, degradation becomes increasingly difficult and a single pass technique results in unacceptable filtration performance. Recirculation of a fraction of the degraded fuel and heat addition in the bypass loop improved low temperature degradation performance. The problem is addressed of blending the AMK additive with Jet A at various base fuel temperatures.

Yavrouian, A.

Characterization of atrial natriuretic peptide degradation by cell-surface peptidase activity on endothelial cells

Atrial natriuretic peptide (ANP) is a fluid-regulating peptide hormone that promotes vasorelaxation, natriuresis, and diuresis. The mechanisms for the release of ANP and for its clearance from the circulation play important roles in modulating its biological effects. Recently, we have reported that the cell surface of an endothelial cell line, CPA47, could degrade 125I-ANP in the presence of EDTA. In this study, we have characterized this degradation of 125I-ANP. The kinetics of ANP degradation by the surface of CPA47 cells were first order, with a Km of 320 +/- 60 nM and Vmax of 35 +/- 14 pmol of ANP degraded/10 min/10(5) cells at pH 7.4. ANP is degraded by the surface of CPA47 cells over a broad pH range from 7.0-8.5. Potato carboxypeptidase inhibitor and bestatin inhibited 125I-ANP degradation, suggesting that this degradative activity on the surface of CPA47 cells has exopeptidase characteristics. The selectivity of CPA47 cell-surface degradation of ANP was demonstrated when 125I-ANP degradation was inhibited in the presence of neuropeptide Y and angiotensin I and II but not bradykinin, bombesin, endothelin-1, or substance P. The C-terminal amino acids phe26 and tyr28 were deduced to be important for ANP interaction with the cell-surface peptidase(s) based on comparison of the IC50 of various ANP analogues and other natriuretic peptides for the inhibition of ANP degradation. These data suggest that a newly characterized divalent cation-independent exopeptidase(s) that selectively recognizes ANP and some other vasoactive peptides exists on the surface of endothelial cells.

NASA Discipline Regulatory Physiology

MODIS Solar Diffuser Degradation Determination and Its Spectral Dependency

This study presents a modeling approach to improve solar diffuser (SD) degradation determination from SD stability monitor (SDSM) measurements. The MODIS instrument uses a SDto calibrate its reflective solar bands (RSBs) on-orbit. Due to the imperfectly designed SDSM sun view screen, the SD reflectance tracked by SDSM has large noise. The SDSM measurements noise is spectrally coherent and can be minimized by normalizing measurements to the least degradeddetector 9 (936 nm). In this study, a SD degradation model is used to determine the SDdegradation's wavelength dependency and the detector 9 degradation is estimated by the model solution.The results show the SD degradations measured at 6 SDSM detectors (554 _ 936 nm) have stable relationships, where the degradation is inversely proportion to 1/wavelength^4. The model estimated SD degradation at SDSM detector 9 wavelength (936 nm) is ~0.9% from 2002 to 2018.Based on the SD degradation model solution, the SD degradation at short/mid wave bands are estimated to improve short/mid wave bands calibration. The model can also be used to improve interpolating SD degradation at SDSM detectors to RSB wavelengths. Compared to linear interpolation, bands 9 and 10 show the largest differences of up to 0.3 and 0.4% respectively. These differences directly impact the calibration coefficients of these bands.

radiometric calibration

S-NPP VIIRS Solar Diffuser Degradation at the View Direction of the Rotating Telescope Assembly

S-NPP VIIRS has been on-orbit for more than nine years since it was launched on October28th,2011. The VIIRS reflective solar bands (RSBs) are calibrated on-orbit primarily by an onboard solar diffuser (SD). The SD on-orbit degradation is tracked by an onboard SD stability monitor(SDSM). The VIIRS RSBs view the SD through a rotating telescope assembly (RTA). The RTA views the SD from a direction that is quite different from that of the SDSM. It has been shown that the SD degrades non-uniformly with respect to the incident and outgoing directions, especially at the short wavelengths. Thus, the SDSM calibration cannot provide an accurate SD degradation estimation for the view direction of the RTA, resulting in long-term drifts in the calibration coefficients derived from the SD and SDSM calibration. S-NPP VIIRS has been scheduled to view the Moon approximately monthly since its launch. The lunar observations can provide accurate long-term trends for the RSB calibration coefficients since the lunar surface reflectance is quite stable. By comparing the SD and lunar calibration results, we can obtain the SD degradation differences at the view directions of the SDSM and RTA and derive the SD degradation at the view direction of the RTA. Moreover, we can also derive the SD degradation in the short-wave infrared (SWIR) spectral range, wherein the SDSM cannot track the SD degradation. In this paper, we will derive the SD degradation for the view direction of the RTA from the SD, SDSM, and lunar calibrations from the visible to SWIR spectral range. We will also simulate the SD degradation with analytical models and compare their performances.

