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DOE OSTI2021

Iron speciation in blast furnace slag cements

Slag-containing pastes and concretes were analysed by element-specific synchrotron-based techniques to determine the speciation of iron on crushed materials through spatially resolved micro-spectroscopic studies. The investigated cement samples were hydrated either in the laboratory, or exposed to river or sea water. Metallic iron, along with minor proportions of iron sulphide and magnetite was detected in the laboratory sample. Iron sulphide, goethite, and siliceous hydrogarnet were discovered in the blended slag cements hydrated in contact with river water for up to 7 years. In contrast, no Fe(0) was observed in blended concretes exposed to sea water. Instead, iron sulphide, iron(II)-hydroxide and -oxide, hematite, magnetite, siliceous hydrogarnet, and goethite were detected as well as ilmenite (FeTiO{sub 3}) in the aggregates. The strong acceleration of Fe oxidation in samples exposed to sea water and the long-term passivation observed in the other samples indicate comparable processes as those occurring on steel bars.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Clinkerless ultra-high strength concrete based on alkali-activated slag at high temperatures

This work investigates the degradation mechanisms of clinkerless alkali-activated slag based ultra-high strength concrete (AAS-UHSC) upon exposure to high temperatures up to 800 °C. The heat-induced mechanical, mineralogical, molecular, microstructural, and pore structure alterations of AAS-UHSC prepared with various activator types, water-to-powder ratios, and fiber incorporation are studied. The results demonstrate the beneficial roles of potassium incorporation on improving the thermal stability and integrity of AAS-UHSC, via suppressing deleterious crystallization and transformation of aluminosilicate phases at high temperature. In contrast to Portland cement clinker-based UHSC, no sign of explosive spalling is observed in AAS-UHSC, likely due to the presence of microcracks that enhance the pore network connectivity. The mechanical degradation of AAS-UHSC at high temperature below 600 °C is resulted from dehydration and decomposition of phases and consecutive thermal cracking, together with enlarged porosity and coarsened pore structure. As the temperature rising to 800 °C, crystallization and transformation of phases, as well as formation of porous microstructure, considerably aggravate the mechanical degradation of AAS-UHSC. In contrast to the thermal damage mitigation by polymeric fibers in conventional UHSC, the fiber incorporation has little positive impact on the thermal resistance of AAS-UHSC.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Physics-Informed Machine Learning Models for Predicting the Progress of Reactive-Mixing

This paper presents a physics-informed machine learning (ML) framework to construct reduced-order models (ROMs) for reactive-transport quantities of interest (QoIs) based on high-fidelity numerical simu-lations. QoIs include species decay, product yield, and degree of mixing. The ROMs for QoIs are applied to quantify and understand how the chemical species evolve over time. First, high-resolution datasets for constructing ROMs are generated by solving anisotropic reaction-di?usion equations using a non-negative finite element formulation for di?erent input parameters. The reactive-mixing model input parameters are: time-scale associated with flipping of velocity, spatial-scale controlling small/large vortex structures of velocity, perturbation parameter of the vortex-based velocity, anisotropic dispersion strength/contrast, and molecular diffusion. Second, random forests, F-test, and mutual information criterion are used to evaluate the importance of model inputs/features with respect to QoIs. We observed that anisotropic dispersion strength/contrast is the most important feature and time-scale associated with flipping of velocity is the least important feature. Third, Support Vector Machines (SVM) and Support Vector Regression (SVR) are used to construct ROMs based on the model inputs. The constructed SVR-ROMs are then used to predict scaling of QoIs. We also present estimates and inequalities on the QoIs, which inform that the species decay, mix, and produce in an exponential fashion. These inequalities also inform that a radial basis function is the most suitable kernel for the SVM/SVR models for QoIs. It is observed that R2-score for SVR-ROMs on unseen data is greater than 0.9, implying that the SVR-ROMs are able to predict the reaction-diffusion system state reasonably well. Finally, in terms of the computational cost, the proposed SVM-ROMs are O(107) times faster than running a high-fidelity finite element simulation for evaluating QoIs. This makes the proposed ML-based ROMs attractive for reactive-transport sensing and real-time monitoring applications as they are significantly faster yet reasonably accurate.

