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At least 1,333 records · Page 74

Evaluation of CSI enhancements for jitter reduction on the EOS AM-1 observatory

A collaborative study between the Goddard Space Flight Center and the Langley Research Center is now underway to investigate the application of Control-Structure Integration (CSI) technologies to the EOS AM-1 spacecraft. Preliminary GN&C pointing studies of EOS AM-1, performed in 1991 and 1992, have indicated the potential for low pointing jitter and stability margins. Hence, a detailed baseline and CSI enhanced jitter assessment has been undertaken. This paper describes the spacecraft jitter pointing requirements, finite element models, and on-board disturbances. The jitter assessment approach being used by the NASA LaRC and various tools developed for efficient simulation and analysis of jitter are presented. In addition, preliminary results are given to show the potential need of CSI technologies for improving pointing performance of the spacecraft.

Belvin, W. K.↗

Electronic structure and optical properties of α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} solid-solution thin films

We have examined the effect of V doping on the electronic and optical properties of epitaxial hematite (α-Fe{sub 2}O{sub 3}) thin films, by employing several characterization techniques and computational modeling. The conductivity of α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} (0 ≤ x ≤ ∼0.5) is enhanced by several orders of magnitude as x is increased, as evidenced by electrical resistivity measurements and x-ray photoelectron spectroscopy core-level and valence-band spectra. Optical absorption shows a reduction in the direct band gap by as much as 0.64 eV for x = 0.53 (E{sub g} = 1.46 eV) relative to that of α-Fe{sub 2}O{sub 3} (E{sub g} = 2.10 eV). Detailed understanding of the character of the optical transitions in the alloys is achieved using first-principles calculations of the ground and excited states. These calculations reveal that V doping results in occupied V 3d orbitals hybridized with Fe orbitals and located at approximately mid-gap in α-Fe{sub 2}O{sub 3}. The lowest energy transitions involve charge transfer from occupied V 3d to unoccupied Fe 3d* orbitals. With a low band gap and high conductivity, α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} is a promising material for photovoltaic and photoelectrochemical applications.

36 MATERIALS SCIENCE↗

Methods for Reducing Normal Tissue Complication Probabilities in Oropharyngeal Cancer: Dose Reduction or Planning Target Volume Elimination

Purpose: Strategies to reduce the toxicities of head and neck radiation (ie, dysphagia [difficulty swallowing] and xerostomia [dry mouth]) are currently underway. However, the predicted benefit of dose and planning target volume (PTV) reduction strategies is unknown. The purpose of the present study was to compare the normal tissue complication probabilities (NTCP) for swallowing and salivary structures in standard plans (70 Gy [P70]), dose-reduced plans (60 Gy [P60]), and plans eliminating the PTV margin. Methods and Materials: A total of 38 oropharyngeal cancer (OPC) plans were analyzed. Standard organ-sparing volumetric modulated arc therapy plans (P70) were created and then modified by eliminating the PTVs and treating the clinical tumor volumes (CTVs) only (C70) or maintaining the PTV but reducing the dose to 60 Gy (P60). NTCP dose models for the pharyngeal constrictors, glottis/supraglottic larynx, parotid glands (PGs), and submandibular glands (SMGs) were analyzed. The minimal clinically important benefit was defined as a mean change in NTCP of >5%. The P70 NTCP thresholds and overlap percentages of the organs at risk with the PTVs (56-59 Gy, vPTV{sub 56}) were evaluated to identify the predictors for NTCP improvement. Results: With the P60 plans, only the ipsilateral PG (iPG) benefited (23.9% vs 16.2%; P<.01). With the C70 plans, only the iPG (23.9% vs 17.5%; P<.01) and contralateral SMG (cSMG) (NTCP 32.1% vs 22.9%; P<.01) benefited. An iPG NTCP threshold of 20% and 30% predicted NTCP benefits for the P60 and C70 plans, respectively (P<.001). A cSMG NTCP threshold of 30% predicted for an NTCP benefit with the C70 plans (P<.001). Furthermore, for the iPG, a vPTV{sub 56} >13% predicted benefit with P60 (P<.001) and C70 (P=.002). For the cSMG, a vPTV{sub 56} >22% predicted benefit with C70 (P<.01). Conclusions: PTV elimination and dose-reduction lowered the NTCP of the iPG, and PTV elimination lowered the NTCP of the cSMG. NTCP thresholds and the percentage of overlap of the PTV with organs at risk can predict which patients will benefit and inform future clinical trial design.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Fort Nelson Test Site - Site Characterization Report

