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DOE OSTI2023

The Interaction between the DOCK7 Protein and the E2 Protein of Classical Swine Fever Virus Is Not Involved with Viral Replication or Pathogenicity

The classical swine fever virus (CSFV) particle consists of three glycoproteins, all of which have been shown to be important proteins involved in many virus functions, including interaction with several host proteins. One of these proteins, E2, has been shown to be directly involved with adsorption to the host cell and important for virus virulence. Using the yeast two-hybrid system, we have previously shown that CSFV E2 specifically interacts with the (DOCK7) dedicator of cytokinesis, a scaffolding protein. In this report, the interaction between E2 and DOCK7 was evaluated. To confirm the yeast two-hybrid results and to determine that DOCK7 interacts in swine cells with E2, we performed co-immunoprecipitation and proximity ligation assay (PLA). After demonstrating the protein interaction in swine cells, E2 amino acid residues Y65, V283, and T149 were determined to be critical for interaction with Dock7 by using a random mutated library of E2 and a reverse yeast two-hybrid approach. That disruption of these three residues with mutations Y65F, V283D, and T149A abrogated the Dock7-E2 protein interaction. These mutations were then introduced into a recombinant CSFV, E2DOCK7v, by a reverse genomics approach using the highly virulent CSFV Brescia isolate as a backbone. E2DOCKv was shown to have similar growth kinetics in swine primary macrophages and SK6 cell cultures to the parental Brescia strain. Similarly, E2DOCK7v demonstrated a similar level of virulence to the parental Brescia when inoculated in domestic pigs. Animals intranasally inoculated with 10 5 TCID 50 developed a lethal form of clinical disease with virological and hematological kinetics changes indistinguishable from that produced by the parental strain. Therefore, interaction between CSFV E2 and host DOCK7 is not critically involved in the process of virus replication and disease production.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2020

Signatures of Velocity-dependent Dark Matter Self-interactions in Milky Way-mass Halos

In this work, we explore the impact of elastic, anisotropic, velocity-dependent dark matter (DM) self-interactions on the host halo and subhalos of Milky Way (MW)--mass systems. We consider a generic self-interacting dark matter (SIDM) model parameterized by the masses of a light mediator and the DM particle. The ratio of these masses, w, sets the velocity scale above which momentum transfer due to DM self-interactions becomes inefficient. We perform high-resolution zoom-in simulations of an MW-mass halo for values of w that span scenarios in which self-interactions either between the host and its subhalos or only within subhalos efficiently transfer momentum, and we study the effects of self-interactions on the host halo and on the abundance, radial distribution, orbital dynamics, and density profiles of subhalos in each case. The abundance and properties of surviving subhalos are consistent with being determined primarily by subhalo--host halo interactions. In particular, subhalos on radial orbits in models with larger values of the cross section at the host halo velocity scale are more susceptible to tidal disruption owing to mass loss from ram pressure stripping caused by self-interactions with the host. This mechanism suppresses the abundance of surviving subhalos relative to collisionless DM simulations, with stronger suppression for larger values of w. Thus, probes of subhalo abundance around MW-mass hosts can be used to place upper limits on the self-interaction cross section at velocity scales of ~200 km s-1, and combining these measurements with the orbital properties and internal dynamics of subhalos may break degeneracies among velocity-dependent SIDM models.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2022

Late-onset Circumstellar Medium Interactions are Rare: An Unbiased GALEX View of Type Ia Supernovae

Abstract Using ultraviolet (UV) light curves, we constrain the circumstellar environments of 1080 Type Ia supernovae (SNe Ia) within z < 0.5 from archival Galaxy Evolution Explorer (GALEX) observations. All SNe Ia are required to have pre- and post-explosion GALEX observations to ensure adequate subtraction of the host-galaxy flux. Using the late-time GALEX observations, we look for the UV excess expected from any interaction between the SN ejecta and circumstellar material (CSM). Four SNe Ia are detected near maximum light, and we compare the GALEX photometry to archival data. However, we find that none of our targets show convincing evidence of CSM interaction. A recent Hubble Space Telescope (HST) survey estimates that ∼6% of SNe Ia may interact with distant CSM, but statistical inferences are complicated by the small sample size and selection effects. By injecting model light curves into our data and then recovering them, we constrain a broad range of CSM interactions based on the CSM interaction start time and the maximum luminosity. Combining our GALEX nondetections with the HST results, we constrain occurrence of late-onset CSM interaction among SNe Ia with moderate CSM interaction, similar to that observed in PTF11kx, to f CSM ≲ 5.1% between 0 and 500 days after discovery and ≲2.7% between 500 and 1000 days after discovery at 90% confidence. For weaker CSM interactions similar to SN 2015cp, we obtain limits of ≲16% and ≲4.8%, respectively, for the same time ranges.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS1979