Mudunuru, Maruti K.↗

DOE OSTI2024

Effect of non-uniform void distributions on the yielding of metals

High-throughput (several thousand) calculations have been carried out to investigate the yield behavior of porous materials with randomly distributed pores, porosity levels over four orders of magnitude and up to a hundred pores per simulation box. To this end, a Galerkin based fast Fourier transform (FFT) formulation was enhanced to deal with high phase contrast materials. In addition, GPU parallelization was employed in solving the governing equation for strain fluctuations using a Krylov iterative solver. Emphasis is laid on the conditions under which percolation of plastically non-deforming zones through the porous network emerge, a regime termed unhomogeneous yielding. By way of contrast, the regime where the plastic strain fluctuations (associated with the heterogeneous void-matrix aggregate) fall below the percolation threshold is defined as homogeneous yielding. Here, we find that nonuniform pore distributions only affect unhomogeneous yielding and have a universal softening effect. The extent of this distribution softening is analyzed as a function of porosity, cell size and number of realizations. Whether the uncovered universal distribution softening has direct implications on failure resistance of porous materials is discussed.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

DOE OSTI2025

Turbulent burning velocity of lean premixed hydrogen/air flames at engine conditions: Effects of turbulence intensity and length scale

For turbulent lean premixed hydrogen flames with strong thermodiffusively instabilities, most previous studies have focused on the influence of turbulence intensity, whereas the role of turbulence length scale is less well understood. Here, this study addresses this gap by conducting direct numerical simulations (DNS) of statistically planar turbulent premixed flames for a lean (ϕ=0.35) hydrogen/air mixture under independently varied turbulence intensity (u') and length scale (l T ) at engine-relevant thermodynamics conditions. Results show that as u' increases, the flame front becomes increasingly wrinkled, forming smaller cellular structures. In contrast, l T variations do not significantly alter the size of these structures. For the turbulent burning velocity (S T ), the normalized S T (i.e., S T /S L , where S L is the laminar flame speed) increases linearly with u', driven by both enhanced flame surface wrinkling (i.e., increased A T /A L ) and enhanced local burning rate (i.e., increased I 0 ). However, increasing l T reduces I 0 , despite a continued increase in A T /A L , resulting in only a marginal increase in S T /S L . To reveal the underlying mechanisms, especially the decreasing trend of I 0 with l T , local flame dynamics analyses are performed. It is found that as l T increases, the interaction between thermodiffusive effects and turbulence weakens due to the reduced tangential strain rate, while the flame curvature remains largely unchanged. This suppresses local reactivity enhancement and thus decreases I 0 , In contrast, an increase in u' enhances the interaction by amplifying both curvature fluctuation and tangential strain rate, leading to increased local reactivity (increased I 0 ). Finally, based on the DNS data, several new scaling models are proposed for the three global properties, S T /S L , A T /A L , and I 0 , and showed improvements compared to existing models. These findings provide new insights into the flame-turbulence interactions in thermodiffusively unstable hydrogen flames. The DNS dataset is also useful for the development of turbulent combustion models applicable to practical engine simulations.

Engine-relevant condition↗

DOE OSTI2020

The effect of lighting environment on task performance in buildings – A review

The effects of indoor environmental conditions on human health, satisfaction, and performance have been the focal point of research for decades. This paper reviews and summarizes the impact of lighting environment on task performance, specifically for the built environment audience. Existing studies included a variety of performance tests on cognitive performance and perception, visual acuity and reaction, memory, reasoning, and labor productivity. Illuminance, luminance ratio and correlated color temperature were found to affect performance in different ways, reflecting the impact of experimental techniques, conditions, performance evaluation methods used and data analysis methods. These were reviewed and categorized, with discussion on limitations related to sample size, modeling approach, carryover effects and other factors affecting individual differences in performance, with recommendations for future improvement. Although no universal conclusions can be made, in general, task performance seems to improve with higher illuminances, contrast ratios in the range of 7–11:1 (while always making sure that glare will not occur in the space) and higher correlated color temperature, while spectral tuning in the red or blue wavelengths has also shown positive effects. To obtain more generic evidence, future studies should be more consistent in terms of experimental procedures and overall light conditions, and also consider the effects of vertical illuminance, daylight provision/control, and outside views on task performance. Finally, studying performance with multi-factorial designs in a human-centered optimized manner (such as deploying variable lighting scenarios optimized for various tasks) can lead to deeper understanding of lighting effects on task performance, and ultimately to improved lighting design and operation in buildings overall.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2022