The Plains CO 2 Reduction (PCOR) Partnership, led by the Energy & Environmental Research Center (EERC), is working with Spectra Energy Transmission (SET) to determine the feasibility of large-scale injection of carbon dioxide (CO 2 ) into a deep brine-saturated carbonate formation near Fort Nelson, British Columbia, Canada, for the purpose of CO 2 storage. Site characterization must be conducted prior to large-scale injection of CO 2 at the Fort Nelson test site. Effective characterization supports modeling; risk assessment; and monitoring, verification, and accounting (MVA) programs that will constantly evolve to suit the project’s needs. Site characterization activities have been conducted to address three critical issues affecting the viability of the Fort Nelson test site: 1) the capacity of the target formation, 2) injectivity, and 3) containment – the potential for leakage of the injected CO 2 into overlying formations and/or the near-surface environment. Geochemical, mineralogical/petrophysical, geomechanical, and hydrogeological data have been collected for the purpose of supporting modeling, risk assessment, and MVA activities. The geology, stratigraphy, and lithology have been evaluated, delineated, and described for the entire sedimentary succession from the base of the Devonian age Presqu’ile reef complex to the top of the Fort Simpson shale (cap rock) in the Fort Nelson project area. The structural elements of the reef complex have been investigated to identify any existing faults and/or fractures that would allow migration of any reservoir and/or injected fluids out of the storage reservoir. On this basis, a geologic model has been built, with particular attention given to the Devonian injection interval and overlying and underlying sealing formations.

54 ENVIRONMENTAL SCIENCES↗

Randomized Preconditioned Solvers for Strong Constraint 4D-Var Data Assimilation

The Strong Constraint 4D Variational (SC-4DVAR) data assimilation method is widely used in climate and weather applications. SC-4DVAR involves solving a minimization problem to compute the maximum a posteriori estimate, which we tackle using the Gauss-Newton method. The computation of the descent direction is expensive since it involves the solution of a large-scale and potentially ill-conditioned linear system, solved using the preconditioned conjugate gradient (PCG) method. Here, to address this cost, we efficiently construct scalable preconditioners using three different randomization techniques, which all rely on a certain low-rank structure involving the Gauss-Newton Hessian. The proposed techniques come with theoretical guarantees on the condition number, and at the same time, are amenable to parallelization. We also develop an adaptive approach to estimate the sketch size and choose between the reuse or recomputation of the preconditioner. We demonstrate the performance and effectiveness of our methodology on two representative model problems—the Burgers and barotropic vorticity equation—showing a drastic reduction in both the number of PCG iterations and the number of Gauss-Newton Hessian products after including the preconditioner construction cost.

Gauss-Newton↗

Atomistic Insight into Cation Effects on Binding Energies in Cu-Catalyzed Carbon Dioxide Reduction

Electrolyte properties in general and electrolyte ions in particular have been shown to have significant effects on the kinetics of electrochemical CO 2 and CO reduction at metal electrodes, but these effects have not yet been fully understood. Here, we investigate the effects of cations at the aqueous electrolyte–Cu(211) interface on adsorbate binding energies and the electrolyte structure using density functional theory (DFT). Charging the interface via explicit Na + has systematic effects on adsorbate–electrolyte interactions and conformations. We describe specific local adsorbate–ion interactions, including direct alkali ion–adsorbate coordination and hydrogen bonding via ion-coordinated water molecules. The relative importance of these specific interactions and purely electrostatic field–adsorbate interactions is investigated by comparing the DFT-calculated ion effects to those predicted by purely electrostatic models of the interface and the adsorbates. We find that the trend in ion effects among different adsorbates at constant surface charge density is well explained by a purely electrostatic interaction model. The binding energy of OCCHO is found to depend strongly on the surface charge density as well as the spatial distribution of ions at constant surface charge density. These effects are also explained by a purely electrostatic local electrostatic field–adsorbate model. This indicates that alkali ion effects can be mainly attributed to purely electrostatic field interactions and that the local field at ion-stabilized active sites can depend significantly on both the overall charge density and on the spatial distribution of ions at constant charge density. This work provides new insight on alkali ion effects on a variety of adsorbates relevant to the CO 2 and CO reduction reactions by describing specific local ion–adsorbate interactions, systematic changes in adsorbate–electrolyte interactions induced by explicit surface charge, and comparisons of the calculated effects on binding energies to simple electrostatic field–adsorbate models to explain trends among various adsorbates and at varying surface charge densities and supercell configurations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tocopherol Activity Correlates with its Location in a Membrane: A New Perspective on the Anti-Oxidant Vitamin E

