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At least 937 records · Page 52
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Extended live-tracking and quantitative characterization of wound healing and cell migration with SiR-Hoechst

Highlights: • SiR-Hoechst is a nuclear dye that enables cell tracking without affecting migration. • Single cell analysis provides multiple migration metrics during wound healing. • Cell density-based report of wound healing is less susceptible to subjective bias. • Cell directionality is an important contributor of early wound recovery. Cell migration is essential to many life processes, including immune response, tissue repair, and cancer progression. A reliable quantitative characterization of the cell migration can therefore aid in the high throughput screening of drug efficacy in wound healing and cancer treatments. In this work, we report what we believe is the first use of SiR-Hoechst for extended live tracking and automated analysis of cell migration and wound healing. We showed through rigorous statistical comparisons that this far-red label does not affect migratory behavior. We observed excellent automated tracking of random cell migration, in which the motility parameters (speed, displacement, path length, directionality ratio, persistence time, and direction autocorrelation) obtained closely match those obtained from manual tracking. We also present an analysis framework to characterize the healing of a scratch wound from the perspective of single cells. The use of SiR-Hoechst is advantageous for the crowded environments in wound healing assays because as long as cell nuclei do not overlap, continuous tracking can be maintained even if there is cell-cell contact. In this paper, we report wound recovery based on the number of cells migrating into the wound over time, normalized by the initial cell count prior to the infliction of the wound. This normalized cell count approach is impervious to operator bias during the arbitration of wound edges and is also robust against variability that arises due to differences in the cell density of different samples. Additional wound healing characteristics were also defined based on the evolution of cell speed and directionality during healing. Not unexpected, the wound healing cells exhibited much higher tendency to maintain the same migratory direction in comparison to the randomly migrating cells. The use of SiR-Hoechst thus greatly simplified the automation of single cell and whole population analysis with high spatial and temporal resolution over extended periods of time.

60 APPLIED LIFE SCIENCES↗
NASA NTRS1994

Deflections of anisotropic sandwich beams with variable face sheets and core thicknesses

A sandwich construction consists of a low-density core material with high strength face sheets bounded to the top and bottom surfaces. The construction has been widely used in the aerospace and marine industries due to its outstanding characteristics such as noise absorption, weight minimization, heat insulation, and better bending stiffness. In sandwich structures used in high-performance aircraft, the face sheets are often made of fiber-reinforced composite materials and the core is made of honeycomb. The structures may also have variable thickness so as to satisfy aerodynamic requirements. In the stress analysis, the constant-thickness face sheets are usually considered as membrane and the core is assumed to be inextensible but deformable in the thickness direction. The static behavior of variable-thickness, isotropic and homogeneous sandwich beams was successfully studied by employing a constant-thickness theory but allowing stiffnesses to vary in accordance with local thickness variations. It has been recently found in a refined theory that the analyses based on the constant thickness theory locally can lead to significant errors in structural responses if the sandwich beam is thickness-tapered and the cores are deformable in transverse shear. The errors arise mainly from two factors: (1) the transverse shear components of the membrane forces in the face sheets alter the transverse shears carried by the core; and (2) the face-sheet membrane strains arise from transverse shear deformation of the core. In practice the variable thickness may not only exist in core but also in face sheets. The thickness-variations may even be a type of step function. In this case the transverse shear stress in the face sheets and bending stress in the core should be taken into account in the refined theory mentioned. In the present study, energy principles are employed in deriving governing equations for general bending of anisotropic sandwich beams with variable thickness in both face sheets and cores. Solutions to these equations are based on a finite difference scheme. As an example in application, a simply supported thickness-tapered sandwich beam subject to a concentrated load at its center is considered. Let W' be the maximum deflection of the beam in which face sheets are considered as membrane, while W'' is that based on using the modified refined theory. It is found that W' is always larger than W'', however, the magnitude of (W'- W'') appears to be insensitive to the change of the taper of the beam.