Field validation of data-driven BSDF and peak extraction models for light-scattering fabric shades

Shading and daylighting systems affect cooling, heating, and lighting energy use by modulating solar radiation through the building façade. Characterizing shading systems holistically and accurately helps designers and engineers evaluate shading systems to achieve energy and non-energy performance goals. These complex fenestration systems can be modeled using Bidirectional Scattering Distribution Functions (BSDF), which map incident radiation to hemispherical distributions of outgoing radiation. Data-driven, tabulated BSDFs are derived from interpolated goniophotometer measured data, then sampled during the raytracing calculation. A peak extraction (PE) algorithm was developed to circumvent limits in BSDF angular resolution, where the specular peak is extracted during simulation by evaluating the BSDF in the through direction and surrounding region. The objective of this study was to validate this measurement and modeling workflow using field monitored data from a full scale testbed with eleven installed fabrics of different weaves, openness factors, and colors and assess the accuracy of the workflow under different adaptation and contrast conditions. Test conditions were limited to clear sky conditions with the sun in the field of view. Results showed that, for tensor tree datasets, vertical illuminance, solar luminance (2.5° apex), and daylight glare probability (DGP) were predicted to within a mean bias error (MBE) error of -456 lx (-12.3%), -3.46e5 (-38.4%), and -0.042 (-7.8%) when full PE occurred. With a binary classification of glare/ no glare, DGP was predicted accurately with a true positive rate of 0.98 and true negative rate of 1.0 using tensor tree data and less accurately with Klems BSDF data, particularly for cases of no glare. The workflow may be of insufficient accuracy to distinguish borderline performance between fabrics using the four-point glare scale, particularly under low adaptation, high contrast daylit conditions. Errors were due to reductions in peak shape and intensity across the BSDF interpolation and data reduction workflow. Future work is needed to better preserve measurement fidelity during interpolation and sampling, which in turn will improve PE performance.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2024

Unique impacts of strong and westward-extended western Pacific subtropical high on ozone pollution over eastern China

As a subtropical anticyclonic high-pressure system that typically forms over the northwestern Pacific Ocean in summer, the Western Pacific subtropical high (WPSH) affects meteorological conditions and ozone pollution in China. The relationship between maximum daily 8-h average ozone (MDA8 O 3 ) concentrations and the extremely strong and westward-extended WPSH occurred in 2022 is investigated using observations, reanalysis data and GEOS-Chem model simulations. The intensity of WPSH has a significant positive correlation with MDA8 O3 over southern China during July-August in 2022, with a correlation coefficient of +0.44, but the correlation is negative (–0.40) in northern China. During the strong WPSH days, MDA8 O 3 increased by 16.5µgm -3 (16.4% relative to July-August average) over southern China and decreased by 19.0µgm -3 (14.5%) in northern China compared to the weak WPSH days. The unique dipole pattern in the relationship between ozone levels and the WPSH in 2022 exhibited a contrast to that during 2015–2021. The difference is primarily due to the extremely strong WPSH intensity and its unusual westward expansion in 2022. In this case, an anomalous anticyclone at 500 hPa dominates over southern China, which creates conditions conducive for ozone formation and accumulation. The anticyclone weakened horizontal winds and reduced the dispersion of ozone, alongside a high temperature and low relative humidity, which favored the chemical production of ozone. In contrast, abnormal northerly winds enhanced ozone diffusion in northern China and the low temperature reduced ozone chemical production. Here, this study reveals the mechanism for the significant impact of strong and westward-extended WPSH on ozone concentrations over China, emphasizing the role of the WPSH location in modulating meteorology and ozone levels.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Sequences of seismic and aseismic slip on bimaterial faults show dominant rupture asymmetry and potential for elevated seismic hazard