Interactions between spacecraft and the charged-particle environment

Spacecraft-environment interactions are defined as the responses of a spacecraft surface to a charged-particle environment. This response can influence spacecraft system performance. Interactions can be divided into two broad categories: spacecraft passive, in which the environment acts on the spacecraft; and spacecraft active, in which the spacecraft causes the interaction. Passive interactions include the spacecraft-charging phenomenon. Active interactions include the relatively new interactions arising from the use of very large spacecraft and space power systems in future missions. To illustrate active interactions, a large power system operating at elevated voltages is considered. Possible interactions are described, available experimental data are reviewed, and the effect on power system performance is estimated.

Stevens, N. J.↗

NASA NTRS1989

Aerodynamic interaction between vortical wakes and lifting two-dimensional bodies

Unsteady rotor wake interactions with the empennage, tail boom, and other aerodynamic surfaces of a helicopter have a significant influence on its aerodynamic performance, the ride quality, and vibration. A numerical method for computing the aerodynamic interaction between an interacting vortex wake and the viscous flow about arbitrary two-dimensional bodies was developed to address this helicopter problem. The method solves for the flow field velocities on a body-fitted computational mesh using finite-difference techniques. The interacting vortex wake is represented by an array of discrete vortices which, in turn, are represented by a finite-core model. The evolution of the interacting vortex wake is calculated by Lagrangian techniques. The viscous flow field of the two-dimensional body is calculated on an Eulerian grid. The flow around circular and elliptic cylinders in the absence of an interacting vortex wake was calculated. These results compare very well with other numerical results and with results obtained from experiment and thereby demonstrate the accuracy of the viscous solution. The interaction of a rotor wake with the flow about a 4 to 1 elliptic cylinder at 45 degree incidence was calculated for a Reynolds number of 3000. The results demonstrate the significant variations in the lift and drag on the elliptic cylinder in the presence of the interacting rotor wake.

Stremel, Paul M.↗

NASA NTRS1989

Inception length to a fully-developed fin-generated shock wave boundary-layer interaction

An experimental study of fin-generated shock wave turbulent boundary-layer interactions confirmed previous observations that, sufficiently far from the fin apex, such interactions become conical. The inception length to conical symmetry was found to increase weakly with Mach number for Mach numbers from 2.5 to 4 and fin angles from 4 to 22 deg. For the range of interactions examined, the inception length was found to depend primarily upon the inviscid shock angle, this angle ranging from 21 to 40 deg. The behavior of the inception length with shock angle can be broadly divided into two categories. For 'weak' interactions with shock angles less than about 35 deg, the inception length decreased as the shock angle increased. For 'strong' interactions with shock angles greater than about 35 deg, the inception region was small and was approximately constant at three boundary-layer thicknesses in length. In the latter, strong interaction case, the inception length was an order of magnitude smaller than that found in the weakest interactions examined, to the extent that strong interactions were practically fully-developed from the apex.

Lu, Frank K.↗

NASA NTRS1992

A Study of Viscous Interaction Effects on Hypersonic Waveriders

The effects of viscous interaction in the analysis and design of improved classes of viscous optimized hypersonic waveriders is examined. The Corda computer program is used to generate viscous optimized hypersonic waveriders from conical flow fields without viscous interaction. Each waverider is optimized for maximum L/D, and comparison studies are made between cases with and without viscous interaction. The results show that aerodynamic performance of the viscous interaction waveriders are reduced due mainly to a large increase in skin-friction drag associated with the viscous interaction phenomena that grows with increasing Mach number and altitude, but some of this performance loss can be recouped by including viscous interactions within the optimization procedure. When the waverider is optimized for viscous interaction, the shape can change dramatically. A significant result of the present work delineates on a velocity-altitude map the region where viscous interaction effects are significant for modern hypersonic waveriders by performing parametric runs to produce L/D, C sub L, and C sub D contour plots for Mach numbers from 6 to 30 at altitudes from 30 to 80 km.