Lu, Chu-Ho↗
NASA NTRS1994

Steps toward determination of the size and structure of the broad-line region in active galactic nuclei. 5: Variability of the ultraviolet continuum and emission lines of NGC 3783

We report on the results of intensive ultraviolet spectral monitoring of the Seyfert 1 galaxy NGC 3783. The nucleus of NGC 3783 was observed with the International Ultraviolet Explorer satellite on a regular basis for a total of 7 months, once every 4 days for the first 172 days and once every other day for the final 50 days. Significant variability was observed in both continuum and emission-line fluxes. The light curves for the continuum fluxes exhibited two well-defined local minima or 'dips,' the first lasting is less than or approximately 20 days and the second is less than or approximately 4 days, with additional episodes of relatively rapid flickering of approximately the same amplitude. As in the case of NGC 5548 (the only other Seyfert galaxy that has been the subject of such an intensive, sustained monitoring effort), the largest continuum variations were seen at the shortest wavelengths, so that the continuum became 'harder' when brighter. The variations in the continuum occurred simultaneously at all wavelengths (delta(t) is less than 2 days). Generally, the amplitude of variability of the emission lines was lower than (or comparable to) that of the continuum. Apart from Mg II (which varied little) and N V (which is relatively weak and badly blended with Ly(alpha), the light curves of the emission lines are very similar to the continuum light curves, in each case with a small systematic delay or 'lag.' As for NGC 5548, the highest ionization lines seem to respond with shorter lags than the lower ionization lines. The lags found for NGC 3783 are considerably shorter than those obtained for NGC 5548, with values of (formally) approximately 0 days for He II + O III), and approximately 4 days for Ly(alpha) and C IV. The data further suggest lags of approximately 4 days for Si IV + O IV) and 8-30 days for Si III + C III). Mg II lagged the 1460 A continuum by approximately 9 days, although this result depends on the method of measuring the line flux and may in fact be due to variability of the underlying Fe II lines. Correlation analysis further shows that the power density spectrum contains substantial unresolved power over timescales of is less than or approximately 2 days, and that the character of the continuum variability may change with time.

Reichert, G. A.↗
NASA NTRS2013

Long-Term Variability of AGN at Hard X-Rays

Variability at all observed wavelengths is a distinctive property of active galactic nuclei (AGN). Hard X-rays provide us with a view of the innermost regions of AGN, mostly unbiased by absorption along the line of sight. Characterizing the intrinsic hard X-ray variability of a large AGN sample and comparing it to the results obtained at lower X-ray energies can significantly contribute to our understanding of the mechanisms underlying the high-energy radiation. Methods. Swift/BAT provides us with the unique opportunity to follow, on time scales of days to years and with a regular sampling, the 14-195 keV emission of the largest AGN sample available up to date for this kind of investigation. As a continuation of an early work on the first 9 months of BAT data, we study the amplitude of the variations, and their dependence on sub-class and on energy, for a sample of 110 radio quiet and radio loud AGN selected from the BAT 58-month survey. About 80 of the AGN in the sample are found to exhibit significant variability on months to years time scales, radio loud sources being the most variable. The amplitude of the variations and their energy dependence are incompatible with variability being driven at hard X-rays by changes of the absorption column density. In general, the variations in the 14-24 and 35-100 keV bands are well correlated, suggesting a common origin of the variability across the BAT energy band. However, radio quiet AGN display on average 10 larger variations at 14-24 keV than at 35-100 keV and a softer-when-brighter behavior for most of the Seyfert galaxies with detectable spectral variability on month time scale. In addition, sources with harder spectra are found to be more variable than softer ones. These properties are generally consistent with a variable power law continuum, in flux and shape, pivoting at energies 50 keV, to which a constant reflection component is superposed. When the same time scales are considered, the timing properties of AGN at hard X-rays are comparable to those at lower energies, with at least some of the differences possibly ascribable to components contributing differently in the two energy domains (e.g., reflection, absorption).

X-rays↗
NASA NTRS2011

Use of MODIS Satellite Images and an Atmospheric Dust Transport Model to Evaluate Juniperus spp. Pollen Phenology and Transport