Here we perform numerical simulations of sequences of earthquake and aseismic slip on planar rate and state faults separating dissimilar material within the 2-D plane strain approximation. We resolve all stages of the earthquake cycle from aseismic slip to fast ruptures while incorporating full inertia effects during seismic event propagation. We show that bimaterial coupling results in favorable nucleation site and subsequent asymmetric rupture propagation. We demonstrate that increasing the material contrast enhances this asymmetry leading to higher slip rates and normal stress drops in the preferred rupture propagation direction. The normal stress drop, induced by the bimaterial effect, leads to strong dynamic weakening of the fault and may destabilize the creeping region on a heterogeneous rate and state fault, resulting in extended rupture propagation. Such rupture penetration into creeping patches may lead to more frequent opening of earthquake gates, causing increased seismic hazard. Furthermore, bimaterial coupling may lead to irregular seismicity pattern in terms of event length, peak slip rates, and hypocenter location, depending on the properties of the creeping patches bordering the seismogenically active part of the fault. Our results highlight robust characteristics of bimaterial interfaces that persist over long sequence of events and suggest the need for further exploration of the role of material contrast in earthquake physics and models of seismic hazard.

58 GEOSCIENCES↗

DOE OSTI2024

Vivianite oxidation is not photocatalyzed

Vivianite is a hydrous Fe2+ phosphate mineral found in anoxic environments that plays an integral role in P cycling and environmental biogeochemistry. Imbued in the vivianite literature dating as far back as 1918 is the notion that vivianite is light-sensitive and susceptible to rapid photooxidation induced entirely by solar light. However, despite an exhaustive search, to our knowledge this conventionally accepted assumption has never been directly tested, nor has the band gap ever been measured. Resolving this question of photochemical control of vivianite redox chemistry is important for performing and interpreting experiments involving vivianite reactivity with contaminants, and potentially iron and phosphate cycling in the photic zone of aquatic systems. The present study was specifically designed to add¬ress this question. Pure synthetic vivianite samples were irradiated in aqueous suspensions with a Xe lamp at conditions mimicking the solar spectrum and compared to dark controls. Particles stirred in anoxic suspensions for up to 66 days showed no detectable oxidation irrespective of light exposure, according to colorimetric Fe2+/Fe3+ assays, micro X-ray diffraction, and Raman spectroscopy. In contrast, the same experiment performed using air-equilibrated suspensions showed systematic oxidation of up to ~80% mol% Fe(II) at 66 days, but again with no detectable light exposure effect. To test for UV reactivity, further experiments on vivianite powders under air versus N2 atmosphere were performed using a Hg lamp with a longpass filter. In contrast to oxidation in air where no effect of light was detected, after 24 hrs irradiation anoxically, 0.78% Fe was oxidized compared to dark controls, and after 13 days only an additional 0.3% Fe was oxidized. The band gap of pure vivianite was measured by the Tauc method to be 3.5 eV. Contrary to previous reports, solar light has minimal impact on the oxidation of pure vivianite, insignificant in particular when compared to its relatively fast oxidation by oxygen exposure. As such, light does not need to be excluded when running typical vivianite laboratory experiments. Long-term storage of natural vivianite in museums or private collections should continue protective measures given that a possible photocatalytic role of impurities cannot yet be ruled out. Nonetheless, at all depths in natural aquatic systems it appears that the primary abiotic control on the reactivity and half-life of vivianite particles should be the dissolved oxygen concentration, not light exposure.

Vivianite, photochemistry, oxidation↗

DOE OSTI2023

Microscale spatiotemporal patterns of water, soil organic carbon, and enzymes in plant litter detritusphere