We show evidence of an antioxidant mechanism for vitamin E which correlates strongly with its physical location in a model lipid bilayer. This data addresses the overlooked problem of the physical distance between the vitamin's reducing hydrogen and lipid acyl chain radicals. Our combined data from neutron diffraction, NMR and UV spectroscopy experiments, all suggest that reduction of reactive oxygen species and lipid radicals occurs specifically at the membrane's hydrophobic-hydrophilic interface. The latter is possible when the acyl chain snorkels to the interface from the hydrocarbon matrix. Moreover, not all model lipids are equal in this regard, as indicated by the small differences in vitamin's location. The present result is a clear example of the importance of lipid diversity in controlling the dynamic structural properties of biological membranes. Importantly, our results suggest that measurements of aToc oxidation kinetics, and its products, should be revisited by taking into consideration the physical properties of the membrane in which the vitamin resides.

Marquardt, Drew↗

HELIOSEISMOLOGY OF A REALISTIC MAGNETOCONVECTIVE SUNSPOT SIMULATION

We compare helioseismic travel-time shifts measured from a realistic magnetoconvective sunspot simulation using both helioseismic holography and time-distance helioseismology, and measured from real sunspots observed with the Helioseismic and Magnetic Imager instrument on board the Solar Dynamics Observatory and the Michelson Doppler Imager instrument on board the Solar and Heliospheric Observatory. We find remarkable similarities in the travel-time shifts measured between the methodologies applied and between the simulated and real sunspots. Forward modeling of the travel-time shifts using either Born or ray approximation kernels and the sound-speed perturbations present in the simulation indicates major disagreements with the measured travel-time shifts. These findings do not substantially change with the application of a correction for the reduction of wave amplitudes in the simulated and real sunspots. Overall, our findings demonstrate the need for new methods for inferring the subsurface structure of sunspots through helioseismic inversions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Reducing Memory Consumption in Calico with Shared Memory

This document details the work to reduce memory consumption in Calico. Calico is SimTools’ Constructive Solid Geometry (CSG) and geometry painting library. It is primarily used to paint material volume fractions in the Eulerian meshes of the physics codes. Calico provides point-in-body checks for the geometry supplied by an Oso model, which are then aggregated by the host codes. In addition, Calico can be used to build Oso models and is used by Ingen for that purpose. Oso models, and thus Calico, provide support for various CSG primitives such as spheres, cylinders, surfaces generated by rotating tabular curve data, and STL files as well as binary combinations of those primitives. Prior to refactoring Calico will run out of memory on CTS-1 machines when 36 MPI ranks are used per node when reading STL models on the order of 1.5 GB. This limitation is a bottleneck in designer workflow. This problem has been alleviated through the use of data structures to both reduce memory consumption and to leverage MPI-3 shared memory. This report details the data structures targeted for refactoring in Calico, the methods and implementation details for reducing memory consumption and leveraging shared memory, and results for one test problem. Results show a memory reduction when loading a 1 GB STL file by a factor of 27.5, from 93.4 to 3.4 GB.