Pollen can be transported great distances. Van de Water et al., 2003 reported Juniperus spp. pollen, a significant aeroallergen was transported 200-600 km. Hence local observations of plant phenology may not be consistent with the timing and source of pollen collected by pollen sampling instruments. Direct detection of pollen via satellite is not practical. A practical alternative combines modeling and phenological observations using ground based sampling and satellite data. The DREAM (Dust REgional Atmospheric Model) is a verified model for atmospheric dust transport modeling using MODIS data products to identify source regions and quantities of dust (Nickovic et al. 2001). The use of satellite data products for studying phenology is well documented (White and Nemani 2006). In the current project MODIS data will provide critical input to the PREAM model providing pollen source location, timing of pollen release, and vegetation type. We are modifying the DREAM model (PREAM - Pollen REgional Atmospheric Model) to incorporate pollen transport. The linkages already exist with DREAM through PHAiRS (Public Health Applications in Remote Sensing) to the public health community. This linkage has the potential to fill this data gap so that the potential association of health effects of pollen can better be tracked for possible linkage with health outcome data which may be associated with asthma, respiratory effects, myocardial infarction, and lost workdays. Juniperus spp. pollen phenology may respond to a wide range of environmental factors such as day length, growing degree-days, precipitation patterns and soil moisture. Species differences are also important. These environmental factors vary over both time and spatial scales. Ground based networks such as the USA National Phenology Network have been established to provide national wide observations of vegetation phenology. However, the density of observers is not adequate to sufficiently document the phenology variability over large regions. Hence the use of satellite data is critical to observe Juniperus spp. pollen phenology. MODIS data was used to observe Juniperus spp. pollen phenology. The MODIS surface reflectance product(MOD09) provided information on the Juniper spp. cone formation and cone density (Fig 1). Ground based observational records of pollen release timing and quantities were used as verification. Techniques developed using MOD09 surface reflectance products will be directly applicable to the next generation sensors such as VIIRS.

Luvall, J. C.↗
DOE OSTI2017

II. Transport of Nearly Incompressible Magnetohydrodynamic Turbulence from 1 to 75 au

The thermal plasma beta in the solar wind and the solar corona is of the order of β∼1 and β≪1. Zank et al. developed 2D and slab turbulence transport model equations of the order of β∼1 and β≪1 using nearly incompressible (NI) theory. We solve the Zank et al. NI MHD coupled turbulence transport equations for the inhomogeneous solar wind from 1 to 75 au, and compare the numerical solutions to Voyager 2 observations. We find that (1) the 2D turbulent energies are larger than the slab energies throughout the heliosphere; (2) the 2D turbulent energies decrease more slowly than the slab turbulent energies within ∼4 au, while the slab energies increase and the 2D energies flatten in the outer heliosphere; (3) the 2D normalized cross-helicity decreases faster than the slab normalized cross-helicity within ∼4 au; (4) the 2D normalized residual energy is more magnetically dominated than the slab; (5) the variance of density fluctuations decreases more rapidly than r{sup −4} within ∼10 au, and more slowly in the outer heliosphere; and (6) the observed variance in magnetic field fluctuations as a function of the thermal plasma beta is described by the two-component turbulence transport model. In summary, the NI MHD two-component Zank et al. turbulence transport model captures the behavior of the forward, backward, and total energies in the fluctuating Elsässer variables, the variance in the magnetic field, kinetic energy, and density fluctuations, the cross-helicities and residual energies, the thermal temperature and plasma beta, and the various correlation lengths.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2019

The Ability of GeoCarb to Constrain the Interannual Variability of Carbon Gases over the Amazon

We perform a number of idealized assimilation experiments with the GEOS constituent data assimilation system to test the ability of GeoCarb retrievals of CO, CO2, and CH4 to constrain the interannual variability of these gases over the Amazon. Retrievals for instruments on other satellites which observe in similar channels (e.g. MOPITT, GOSAT, and OCO-2) are limited due to persistent cloud coverage. Given its ability to sample the same location multiple times in one day, the expectation is that GeoCarb retrievals will return more soundings than those from previous missions. The goal of the assimilation experiments is to understand which scanning strategies lead to the best sounding densities and thus have the best chance of constraining interannual variability in the carbon species. The experiments each begin by picking a given year at random from a nature run (i.e., a model simulation meant to represent the truth). The model fields are sampled according to a given strategy and then screened to account for cloud coverage. Next, we pick another year at random and assimilate the synthetic GeoCarb samples into the GEOS model for that year. The output of the assimilation, 6-hourly, 3D fields of each constituent, is then directly comparable to the nature run. This comparison allows us to evaluate the ability of GeoCarb measurements to constrain the interannual variability of each gas.

Weir, B.↗
NASA NTRS1991

Optical polarization of a complete sample of radio sources

The radio and optical properties of a complete 5 GHz sample of strong radio sources are studied. High polarization is strongly correlated with the fraction of the total 5 GHz flux density found in a milliarcsec core. The detection rate of radio galaxies containing optical cores with high polarization is consistent with the hypothesis that all radio sources contain optically polarized cores, with strength proportional to the core radio flux density. High optical polarization, optical power-law fraction, line-to-continuum ratio, emission lines of small equivalent widths, and large amplitude flux variability are all strongly correlated with the fraction of the 5 GHz radio flux density that is unresolved on VLBI scales. The distributions of these properties are well matched by a model where radio and optical radiation have the same beaming geometry and with Doppler boosting of a factor of 10-100 in the optical. A striking alignment of the position angle of the VLBI structure axis and the position angle of optical polarization in highly polarized sources is confirmed.