SNPP VIIRS

Biogeochemical Controls on Wood Degradation as a Source of Bioavailable Carbon in Denitrifying Bioreactors

Woodchip bioreactors (WBRs) are important tools for the removal of nitrate in agricultural drainage, but their effectiveness is often limited by the slow degradation of lignocellulosic wood residues into bioavailable forms of carbon that fuel denitrifying microorganisms. Here, we examine biogeochemical factors regulating wood degradation in saturated woodchip beds, with a focus on the effects of dissolved oxygen (DO), iron (Fe), and manganese (Mn) in generating oxidative activity that can enhance wood decomposition. Woodchips from a 10-year-old WBR were characterized with bulk techniques and a novel combination of μX-ray scattering, μXRF, and μXANES to visualize the depletion of crystalline cellulose as a proxy for wood degradation. Woodchips from upstream portions of the reactor exhibited the greatest degradation, probably due to greater DO exposure, and degradation was localized to a 100 to 200 μm thick surface layer that was also associated with higher concentrations of Fe and Mn. Greater degradation was associated with faster nitrate removal. μXANES analysis of Fe and Mn in the surface layer indicated the presence of a microenvironment in which oxygenation reactions of Fe(II) and Mn(II) could contribute to the formation of reactive oxidants involved in the degradation of lignocellulose. In conclusion, our results provide new insight into biogeochemical properties that influence wood decomposition in WBRs at both micro- and macroscales and how these wood degradation processes are coupled with denitrification.

36 MATERIALS SCIENCE

Multiscale Characterization of Electrode-Induced Degradation in Perovskite Solar Cells

The stability of metal-halide-perovskite (MHP) solar cells must be understood and improved for the commercial viability of MHP technologies. Here, we apply multiscale characterization methods to study degradation modes, specifically electrode corrosion, for p-i-n MHP partial device stacks and full devices that are stored in the dark under an inert atmosphere. Our multiscale characterization approaches include full-device electro-optical performance using current-voltage (JV) curves and spatial imaging with electroluminescence (EL) and photoluminescence (PL). We further correlate interface properties using cross-sectional Kelvin probe force microscopy, which maps the nanoscale electric field properties, and electron microscopy, which demonstrates structural and chemical features. Devices stored as a full device stack degrade primarily by metal (Ag) electrode diffusion into the absorber, with formation of AgI byproducts and Ag accumulation near the indium tin oxide (ITO) contact. This causes decomposition of the perovskite absorber domains, loss of the potential drop at the electron transport layer (ETL)/perovskite interface near the metal contact, and increased equivalent resistance at the perovskite/hole transport layer (HTL) interface near the ITO contact. The devices stored without metal show a different degradation pathway dominated by corrosion of the ITO, creating voids at the ITO electrode surface with diffusion of In and Sn into the absorber. We conclude that metal electrode-induced degradation is the most severe degradation pathway under dark storage, but that ITO corrosion and absorber instability must also be mitigated. We further demonstrate mitigation of these degradation pathways by changes to the device stack, including a SnO x blocking layer at the ETL side and replacing ITO with FTO at the HTL side. These results provide a useful demonstration of specific dark degradation pathways at each electrode interface, as well as a unique multiscale example that links degradation of chemical, structural, and electrical interface properties to the full-device electro-optical characteristics.