Understanding biophysical and biochemical processes in detritusphere is critical to quantifying and modeling plant residue decomposition dynamics and subsequent soil organic carbon (C) accrual. The objectives of the study were to explore (i) micro-environmental conditions within the detritusphere formed around decomposing corn and soybean leaves, and (ii) the relationships between moisture distribution, enzyme activity, and C dynamics during decomposition. We assessed spatial and temporal dynamics of moisture distribution using X-ray and neutron computed tomography, and activities of β-glucosidase and chitinase, two enzymes involved in soil C and N processing, using zymography. We used 13 C labeled residue to track residue contribution to atmospheric CO 2 and soil organic C. Moisture redistribution pattern varied depending on the residue type. While the water was immediately absorbed by the corn leaves and maintained afterward, switchgrass leaves absorbed water more slowly and created water-deficient zones within ~1mm from the residue. This initial moisture depletion led to lower chitinase activity and residue-derived CO 2 emissions in switchgrass. In contrast to chitinase, β-glucosidase activity was influenced by a combination of vegetation history and residue type, and it was higher when the origin of the residue matched the vegetation history of the soil. Pore size had an opposite impact on the studied enzymes, supporting the notion that contrasting soil pore architecture can stimulate activities of different enzymes through a selection of dominant enzyme producers. We concluded that the decomposition dynamics of plant residues is not only a simple function of residue chemistry, but rather a combined effect of the vegetation history, in part through its effect on microbial community composition, the plant residue chemical and likely physical characteristics, and the soil pore structure in the detritusphere. Together, they create temporally dynamic micro-environmental conditions influencing decomposition. Specifically, our study demonstrated that the initial micro-environment formulated in detritusphere can play an important role in enzyme activities and consequent C dynamics.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

An interlaboratory comparison of mid-infrared spectra acquisition: Instruments and procedures matter

Diffuse reflectance spectroscopy has been extensively employed to deliver timely and cost-effective predictions of a number of soil properties. However, although several soil spectral laboratories have been established worldwide, the distinct characteristics of instruments and operations still hamper further integration and interoperability across mid-infrared (MIR) soil spectral libraries. In this study, we conducted a large-scale ring trial experiment to understand the lab-to-lab variability of multiple MIR instruments. By developing a systematic evaluation of different mathematical treatments with modeling algorithms, including regular preprocessing and spectral standardization, we quantified and evaluated instruments' dissimilarity and how this impacts internal and shared model performance. We found that all instruments delivered good predictions when calibrated internally using the same instruments' characteristics and standard operating procedures by solely relying on regular spectral preprocessing that accounts for light scattering and multiplicative/additive effects, e.g., using standard normal variate (SNV). When performing model transfer from a large public library (the USDA NSSCKSSL MIR library) to secondary instruments, good performance was also achieved by regular preprocessing (e. g., SNV) if both instruments shared the same manufacturer. However, significant differences between the KSSL MIR library and contrasting ring trial instruments responses were evident and confirmed by a semi-unsupervised spectral clustering. For heavily contrasting setups, spectral standardization was necessary before transferring prediction models. Non-linear model types like Cubist and memory-based learning delivered more precise estimates because they seemed to be less sensitive to spectral variations than global partial least square regression. In summary, the results from this study can assist new laboratories in building spectroscopy capacity utilizing existing MIR spectral libraries and support the recent global efforts to make soil spectroscopy universally accessible with centralized or shared operating procedures.

58 GEOSCIENCES↗

DOE OSTI2021

Rheological investigation of effect of high temperature on geothermal drilling fluids additives and lost circulation materials

High temperatures (HT) and the corrosive environment make the design of a geothermal drilling fluid a highly complex task. The presence of HT exacerbates the problems due to thermal degradation. Geothermal aquifers usually combine high-temperature and complex chemistry, making them highly corrosive. Although geothermal drilling fluids are exposed to thermal degradation, research of the effect on mud rheological properties in temperatures near or above 149°C (300°F) is limited. In this study, a High Pressure-High Temperature (HPHT) rheology setup was used to measure drilling fluids' properties up to 204.4°C (400°F). Rheological behavior of viscosity, density, lost circulation, and alkalinity control additives were analyzed at HT. It was found experimentally that Bentonite alone is thermally stable at HT. In contrast, Caustic Soda showed a tendency to gelate at temperatures above 93.3°C (200°F), adversely affecting mud rheology. Alkalinity control materials to replace Caustic Soda were evaluated. Among them, Lime presented the best thermal stability at 204.4°C with a range of variation of 0.0024 Pa.s (2.4 cP) on apparent viscosity after three consecutive tests. Besides, it was tested 11 different lost circulation materials (LCM) for understanding their rheological behavior at HT. Further, it was found that HT has less impact on fine granular materials rheological behavior with an average increase of 17.7% compared with the baseline. In contrast, flaky, fibrous, and coarse granular materials presented a more apparent impact in WBM rheology with a deviation of 166% compared with the baseline.