Chang, Jinhwa↗

NASA NTRS1993

Quasiconical free interaction between a swept shock and a turbulent boundary layer

Previous observations that fin-generated interactions are quasi-conical in nature were further confirmed by surface pressure measurements spanning Mach 2.5-3.5, which encompassed unseparated through strongly separated interactions. For strongly separated interactions in which the shock wave is bifurcated into a lambda-foot structure, the conical free interaction hypothesis was validated through an appropriate scaling of the far-field surface pressure distribution. The behavior of the lambda-foot structure, such as the decrease of the slope of the separation shock with interaction strength, was explained by invoking the conical free interaction hypothesis. Through the conical free interaction hypothesis, it was further shown that the triple-shock intersection behaves in a complicated manner with changes in interaction strength.

Lu, Frank K.↗

NASA NTRS1993

Cognitive engineering models: A prerequisite to the design of human-computer interaction in complex dynamic systems

This chapter examines a class of human-computer interaction applications, specifically the design of human-computer interaction for the operators of complex systems. Such systems include space systems (e.g., manned systems such as the Shuttle or space station, and unmanned systems such as NASA scientific satellites), aviation systems (e.g., the flight deck of 'glass cockpit' airplanes or air traffic control) and industrial systems (e.g., power plants, telephone networks, and sophisticated, e.g., 'lights out,' manufacturing facilities). The main body of human-computer interaction (HCI) research complements but does not directly address the primary issues involved in human-computer interaction design for operators of complex systems. Interfaces to complex systems are somewhat special. The 'user' in such systems - i.e., the human operator responsible for safe and effective system operation - is highly skilled, someone who in human-machine systems engineering is sometimes characterized as 'well trained, well motivated'. The 'job' or task context is paramount and, thus, human-computer interaction is subordinate to human job interaction. The design of human interaction with complex systems, i.e., the design of human job interaction, is sometimes called cognitive engineering.

Mitchell, Christine M.↗

NASA NTRS1999

Combustion of Interacting Droplet Arrays in a Microgravity Environment

Investigations into droplet interactions date back to Rex et al. Recently, Annamalai and Ryan and Annamalai published extensive reviews of droplet array and cloud combustion studies. The authors studied the change in the burning rate constant, k, (relative to that of the single droplet) that results from interactions. Under certain conditions, there exists a separation distance where the droplet lifetime reaches a minimum, or average burning rate constant is a maximum . Additionally, since inter-droplet separation distance, L, increases relative to the droplet size, D, as the burning proceeds, the burning rate is not constant throughout the burn, but changes continuously with time. Only Law and co-workers and Mikami et al. studied interactions under conditions where buoyant forces were negligible. Comparing their results with existing theory, Law and co-workers found that theory over predicted the persistency and intensity of droplet interactions. The droplet interactions also depended on the initial array configuration as well as the instantaneous array configuration. They also concluded that droplet heating was retarded due to interactions and that the burning process did not follow the "D-squared" law. Mikami et al. studied the combustion of a two-droplet array of heptane burning in air at one atm pressure in microgravity. They showed that the instantaneous burning rate constant increases throughout the droplet lifetime, even for a single droplet. Also, the burn time of the array reached a minimum at a critical inter-droplet spacing. In this article, we examine droplet interactions in normal and microgravity environments. The microgravity experiments were in the NASA GRC 2.2 and 5.2 second drop towers, and the JAMIC (Japan Microgravity Center) 10 second drop tower. Special emphasis is directed to combustion under conditions that yield finite extinction diameters, and to determine how droplet interactions affect the extinction process.

Dietrich, D. L.↗

NASA NTRS2000

Numerical Study of Rarefied Hypersonic Flow Interacting with a Continuum Jet

An uncoupled Computational Fluid Dynamics-Direct Simulation Monte Carlo (CFD-DSMC) technique is developed and applied to provide solutions for continuum jets interacting with rarefied external flows. The technique is based on a correlation of the appropriate Bird breakdown parameter for a transitional-rarefied condition that defines a surface within which the continuum solution is unaffected by the external flow-jet interaction. The method is applied to two problems to assess and demonstrate its validity; one of a jet interaction in the transitional-rarefied flow regime and the other in the moderately rarefied regime. Results show that the appropriate Bird breakdown surface for uncoupling the continuum and non-continuum solutions is a function of a non-dimensional parameter relating the momentum flux and collisionality between the two interacting flows. The correlation is exploited for the simulation of a jet interaction modeled for an experimental condition in the transitional-rarefied flow regime and the validity of the correlation is demonstrated. The uncoupled technique is also applied to an aerobraking flight condition for the Mars Global Surveyor spacecraft with attitude control system jet interaction. Aerodynamic yawing moment coefficients for cases without and with jet interaction at various angles-of-attack were predicted, and results from the present method compare well with values published previously. The flow field and surface properties are analyzed in some detail to describe the mechanism by which the jet interaction affects the aerodynamics.