14 SOLAR ENERGY

Degradation and deforestation increase the sensitivity of the Amazon Forest to climate extremes

About 40% of the Brazilian Amazon has been deforested or suffered changes in forest structure through degradation (selective logging, fires, and fragmentation). The impact of forest degradation on the forest’s sensitivity to climate extremes has not been fully explored because of a lack of data and the complex interplay of forest structure and climate drivers. Here, we combined forest structure data from 545 airborne lidar transects (375 ha each) across the Brazilian Amazon with the Ecosystem Demography Model (ED2). We explore the forest’s functional response to near-present (1981–2019) climate extremes under observed forest structure from lidar ( Control ) and two forest structure change scenarios: (1) forest recovery by excluding all future deforestation and degradation ( Recovery ) and (2) expansion of selective logging and deforestation ( Degradation ). Using the Control simulation, we found a close and positive association between local forest aboveground biomass and the predicted gross primary productivity (GPP) and evapotranspiration (ET). Moreover, both GPP and ET respond negatively to extremes in vapor pressure deficit and downwelling shortwave irradiance in degraded forests in Eastern and Southern Amazon, indicating high sensitivity to droughts. Locally high-biomass forest patches showed little or no negative response of GPP and ET to extreme drought conditions whereas low-biomass forest patches in the same locations—typically degraded forest canopies—responded negatively to higher moisture stress. The results from the Recovery scenario showed similar results to simulations with observed structure; however, under the Degradation scenario, low-biomass forest patches became more abundant, resulting in more regions where GPP and ET are negatively impacted by hot drought conditions according to the ED2 model. Our results suggest that local forest structure is a critical determinant of an ecosystem’s response to climate variability, and that the loss of canopy trees in the Amazon through forest degradation could increase and expand forest vulnerability to droughts.

54 ENVIRONMENTAL SCIENCES

Investigating the Crosslinking, Degradation, and Adhesion Behavior of Photovoltaic Encapsulants Under Thermal Accelerated Aging

Degradation of photovoltaic (PV) module encapsulant characteristics that lead to mechanical embrittlement and delamination remains a cause of failure in solar installations. A multiscale reliability model connecting the encapsulant mechanical and fracture properties to the degraded molecular structure and interfacial bonding to adjacent solar cell and glass substrates was previously published. The model, developed primarily for poly(ethylene-co-vinyl acetate) acetate (EVA) encapsulants, remains to be experimentally validated. Determining the degradation and crosslinking kinetics of alternative encapsulants, such as polyolefin elastomer (POE) and EVA/POE/EVA composites (EPE), can generalize the model. In this work, we subject fully cured EVA, POE, and EPE encapsulants to accelerated thermal aging to determine how high temperatures impact reaction kinetics. An increase in gel content (crosslinking) and decrease in crystallinity of the encapsulants under hot-aerobic (90 degrees C, 22% RH) and hot-anaerobic (90 degrees C, sealed in N 2 air) aging were observed, even in the absence of UV and crosslinking initiators. Fourier transform infrared spectroscopy (FTIR)-attenuated total reflectance analysis showed insignificant encapsulant degradation, demonstrating the critical role of UV and moisture in accelerating degradation. Adhesion testing performed on coupon-level specimens (cell/encapsulant/glass laminates) showed decreases in adhesion energy, Gc , from 5000 h of hot-dry (90 degrees C, ~1% RH) and hot-humid (90 degrees C, 60% RH) aging. POE coupons demonstrated the best stability, followed by EPE then EVA. For EVA and POE, hot-humid aged coupons experienced a larger decrease in Gc due to enhanced hydrolytic degradation. Hot-dry aging condition demonstrated that thermal degradation of the interface could be significant even if the encapsulant experiences negligible degradation in the absence of UV and elevated humidity.

accelerated aging

Bisphenol A degradation by manganese oxides at circumneutral pH: Quantitative evaluation of dissolved Mn(III) species with pyrophosphate

Although trivalent manganese (Mn(III)) species have been recognized as crucial intermediates in the degradation of organic contaminants by Mn oxides, quantitative research on their specific roles remains scarce. Here, our study investigated the degradation processes of an organic pollutant, Bisphenol A (BPA), by dissolved Mn(III) and Mn(III)-bearing oxides, and elucidated the differences of the underlying mechanisms and reaction pathways between several Mn oxides and dissolved Mn(III). Our results indicated that BPA degradation rates with Mn(III)-bearing oxides alone follow the order: δ-MnO 2 >> γ-MnOOH > Mn 3 O 4 . Adding pyrophosphate (PP) significantly enhanced BPA degradation by promoting the formation of Mn(III)-PP complexes and exposing more reactive sites, achieved through destabilizing the crystal structure and mitigating of Mn(II) readsorption, particularly in γ-MnOOH and Mn 3 O 4 . Our kinetic model revealed that heterogeneous degradation by Mn oxides is the predominant reaction pathway, accounting for 61.4 %, 87.8 %, and 73.8 % of the total degraded BPA for δ-MnO 2 , γ-MnOOH, and Mn 3 O 4 , respectively, even in the presence of significant amount of dissolved Mn(III) intermediates due to high PP concentrations. These results offer mechanistic details on BPA degradation by Mn oxides and the influence of ligand concentration, providing helpful insights for optimizing degradation strategies of organic pollutants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Mechanistic insights into a heterobifunctional degrader-induced PTPN2/N1 complex