97 MATHEMATICS AND COMPUTING↗

NASA Tech Briefs, February 2011

Topics covered include: Multi-Segment Radius Measurement Using an Absolute Distance Meter Through a Null Assembly; Fiber-Optic Magnetic-Field-Strength Measurement System for Lightning Detection; Photocatalytic Active Radiation Measurements and Use; Computer Generated Hologram System for Wavefront Measurement System Calibration; Non-Contact Thermal Properties Measurement with Low-Power Laser and IR Camera System; SpaceCube 2.0: An Advanced Hybrid Onboard Data Processor; CMOS Imager Has Better Cross-Talk and Full-Well Performance; High-Performance Wireless Telemetry; Telemetry-Based Ranging; JWST Wavefront Control Toolbox; Java Image I/O for VICAR, PDS, and ISIS; X-Band Acquisition Aid Software; Antimicrobial-Coated Granules for Disinfecting Water; Range 7 Scanner Integration with PaR Robot Scanning System; Methods of Antimicrobial Coating of Diverse Materials; High-Operating-Temperature Barrier Infrared Detector with Tailorable Cutoff Wavelength; A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane; Thermally Conductive Tape Based on Carbon Nanotube Arrays; Two Catalysts for Selective Oxidation of Contaminant Gases; Nanoscale Metal Oxide Semiconductors for Gas Sensing; Lightweight, Ultra-High-Temperature, CMC-Lined Carbon/Carbon Structures; Sample Acquisition and Handling System from a Remote Platform; Improved Rare-Earth Emitter Hollow Cathode; High-Temperature Smart Structures for Engine Noise Reduction and Performance Enhancement; Cryogenic Scan Mechanism for Fourier Transform Spectrometer; Piezoelectric Rotary Tube Motor; Thermoelectric Energy Conversion Technology for High-Altitude Airships; Combustor Computations for CO2-Neutral Aviation; Use of Dynamic Distortion to Predict and Alleviate Loss of Control; Cycle Time Reduction in Trapped Mercury Ion Atomic Frequency Standards; and A (201)Hg+ Comagnetometer for (199)Hg+ Trapped Ion Space Atomic Clocks.

Source record↗

Helioseismology of a Realistic Magnetoconvective Sunspot Simulation

We compare helioseismic travel-time shifts measured from a realistic magnetoconvective sunspot simulation using both helioseismic holography and time-distance helioseismology, and measured from real sunspots observed with the Helioseismic and Magnetic Imager instrument on board the Solar Dynamics Observatory and the Michelson Doppler Imager instrument on board the Solar and Heliospheric Observatory. We find remarkable similarities in the travel-time shifts measured between the methodologies applied and between the simulated and real sunspots. Forward modeling of the travel-time shifts using either Born or ray approximation kernels and the sound-speed perturbations present in the simulation indicates major disagreements with the measured travel-time shifts. These findings do not substantially change with the application of a correction for the reduction of wave amplitudes in the simulated and real sunspots. Overall, our findings demonstrate the need for new methods for inferring the subsurface structure of sunspots through helioseismic inversions.

Sun-interior↗

Internal Structural Design of the Common Research Model Wing Box for Aeroelastic Tailoring

This work explores the use of alternative internal structural designs within a full-scale wing box structure for aeroelastic tailoring, with a focus on curvilinear spars, ribs, and stringers. The baseline wing model is a fully-populated, cantilevered wing box structure of the Common Research Model (CRM). Metrics of interest include the wing weight, the onset of dynamic flutter, and the static aeroelastic stresses. Twelve parametric studies alter the number of internal structural members along with their location, orientation, and curvature. Additional evaluation metrics are considered to identify design trends that lead to lighter-weight, aeroelastically stable wing designs. The best designs of the individual studies are compared and discussed, with a focus on weight reduction and flutter resistance. The largest weight reductions were obtained by removing the inner spar, and performance was maintained by shifting stringers forward and/or using curvilinear ribs: 5.6% weight reduction, a 13.9% improvement in flutter speed, but a 3.0% increase in stress levels. Flutter resistance was also maintained using straight-rotated ribs although the design had a 4.2% lower flutter speed than the curved ribs of similar weight and stress levels were higher. For some configurations, the differences between curved and straight ribs were smaller, which provides motivation for future optimization-based studies to fully exploit the trade-offs.

Jutte, Christine V.↗

Multi-point Jig Twist Optimization of Mach 0.745 Transonic Truss-Braced Wing Aircraft and High-Fidelity CFD Validation