Glass, Christopher E.↗

NASA NTRS2000

Effective Potential Energies and Transport Cross Sections for Interactions of Hydrogen and Nitrogen

The interaction energies for N2-He and N2-H2 are calculated by accurate ab initio methods. The virial coefficient and differential scattering cross section for N2-H2 are calculated; the theoretical results are compared with experimental data. The transport collision integrals for N2-H2 and N2-N2 interactions are calculated and tabulated; the results yield transport coefficients that compare well with measured data. Transport coefficients are found to be determined accurately from the interaction energies for a specific configuration of the molecule formed from the interaction partners. Comparisons with results of measurement and accurate calculations demonstrate that the transport properties of complex molecular interactions can be determined rapidly and fairly accurately from the interaction energies of simpler system using combination rules for the short-range parameters of effective interaction energies and the coefficients for the long-range forces. The coefficients for a two-parameter temperature expansion of diffusion and viscosity are tabulated for a realistic universal potential energy that is based primarily on the results of very accurate calculations of the He-He interaction energy.

Stallcop, James R.↗

NASA NTRS2000

First Astronaut- Rover Interaction Field Test

The first Astronaut - Rover (ASRO) Interaction field test was conducted successfully on February 22-27, 1999, in Silver Lake, Mojave Desert, California in a representative planetary surface terrain. This test was a joint effort between the NASA Ames Research Center , Moffett Field, California and the NASA Johnson Space Center, Houston, Texas. As prototype advanced planetary surface space suit and rover technologies are being developed for human planetary surface exploration , it has been determined that it is important to better understand the potential interaction and benefits of an EVA astronaut interacting with a robotic rover . This interaction between an EVA astronaut and a robotic rover is seen as complementary and can greatly enhance the productivity and safety of surface excursions . This test also identified design requirements and options in an advanced space suit and robotic rover. The test objectives were: 1. To identify the operational domains where the EVA astronauts and rover are complementary and can interact and thus collaborate in a safe , productive and cost- effective way, 2. To identify preliminary requirements and recommendations for advanced space suits and rovers that facilitate their cooperative and complementary interaction, 3. To develop operational procedures for the astronaut-rover teams in the identified domains, 4. To test these procedures during representative mission scenarios during field tests by simulating the exploration of a planetary surface by an EVA crew interacting with a robotic rover, 5. To train a space suited test subject, simulated Earth-based and l or lander-based science teams, and robotic vehicle operators in mission configurations, and 6. To evaluate and understand socio-technical aspects of the astronaut - rover interaction experiment in order to guide future technologies and designs. Test results and areas for future research in the design of planetary space suits will be discussed .

Kosmo, Joseph J.↗

NASA NTRS2012

CME Interaction with Large-Scale Coronal Structures

This talk presents some key observations that highlight the importance of CME interaction with other large scale structures such as CMEs and coronal holes . Such interactions depend on the phase of the solar cycle: during maximum, CMEs are ejected more frequently, so CME-CME interaction becomes dominant. During the rise phase, the polar coronal holes are strong, so the interaction between polar coronal holes and CMEs is important, which also leads to a possible increase in the number of interplanetary CMEs observed as magnetic clouds. During the declining phase, there are more equatorial coronal holes, so CMEs originating near these coronal holes are easily deflected. CMEs can be deflected toward and away from the Sun-Earth line resulting in interesting geospace consequences. For example, the largest geomagnetic storm of solar cycle 23 was due to a CME that was deflected towards the Sun-earth line from E22. CME deflection away from the Sun-Earth line diminishes the chance of a CME producing a geomagnetic storm. CME interaction in the coronagraphic field of view was first identified using enhanced radio emission, which is an indication of acceleration of low energy (approx.10 keV) electrons in the interaction site. CME interaction, therefore, may also have implications for proton acceleration. For example, solar energetic particle events typically occur with a higher intensity, whenever multiple CMEs occur in quick succession from the same source region. CME deflection may also have implications to the arrival of energetic particles to earth because magnetic connectivity may be changed by the interaction. I illustrate the above points using examples from SOHO, STEREO, Wind, and ACE data .