15 GEOTHERMAL ENERGY↗

DOE OSTI2021

Quantitative Bioluminescence Tomography-Guided Conformal Irradiation for Preclinical Radiation Research

Widely used cone beam computed tomography (CBCT)-guided irradiators in preclinical radiation research are limited to localize soft tissue target because of low imaging contrast. Knowledge of target volume is a fundamental need for radiation therapy (RT). Without such information to guide radiation, normal tissue can be overirradiated, introducing experimental uncertainties. This led us to develop high-contrast quantitative bioluminescence tomography (QBLT) for guidance. The use of a 3-dimensional bioluminescence signal, related to cell viability, for preclinical radiation research is one step toward biology-guided RT.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

DOE OSTI2020

The effect of magnetic susceptibility and magnetic field strength on porosity estimates determined from low-field nuclear magnetic resonance

The presence of materials with high magnetic susceptibility are known to have an impact on 1H nuclear magnetic resonance (NMR) measurements and in laboratory data this often results in poor estimates of porosity from NMR data. To quantify and understand the cause of the poor NMR porosity estimations, in this laboratory study, we examine the effect of magnetic susceptibility, NMR measurement parameters, and NMR instrument design on NMR measurements. Data were collected with two instruments, each with a different Larmor frequency (2 MHz and 485 kHz), on water-saturated unconsolidated sediments with magnetic susceptibility values ranging from 3.6 × 10 -6 to 7020 × 10 -6 SI. The results show that for materials with low magnetic susceptibility (<378 × 10 -6 SI), the gravimetric porosity is accurately predicted from the NMR measurements. For the samples with high magnetic susceptibility (>987 × 10 -6 SI) the gravimetric porosity is poorly predicted from the 2 MHz NMR measurements made at all echo times (from 0.2 to 3.0 ms). In contrast, the gravimetric porosity is more accurately predicted at an echo time of 0.2 ms for measurements made using the 485 kHz instrument, although at larger echo times (>1.0 ms), the porosity estimate becomes poor. The 485 kHz NMR instrument has non-zero internal magnetic field gradients, similar to those found in borehole instruments, in contrast to the 2 MHz NMR instrument, which has a homogeneous applied magnetic field. Finally, we conclude that differences is the magnetic field strength and higher magnetic field inhomogeneities in the 485 kHz NMR instrument contribute to a reduction of the impact of inhomogeneities in the magnetic field caused by materials with high magnetic susceptibility, allowing for improved porosity estimation. These results indicate that NMR measurements collected at short echo times in low, inhomogeneous static fields, e.g., borehole instruments, may provide accurate estimates of porosity in water saturated sediments, even in the presence of magnetic minerals.

58 GEOSCIENCES↗

DOE OSTI2025

Insight Into the High-Potential Branch of the Alternate Nad+-Dependent NADPH:Ferredoxin Oxidoreductase II (NfnII) from Pyrococcus Furiosus. Evidence for the Gating Step in Electron Bifurcation