Impey, C. D.↗
DOE OSTI2017

Planck intermediate results: LII. Planet flux densities

Measurements of flux density are described for five planets, Mars, Jupiter, Saturn, Uranus, and Neptune, across the six Planck High Frequency Instrument frequency bands (100-857 GHz) and these are then compared with models and existing data. In our analysis, we have also included estimates of the brightness of Jupiter and Saturn at the three frequencies of the Planck Low Frequency Instrument (30, 44, and 70 GHz). The results provide constraints on the intrinsic brightness and the brightness time-variability of these planets. The majority of the planet flux density estimates are limited by systematic errors, but still yield better than 1% measurements in many cases. Applying data from Planck HFI, the Wilkinson Microwave Anisotropy Probe (WMAP), and the Atacama Cosmology Telescope (ACT) to a model that incorporates contributions from Saturn's rings to the planet's total flux density suggests a best fit value for the spectral index of Saturn's ring system of β ring = 2.30 ± 0.03 over the 30-1000 GHz frequency range. Estimates of the polarization amplitude of the planets have also been made in the four bands that have polarization-sensitive detectors (100-353 GHz); this analysis provides a 95% confidence level upper limit on Mars's polarization of 1.8, 1.7, 1.2, and 1.7% at 100, 143, 217, and 353 GHz, respectively. The average ratio between the Planck -HFI measurements and the adopted model predictions for all five planets (excluding Jupiter observations for 353 GHz) is 1.004, 1.002, 1.021, and 1.033 for 100, 143, 217, and 353 GHz, respectively. Model predictions for planet thermodynamic temperatures are therefore consistent with the absolute calibration of Planck -HFI detectors at about the three-percent level. We compare our measurements with published results from recent cosmic microwave background experiments. In particular, we observe that the flux densities measured by Planck HFI and WMAP agree to within 2%. These results allow experiments operating in the mm-wavelength range to cross-calibrate against Planck and improve models of radiative transport used in planetary science.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

Hybrid-Electric Turbocharger and High-Speed SiC Variable-Frequency Drive Using Sensorless Control Algorithm

Electrically assisted engine boosting systems lend themselves to better throttle response, wider effective operating ranges, and can provide the ability to extract excess energy during deceleration and high-load events (and store it in a vehicle's onboard batteries). This can lead to better overall vehicle performance, emissions, and efficiency while allowing for further engine downsizing and increased power density. In this research effort, a hybrid-electric turbocharger, variable-frequency drive (VFD), and novel sensorless control algorithm were developed. An 11 kW permanent-magnet (PM) machine was coupled to a commercial turbocharger via an in-line, bolt-on housing attached to the compressor inlet. A high-efficiency, high-temperature VFD, consisting of custom control and power electronics, was also developed. The VFD uses SiC MOSFETS to achieve high-switching frequency and can be cooled using an existing engine coolant loop operating at up to 105 °C at an efficiency greater than 98%. A digital sliding mode-observer sensorless speed control algorithm was created to command and regulate speed and achieved ramp rates of over 68,000 rpm/s. A two-machine benchtop motor/generator test stand was constructed for initial testing and tuning of the VFD and sensorless control algorithm. A gas blow-down test stand was constructed to test the mechanical operation of the hybrid-electric turbocharger and speed control using the VFD. In addition, a liquid-pump cart was assembled for high-temperature testing of the VFD. Initial on-engine testing is planned for later this year. This paper intends to present a design overview of the in-line, hybrid-electric device, VFD, and performance characterization of the electronics and sensorless control algorithm.

Engineering↗
NASA NTRS2004

On the Inversion for Mass (Re)Distribution from Global (Time-Variable) Gravity Field

The well-known non-uniqueness of the gravitational inverse problem states the following: The external gravity field, even if completely and exactly known, cannot Uniquely determine the density distribution of the body that produces the gravity field. This is an intrinsic property of a field that obeys the Laplace equation, as already treated in mathematical as well as geophysical literature. In this paper we provide conceptual insight by examining the problem in terms of spherical harmonic expansion of the global gravity field. By comparing the multipoles and the moments of the density function, we show that in 3-S the degree of knowledge deficiency in trying to inversely recover the density distribution from external gravity field is (n+l)(n+2)/2 - (2n+l) = n(n-1)/2 for each harmonic degree n. On the other hand, on a 2-D spherical shell we show via a simple relationship that the inverse solution of the surface density distribution is unique. The latter applies quite readily in the inversion of time-variable gravity signals (such as those observed by the GRACE space mission) where the sources over a wide range of the scales largely come from the Earth's Surface.