This paper presents a multi-point jig twist optimization study of the Mach 0.745 Transonic Truss-Braced Wing (TTBW) aircraft using an in-house developed aero-structural analysis solver VSPAERO coupled to BEAM3D. A vortex-lattice model of the TTBW model is developed, and a transonic small disturbance /integral boundary layer correction method is implemented in the VSPAERO model to account for transonic and viscous flow effects. A correction method for the wing-strut interference aerodynamics is developed and applied to the VSPAERO solver. Also, a structural dynamic finite-element model of the TTBW aircraft is developed. This finite-element model includes the geometric nonlinear effect due to the tension in the struts which causes a deflection-dependent nonlinear stiffness. The VSPAERO model is coupled to the corresponding finite-element model to provide a rapid aero-structural analysis. The VSPAERO model has been validated against wind tunnel test data and FUN3D CFD simulation data. Three different flight conditions corresponding to Mach 0.745 at 40,000 ft are selected for the TTBW aircraft jig twist optimization to reduce the drag coefficients at the design and off-design cruise lift coefficients. The preliminary optimization results show that the TTBW aircraft with the optimized jig twist achieves a drag reduction of about 9 counts, 7 counts, and8 counts corresponding to the lift coefficients 0.68, 0.73, and 0.78, respectively. A high-fidelity CFD solver FUN3D is used to validate the jig twist optimization.

Multi-point↗

Approximation methods for control of structural acoustics models with piezoceramic actuators

The active control of acoustic pressure in a 2-D cavity with a flexible boundary (a beam) is considered. Specifically, this control is implemented via piezoceramic patches on the beam which produces pure bending moments. The incorporation of the feedback control in this manner leads to a system with an unbounded input term. Approximation methods in this manner leads to a system with an unbounded input term. Approximation methods in this manner leads to a system with an unbounded input team. Approximation methods in the context of linear quadratic regulator (LQR) state space control formulation are discussed and numerical results demonstrating the effectiveness of this approach in computing feedback controls for noise reduction are presented.

Banks, H. T.↗

Pesticide risk perceptions and the differences between farmers and extensionists: Towards a knowledge-in-context model

A growing body of literature analyzes farmer perceptions of pesticide risk, but much less attention has been given to differences in risk perception between farmers and technical experts. Furthermore, inconsistencies in knowledge have too easily been explained in terms of lack of knowledge rather than exploring the underlying reasons for particular forms of thinking about pesticide risks. By doing this, the division between expert and lay knowledge has been deepened rather than transcended. Objective: This study aims to understand differences and similarities among the perceptions of pesticide risks of farmers, farm workers, and technical experts such as extensionists, by applying a social science approach towards knowledge and risk attitudes. Methods: Semi-structured interviews and field observations were conducted to smallholders, farm workers, extensionists, health professionals and scientists involved in the use and handling of pesticides. Subsequently, a survey was carried out to quantify the farmers and extensionists' acceptance or rejection of typical assertions expressed previously in the semi-structured interviews. Results: Smallholders showed to gain knowledge from their own experiences and to adapt pesticides practices, which is a potential basis for transforming notions of pesticide safety and risk reduction strategies. Though extensionists have received formal education, they sometimes develop ideas deviating from the technical perspective. The risk perception of the studied actors appeared to vary according to their role in the agricultural labor process; they varied much less than expected according to their schooling level. Conclusions: Commitment to the technical perspective is not dramatically different for extensionists on the one hand and farmers as well as farm workers on the other hand. Ideas about a supposed lack of knowledge by farmers and the need of formal training are too much driven by a deficit model of knowledge. Further research on risk perceptions of pesticides and training of rural people will benefit from the development of a knowledge-in-context model. -- Highlights: • Researching perceptions of farmers' extensionists and other professionals. • Experts as well as farmers deviate from the technical perspective. • Blaming who is responsible for pesticide problems creates expert-lay division. • Qualitative and quantitative methods, not as complementary but integrated. • Knowledge-in-context model as an alternative to the knowledge-deficit model.

60 APPLIED LIFE SCIENCES↗

The Dynamics of Shock Dispersion and Interactions in Supersonic Freestreams with Counterflowing Jets