We have investigated the rapid-reaction kinetics of the NAD+-dependent NADPH:ferredoxin oxidoreductase II (NfnII) from Pyrococcus furiosus, permitting a comparison with recent work done with the paralog NfnI from the same organism. The half-potentials of the electron-bifurcating L-FAD are highly crossed in both NfnI, meaning the potential for the quinone/semiquinone couple is significantly lower than that for the semiquinone/hydroquinone couple so that the semiquinone oxidation state is thermodynamically unstable. The same appears to be the case with NfnII on the basis of its similar behavior in transient absorption spectroscopy experiments and the absence of any evidence for FAD*- accumulation in the course of reductive titrations (which would be manifested as a transient increase in absorbance at ~380 nm)1. Reductive titrations with both the one-electron donor sodium dithionite and the obligate two-electron donor NADPH demonstrate that, in contrast to NfnI, little FADH* accumulates in the high-potential pathway of NfnII in the course of reduction, as reflected in the absence of a transient increase in absorbance in the 500-600 nm region. This indicates that the half-potentials of the S-FAD are crossed in NfnII by a minimum of 120 mV. Rapid-reaction experiments mixing oxidized NfnII with NADPH also show no evidence of S-FADH* accumulation. Furthermore, the enzyme is only partially reduced at the end of the reaction with NADPH, indicating that there is little electron transfer into the high-potential pathway of NfnII. When the reaction is carried out in the presence of the one-electron carrier ferredoxin, only approximately one equivalent of ferredoxin becomes reduced, in contrast to the maximum of three equivalents seen with NfnI. This is consistent with only a single electron bifurcation event taking place under these conditions with NfnII, with only a single high-potential electron passing into the [2Fe-2S] cluster of the high-potential pathway of NfnII but not progressing further to the S-FAD. This accounts for the observation that NfnII has greatly reduced bifurcating activity compared to NfnI. The lack of electron transfer into the S-FAD of NfnII due to its crossed half-potentials prevents successive bifurcation activity and indicates that electron transfer within the high-potential branch gates bifurcation activity in NfnI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Adsorption of Non-Ionic Surfactant and Monoclonal Antibody on Siliconized Surface Studied by Neutron Reflectometry

The adsorption of monoclonal antibodies (mAbs) on hydrophobic surfaces is known to cause protein aggregation and degradation. Therefore, surfactants, such as Poloxamer 188, are widely used in therapeutic formulations to stabilize mAbs and protect mAbs from interacting with liquid-solid interfaces. Here, the adsorption of Poloxamer 188, one mAb and their competitive adsorption on a model hydrophobic siliconized surface is investigated with neutron scattering coupled with contrast variation to determine the molecular structure of adsorbed layers for each case. Small angle neutron scattering measurements of the affinity of Poloxamer 188 to this mAb indicate that there is negligible binding at these solution conditions. Neutron reflectometry measurements of the mAb show irreversible adsorption on the siliconized surface, which cannot be washed off with neat buffer. Poloxamer 188 can be adsorbed on the surface already occupied by mAb, which enables partial removal of some adsorbed mAb by washing with buffer. The adsorption of the surfactant introduces significant conformational changes for mAb molecules that remain on the surface. In contrast, if the siliconized surface is first saturated with the surfactant, no adsorption of mAb is observed. Competitive adsorption of mAb and Poloxamer 188 from solution leads to a surface dominantly occupied with surfactant molecules, whereas only a minor amount of mAb absorbs. These findings clearly indicate that Poloxamer 188 can protect against mAb adsorption as well as modify the adsorbed conformation of previously adsorbed mAb.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Constraint energy minimizing generalized multiscale finite element method for multi-continuum Richards equations

In fluid flow simulation, the multi-continuum model is a useful strategy. When the heterogeneity and contrast of coefficients are high, the system becomes multiscale, and some kinds of reduced order methods are demanded. Combining these techniques with nonlinearity, we will consider in this paper a dual-continuum model which is generalized as a multi-continuum model for a coupled system of nonlinear Richards equations as unsaturated flows, in complex heterogeneous fractured porous media; and we will solve it by a novel multiscale approach utilizing the constraint energy minimizing generalized multiscale finite element method (CEM-GMsFEM). In particular, such a nonlinear system will be discretized in time and then linearized by Picard iteration (whose global convergence is proved theoretically). Subsequently, we tackle the resulting linearized equations by the CEM-GMsFEM and obtain proper offline multiscale basis functions to span the multiscale space (which contains the pressure solution). More specifically, we first introduce two new sources of samples, and the GMsFEM is used over each coarse block to build local auxiliary multiscale basis functions via solving local spectral problems, that are crucial for detecting high-contrast channels. Second, per oversampled coarse region, local multiscale basis functions are created through the CEM as constrainedly minimizing an energy functional. Various numerical tests for our approach reveal that the error converges with the coarse-grid size and that only few oversampling layers as well as basis functions are needed.

97 MATHEMATICS AND COMPUTING↗