Gopalswarny, Nat↗

DOE OSTI2022

Towards a neutron multiplicity measurement with the Accelerator Neutrino Neutron Interaction Experiment

The Accelerator Neutrino Neutron Interaction Experiment (ANNIE) is a 26 ton Gadolinium (Gd)-loaded water Cherenkov detector located on the Booster Neutrino Beam line at Fermilab. Its main goals are the measurement of the neutron multiplicity in neutrino-nucleus interactions as well as the cross-section of Charged Current Quasi-Elastic (CCQE) neutrino interactions on water. Besides the physics goals, the experiment also aims to be a testbed for new technologies such as Large Area Picosecond Photodetectors (LAPPDs) and Water-based Liquid Scintillators (WbLS). This thesis presents a preliminary measurement of the neutron multiplicity with {ANNIE}, using an analysis conducted on a fraction of the 2021 beam year. As preparatory measures, the efficiency of ANNIE's Front Muon Veto (FMV) was determined to be {$\bar{\varepsilon}_{\mathrm{FMV}} = (95.6 \pm 1.6)\%$} while the average efficiency for active scintillator paddles in the Muon Range Detector (MRD) was found to be {$\bar{\varepsilon}_ {\mathrm{MRD}} = (92.1 \pm 7.9)\%$}. Furthermore, the simulation framework used for ANNIE was validated and adapted to reproduce the experimental data by comparing the detector response for samples of Michel electrons, Americium Beryllium neutrons, and through-going muons. The analysis finds average neutron yields of {$\bar{n}_{\mathrm{data}} (\mathrm{beam}) = (0.272 \pm 0.010_{\mathrm{stat}})$} for an inclusive set of all identified muon neutrino candidates and {$\bar{n}_{\mathrm{data}} (\mathrm{beam,FV}) = (0.287 \pm 0.044_{\mathrm{stat}})$ for interactions which happened inside of the Fiducial Volume of ANNIE, which was optimized to increase the neutron detection acceptance. The presented neutron multiplicity values represent the number of detected neutrons after all event selection cuts and are not yet corrected for the neutron detection efficiency. An equivalent analysis on a simulated beam sample predicts neutron yields of $\bar{n}_{\mathrm{MC}}(\mathrm{beam}) = (0.515 \pm 0.0 07_{\mathrm{stat}})$ and $\bar{n}_{\mathrm{MC}}(\mathrm{beam,FV}) = (0.627 \pm 0.031_{\mathrm{stat}})$, indicating that the models tend to overpredict the number of neutrons produced in such interactions. Systematic errors have been briefly considered to contribute {$\sigma_{\mathrm{sys,FMV}} \sim 0.01\,$neutrons/$\nu$-interaction} due to the slight FMV inefficiency and {$\sigma_{\mathrm{sys,n}} \sim 0.05\,$neutrons/$\nu$-interaction} due to the neutron detection efficiency. Simulation studies further highlighted the importance of neutron detection in Diffuse Supernova Background (DSNB) searches. A combination of neutron tagging and Convolutional Neural Networks was found to reduce the most relevant Neutral Current Quasi-Elastic (NCQE) interaction background below the signal level, achieving a Signal-to-Background ratio of 4:1. In a further study, we investigated the positive impact of a deployment of a WbLS target on the energy reconstruction in ANNIE. WbLS provides a scintillation signal from hadronic recoils in addition to the charged lepton that can be included in neutrino energy reconstruction. It was found that a deployed WbLS volume in ANNIE improves the neutrino energy reconstruction from 14\% to 12\%, with the potential of going beyond this if more sophisticated reconstruction algorithms are developed in the future.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2026

Neutrino-Argon Cross Sections in MicroBooNE: Measurements Spanning Multiple Interaction Channels, Final States, and Neutrino Fluxes