Chao, Benjamin F.↗
DOE OSTI2024

Exploring Spin‐Orbit Effects in a [Cu 6 Tl] + Nanocluster Featuring an Uncommon Tl−H Interaction

Reaction of [CuH(PPh 3 )] 6 with 1 equiv. of Tl(OTf) results in formation of [Cu 6 TlH 6 (PPh 3 ) 6 ][OTf] ([1]OTf]), which can be isolated in good yields. Variable-temperature 1 H NMR spectroscopy, in combination with density functional theory (DFT) calculations, confirms the presence of a rare Tl−H orbital interaction. According to DFT, the 1 H chemical shift of the Tl-adjacent hydride ligands of [1] + includes 7.7 ppm of deshielding due to spin-orbit effects from the heavy Tl atom. In conclusion, this study provides valuable new insights into a rare class of metal hydrides, given that [1][OTf] is only the third isolable species reported to contain a Tl−H interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Applying NIR and MIR spectroscopy for C and soil property prediction in northern cold-region ecosystems. Which approach works better?

Here, developing reliable predictions of soil attributes is necessary to understand northern cold-region climate-soil feedback. Calibration models using near-infrared (NIR) and mid-infrared (MIR) spectroscopy were developed to predict eight commonly measured soil properties for 119 soil samples representing a range of vegetation types, parent materials, and soil types spanning >23° of latitude from southeast Alaska to the Canadian high Arctic. In order to obtain a more accurate prediction, this study compared the performance of linear and non-linear calibration techniques, including lasso regression (Lasso), support vector machine (SVM), random forest (RF) and classic partial least squares (PLS) to predict different soil properties of these soils. Comparing the four models, we noticed that their performance was quite similar for MIR overall, while NIR achieved better results with a PLS model for our dataset. PLS coupled with MIR showed a better performance for soil parameters, such as total organic carbon (TOC), total nitrogen (TN), cation exchange capacity (CEC) and clay (R-squared of 0.9, 0.81, 0.80, and 0.84) when compared with NIR (R-squared of 0.85, 0.72, 0.81 and 0.68). However, using either MIR or NIR spectroscopy, PLS predictions for bulk density (BD) and sand content were not accurate. The variable importance analysis based on the PLS model successfully estimated the relative contribution of wavelengths influencing soil property predictions most. Overall, TOC, TN, CEC and clay mineral predictions are closely related to the occurrence of specific spectral bands in the MIR region. For example, wavelengths at 2978 and 1761 cm -1 for TOC and TN, as well as at 3064 cm -1 for CEC, were selected as the most influential predictor variables. We demonstrated that MIR spectroscopy is a powerful tool for more extensive monitoring in soils of the northern cold climate region; however, NIR could be utilized for rapid estimates when the highest accuracy is not essential.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Strain localization and dynamic recrystallization in polycrystalline metals: Thermodynamic theory and simulation framework

We describe a theoretical and computational framework for adiabatic shear banding (ASB) and dynamic recrystallization (DRX) in polycrystalline materials. The Langer-Bouchbinder-Lookman (LBL) thermodynamic theory of polycrystalline plasticity, which we recently reformulated to describe DRX via the inclusion of the grain boundary density or the grain size as an internal state variable, provides a convenient and self-consistent way to represent the viscoplastic and thermal behavior of the material, with minimal ad-hoc assumptions regarding the initiation of yielding or onset of shear banding. Here, we implement the LBL-DRX theory in conjunction with a finite-element computational framework. Favorable comparison to experimental measurements on a top-hat AISI 316L stainless steel sample compressed with a split-Hopkinson pressure bar suggests the accuracy and usefulness of the LBL-DRX framework, and demonstrates the crucial role of DRX in strain localization.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A Semi-Empirical Density Law for Ternary, Homogeneous PuCl 3 /HCl/H 2 O Solutions