PTPN2 (protein tyrosine phosphatase non-receptor type 2, or TC-PTP) and PTPN1 are attractive immuno-oncology targets, with the deletion of Ptpn1 and Ptpn2 improving response to immunotherapy in disease models. Targeted protein degradation has emerged as a promising approach to drug challenging targets including phosphatases. We developed potent PTPN2/N1 dual heterobifunctional degraders (Cmpd-1 and Cmpd-2) which facilitate efficient complex assembly with E3 ubiquitin ligase CRL4 CRBN , and mediate potent PTPN2/N1 degradation in cells and mice. To provide mechanistic insights into the cooperative complex formation introduced by degraders, we employed a combination of structural approaches. Our crystal structure reveals how PTPN2 is recognized by the tri-substituted thiophene moiety of the degrader. We further determined a high-resolution structure of DDB1-CRBN/Cmpd-1/PTPN2 using single-particle cryo-electron microscopy (cryo-EM). This structure reveals that the degrader induces proximity between CRBN and PTPN2, albeit the large conformational heterogeneity of this ternary complex. The molecular dynamic (MD)-simulations constructed based on the cryo-EM structure exhibited a large rigid body movement of PTPN2 and illustrated the dynamic interactions between PTPN2 and CRBN. Together, our study demonstrates the development of PTPN2/N1 heterobifunctional degraders with potential applications in cancer immunotherapy. Furthermore, the developed structural workflow could help to understand the dynamic nature of degrader-induced cooperative ternary complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Impacts of the Angular Dependence of the Solar Diffuser BRDF Degradation Factor on the SNPP VIIRS Reflective Solar Band On-Orbit Radiometric Calibration

Using an onboard sunlit solar diffuser (SD) as the primary radiance source, the visible infrared imaging radiometer suite (VIIRS) on the Suomi National Polar-orbiting Partnership satellite regularly performs radiometric calibration of its reflective solar bands (RSBs). The SD bidirectional reflectance distribution function (BRDF) value decreases over time. A numerical degradation factor is used to quantify the degradation and is determined by an onboard SD stability monitor (SDSM), which observes the sun and the sunlit SD at almost the same time. We had shown previously that the BRDF degradation factor was angle-dependent. Consequently, due to that the SDSM and the RSB view the SD at very different angles relative to both the solar and the SD surface normal vectors, directly applying the BRDF degradation factor determined by the SDSM to the VIIRS RSB calibration can result in large systematic errors. We develop a phenomenological model to calculate the BRDF degradation factor for the RSB SD view from the degradation factor for the SDSM SD view. Using the yearly undulations observed in the VIIRS detector gains for the M1-M4 bands calculated with the SD BRDF degradation factor for the SDSM SD view and the difference between the VIIRS detector gains calculated from the SD and the lunar observations, we obtain the model parameter values and thus establish the relation between the BRDF degradation factors for the RSB and the SDSM SD view directions.

Lei, Ning

Towards Designing Graceful Degradation into Trajectory Based Operations: A Human-Systems Integration Approach

One of the most fundamental changes to the air traffic management system in NextGen is the concept of trajectory based operations (TBO). With the introduction of such change, system safety and resilience is a critical concern, in particular, the ability of systems to gracefully degrade. In order to design graceful degradation into a TBO envrionment, knowledge of the potential causes of degradation, and appropriate solutions, is required. In addition, previous research has predominantly explored the technological contribution to graceful degradation, frequently neglecting to consider the role of the human operator, specifically, air traffic controllers (ATCOs). This is out of step with real-world operations, and potentially limits an ecologically valid understanding of achieving graceful degradation in an air traffic control (ATC) environment. The following literature review aims to identify and summarize the literature to date on the potential causes of degradation in ATC and the solutions that may be applied within a TBO context, with a specific focus on the contribution of the air traffic controller. A framework of graceful degradation, developed from the literature, is presented. It is argued that in order to achieve graceful degradation within TBO, a human-system integration approach must be applied.

human-system integration