Neutrinos are one of the most elusive particles in the Standard Model of particle physics due to their tiny interaction cross section, which makes them challenging to detect and study. There are three known flavors of neutrinos, and any given neutrino probabilistically oscillates between them as a function of the particle's energy and propagation distance. Experimental characterization of these oscillations elucidates fundamental properties of the neutrino and the Standard Model. Meeting the precision goals of ongoing and future oscillation measurements requires detailed modeling of the way neutrinos interact with nuclear matter. Precision modeling of these interactions is a challenging theoretical problem, rich with intricate physics effects to explore, and requires input from equally precise measurements of neutrino-nucleus interaction cross sections spanning a broad range of scattering channels. To fill this need, there is an ongoing multi-experiment effort to measure these cross sections across energies, interaction channels, and nuclear targets. This thesis describes three analyses reporting neutrino-argon cross section measurements with data from the MicroBooNE liquid argon time projection chamber detector. These span multiple interaction channels, final state topologies, and neutrino fluxes. The first analysis is a set of inclusive charged current muon neutrino cross section measurements for final states with and without protons, which provides a unique view of the hadronic final state produced in these interactions. Second is a set of cross section measurements for neutral current neutral pion production, which provides a vital dataset on this under-characterized channel. Third is significant progress on measuring neutrinos produced by kaons decaying at rest, which represents a unique opportunity to measure cross sections with a mono-energetic flux of neutrinos. These measurements are accompanied by a modeling study in the GiBUU theory framework, which probes the sensitivity of the muon neutrino and pion production measurements to the modeling of nucleon-nucleon final state interactions in neutrino-nucleus scattering.

Bogart, Benjamin [Michigan U.]↗

DOE OSTI2025

Effect of tert -Butyl Substitution on the Interactions of Cobalt Phthalocyanine with a Carbon Monoxide-Functionalized Tip

Supported cobalt phthalocyanines (CoPc) are promising catalysts for CO 2 reduction, a critical process for mitigating greenhouse gas emissions. Enhancing the catalytic performance of CoPc involves modifying the interaction between the cobalt center and intermediate species. This study focuses on the effects of tert-butyl substitution on CoPc using (tert-butyl) 4 CoPc, where the substitution can both directly alter the molecule’s intramolecular electronic structure and indirectly alter it by the bulky group weakening the interaction with the support. Toward this end, we investigated the structural and chemical properties of (tert-butyl) 4 CoPc on a Ag(111) surface at the single-molecule level using three-dimensional atomic force microscopy (AFM) with a CO-terminated tip and discussed them in comparison with data for unmodified CoPc and amino-substituted CoPc. Notably, distance-dependent force measurements revealed anomalies in the tert-butyl groups’ force curves, attributed to their rotational flexibility. The tert-butyl (t-butyl) groups were also observed to increase the attraction of the central Co atom to CO, but this effect was attributed largely to enhanced interactions of the back of the tip with the peripheral t-butyl groups. In conclusion, while this longer-range interaction would not be expected to impact the interaction of small molecules with the catalytic center, the results reveal the ability of AFM to characterize longer range environmental interactions that can enhance adsorption and subsequent reactions of larger molecules, as well as the role side chains that offer configurational adaptability may play in these interactions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2020

Effects of Noncovalent Interactions on High-Spin Fe(IV)–Oxido Complexes

High-valent nonheme Fe IV –oxido species are key intermediates in biological oxidation, and their properties are proposed to be influenced by the unique microenvironments present in protein active sites. Microenvironments are regulated by noncovalent interactions, such as hydrogen bonds (H-bonds) and electrostatic interactions; however, there is little quantitative information about how these interactions affect crucial properties of high valent metal–oxido complexes. To address this knowledge gap, we introduced a series of Fe IV –oxido complexes that have the same S = 2 spin ground state as those found in nature and then systematically probed the effects of noncovalent interactions on their electronic, structural, and vibrational properties. The key design feature that provides access to these complexes is the new tripodal ligand [poat] 3– , which contains phosphinic amido groups. An important structural aspect of [Fe IV poat(O)] - is the inclusion of an auxiliary site capable of binding a Lewis acid (LA II ); we used this unique feature to further modulate the electrostatic environment around the Fe–oxido unit. Experimentally, studies confirmed that H-bonds and LA II s can interact directly with the oxido ligand in Fe IV –oxido complexes, which weakens the Fe=O bond and has an impact on the electronic structure. Additionally, we found that relatively large vibrational changes in the Fe–oxido unit correlate with small structural changes that could be difficult to measure, especially within a protein active site. Our work demonstrates the important role of noncovalent interactions on the properties of metal complexes, and that these interactions need to be considered when developing effective oxidants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