An active flow control concept using counterflowing jets to significantly modify the external flowfields and strongly weaken or disperse the shock-waves of supersonic and hypersonic vehicles to reduce the aerothermal loads and wave drag was investigated. Experiments were conducted in a trisonic blow-down wind-tunnel, complemented by pre-test computational fluid dynamics (CFD) analysis of a 2.6% scale model of Apollo capsule, with and without counterflowing jets, in Mach 3.48 and 4.0 freestreams, to assess the potential aerothermal and aerodynamic benefits of this concept. The model was instrumented with heat flux gauges, thermocouples and pressure taps, and employed five counterflowing jet nozzles (three sonic and other two supersonic with design Mach numbers of 2.44 and 2.94) and nozzle exit diameters ranging from 0.25 to 0.5 inch. Schlieren data show that at low jet flow rates of 0.05 and 0.1lb(sub m)/sec, the interactions result in a long penetration mode (LPM) jet, while the short penetration mode (SPM) jet is observed at flow rates greater than 0.1 lb(sub m)/sec., consistent with the pre-test CFD predictions. For the LPM, the jet appears to be nearly fully-expanded, resulting in a very unsteady and oscillatory flow structure in which the bow shock becomes highly dispersed such that it is no longer discernable. Higher speed camera Schlieren data reveal the shock to be dispersed into striations of compression waves, which suddenly coalesce to a weaker bow shock with a larger standoff distance as the flow rate reached a critical value. The pronounced shock dispersion could significantly impact the aerodynamic performance (L/D) and heat flux reduction of spacecraft in atmospheric entry and re-entry, and could also attenuate the entropy layer in hypersonic blunt body flows. For heat transfer, the results show significant reduction in heat flux, even giving negative heat flux for some of the SPM interactions, indicating that the flow wetting the model is cooling, instead of heating the model, which could significantly impact the requirements and design of thermal protection system. These findings strongly suggest that the application of counterflowing jets as active flow control could have strong impact on supersonic and hypersonic vehicle design and performance.

Daso, Endwell O.↗

Drug Delivery Through the Skin: Molecular Simulations of Barrier Lipids to Design more Effective Noninvasive Dermal and Transdermal Delivery Systems for Small Molecules Biologics and Cosmetics

The delivery of drugs through the skin provides a convenient route of administration that is often preferable to injection because it is noninvasive and can typically be self-administered. These two factors alone result in a significant reduction of medical complications and improvement in patient compliance. Unfortunately, a significant obstacle to dermal and transdermal drug delivery alike is the resilient barrier that the epidermal layers of the skin, primarily the stratum corneum, presents for the diffusion of exogenous chemical agents. Further advancement of transdermal drug delivery requires the development of novel delivery systems that are suitable for modern, macromolecular protein and nucleotide therapeutic agents. Significant effort has already been devoted to obtain a functional understanding of the physical barrier properties imparted by the epidermis, specifically the membrane structures of the stratum corneum. However, structural observations of membrane systems are often hindered by low resolutions, making it difficult to resolve the molecular mechanisms related to interactions between lipids found within the stratum corneum. Several models describing the molecular diffusion of drug molecules through the stratum corneum have now been postulated, where chemical permeation enhancers are thought to disrupt the underlying lipid structure, resulting in enhanced permeability. Recent investigations using biphasic vesicles also suggested a possibility for novel mechanisms involving the formation of complex polymorphic lipid phases. In this review, we discuss the advantages and limitations of permeation-enhancing strategies and how computational simulations, at the atomic scale, coupled with physical observations can provide insight into the mechanisms of diffusion through the stratum corneum.

59 BASIC BIOLOGICAL SCIENCES↗

A mononuclear nonheme {FeNO} 6 complex: synthesis and structural and spectroscopic characterization

While the synthesis and characterization of {FeNO} 7,8,9 complexes have been well documented in heme and nonheme iron models, {FeNO} 6 complexes have been less clearly understood. Herein, we report the synthesis and structural and spectroscopic characterization of mononuclear nonheme {FeNO} 6 and iron(III)–nitrito complexes bearing a tetraamido macrocyclic ligand (TAML), such as [(TAML)Fe III (NO)] - and [(TAML)Fe III (NO 2 )] 2- , respectively. First, direct addition of NO (g) to [Fe III (TAML)] - results in the formation of [(TAML)Fe III (NO)] - , which is sensitive to moisture and air. The spectroscopic data of [(TAML)Fe III (NO)] - , such as 1 H nuclear magnetic resonance and X-ray absorption spectroscopies, combined with computational study suggest the neutral nature of nitric oxide with a diamagnetic Fe center (S = 0). We also provide alternative pathways for the generation of [(TAML)Fe III (NO)] - , such as the iron–nitrite reduction triggered by protonation in the presence of ferrocene, which acts as an electron donor, and the photochemical iron–nitrite reduction. To the best of our knowledge, the present study reports the first photochemical nitrite reduction in nonheme iron models.

36 MATERIALS SCIENCE↗