Nuclear material operations pose unique hazards that are not encountered in other chemical, energy, or manufacturing industries. One of these hazards is the potential for a nuclear criticality accident when handling fissile isotopes such as 235 U and 239 Pu. These hazards are particularly high when fissile material is dissolved in solution as the neutron behaviors of the system can change rapidly with the physical and chemical changes accessible in solution. Current estimates of solution density used for criticality safety are outdated and hinder fissile material handling. Developing new estimates for these safety calculations requires experimental characterization and the derivation of empirical density models. We have derived a density law describing PuCl 3 /HCl/H 2 O solutions from experimental data characterizing solution density. Density data was treated using a Pitzer-derived eight-parameter equation, defining density as a function of analyte concentrations, temperature, and interactions between these variables. The model is predictive across the concentration and temperature ranges from which it was derived. The potential effects of varying oxidation states of plutonium, which are easily accessible in aqueous media, on the bulk solution density of the ternary system were also investigated. The resulting Pitzer-derived density law was applied to a nuclear criticality safety model, and the impact of the experimental characterization of solution density relative to previous estimates was demonstrated to be significant and suggest that the current approach to estimating density in nuclear criticality safety calculations may lead to overly conservative controls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Machine Learning Self-Diffusion Prediction for Lennard-Jones Fluids in Pores

Predicting the diffusion coefficient of fluids under nanoconfinement is important for many applications including the extraction of shale gas from kerogen and product turnover in porous catalysts. Due to the large number of important variables, including pore shape and size, fluid temperature and density, and the fluid–wall interaction strength, simulating diffusion coefficients using molecular dynamics (MD) in a systematic study could prove to be prohibitively expensive. Here, we use machine learning models trained on a subset of MD data to predict the self-diffusion coefficients of Lennard-Jones fluids in pores. Our MD data set contains 2280 simulations of ideal slit pore, cylindrical pore, and hexagonal pore geometries. We use the forward feature selection method to determine the most useful features (i.e., descriptors) for developing an artificial neutral network (ANN) model with an emphasis on easily acquired features. Our model shows good predictive ability with a coefficient of determination (i.e., R 2 ) of ~0.99 and a mean squared error of ~2.9 × 10 –5 . Finally, we propose an alteration to our feature set that will allow the ANN model to be applied to nonideal pore geometries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

2D-Covalent Organic Frameworks with Interlayer Hydrogen Bonding Oriented through Designed Nonplanarity

We report the synthesis and characterization of a new class of 2D-covalent organic frameworks, called COFamides, whose layers are held together by amide hydrogen bonds. To accomplish this, we have designed monomers with a nonplanar structure that arises from steric crowding, forcing the amide side groups out of plane with the COF sheets orienting the hydrogen bonds between the layers. Here, the presence of these hydrogen bonds provides significant structural stabilization as demonstrated by comparison to control structures that lack hydrogen bonding capability, resulting in lower surface area and crystallinity. We have characterized both azine and imine-linked versions of these COFs, named COFamide-1 and -2, respectively, for their surface areas, pore sizes, and crystallinity. In addition to these more conventional characterization methods, we also used variable temperature infrared spectroscopy methods and van der Waals density functional calculations to directly observe the presence of hydrogen bonding.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Nature of the Reactive Biferric Peroxy Intermediate P′ in the Arylamine Oxygenases and Related Binuclear Fe Enzymes

Binuclear nonheme iron enzymes activate O 2 to perform a wide range of chemical transformations. The process of O 2 activation typically involves a biferric peroxy-level intermediate P. It has been previously found that this intermediate undergoes further activation, either protonation or rearrangement to form P′ or further oxidation to form high-valent intermediates Q or X. Here, this study defines the structure of the P′ intermediate in the N-oxygenases CmlI (and AurF based on previous data) using nuclear resonance vibrational spectroscopy (NRVS) in conjugation with density functional theory (DFT) calculations. These results, combined with variable temperature variable field (VTVH) magnetic circular dichroism (MCD) spectroscopy on the 1-electron cryoreduced P′, define the structure of the P′ intermediate as a μ-1,2-hydroxoperoxo biferric site with a second hydroxide bridge. Reaction coordinate calculations demonstrate that single electron transfer (SET) is facilitated by protonation of the peroxo, activating its reductive cleavage, and that the additional hydroxide bridge does not impact this reaction. VTVH MCD studies further reveal that the hydroxide bridge is absent in the biferrous site, suggesting that during the O 2 reaction with the biferrous site, a water molecule forms the hydroxide bridge in providing the proton that activates the peroxide in P′ for reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