SEARCH · Engineering Papers

Results for “Substrate Specificity”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 595 records · Page 33

All sources NASA NTRS DOE OSTI

DOE OSTI2025

Time-resolved chemically-selective spectroscopic investigation of the redox reaction between hematite and aluminium

Thermite reactions –highly energetic redox processes between a metal and an oxide—are used in welding, propulsion, and the fabrication of advanced materials. When reduced to the nanoscale, these reactions exhibit enhanced energetic performance, but their ultrafast dynamics remain poorly understood. Gaining insight into charge transfer during these processes is essential for advancing applications in energy conversion and materials design. Here we show that the reaction between aluminium and hematite, a common iron oxide, can be tracked with femtosecond resolution using extreme ultraviolet (EUV) time-resolved absorption spectroscopy at the Fe M 2,3 and Al L 2,3 edges. By exciting the system with an ultrashort optical pulse and probing element-specific absorption changes, we observe an early spectral shift that reveals the formation of localized charge carriers (polarons). Comparing samples with different supporting substrates highlights ultrafast electron transfer from aluminium to hematite. These results demonstrate an approach to investigating charge flow in energetic materials and provide a basis for studying fast chemical reactions with chemical specificity.

Electron transfer↗

NASA NTRS2013

Opto-mechanical Analyses for Performance Optimization of Lightweight Grazing-incidence Mirrors

New technology in grazing-incidence mirror fabrication and assembly is necessary to achieve sub-arcsecond optics for large-area x-ray telescopes. In order to define specifications, an understanding of performance sensitivity to design parameters is crucial. MSFC is undertaking a systematic study to specify a mounting approach, mirror substrate, and testing method. Because the lightweight mirrors are typically flimsy, they are susceptible to significant distortion due to mounting and gravitational forces. Material properties of the mirror substrate along with its thickness and dimensions significantly affect the distortions caused by mounting and gravity. A parametric study of these properties and their relationship to mounting and testing schemes will indicate specifications for the design of the next generation of lightweight grazing-incidence mirrors. Initial results will be reported.

Roche, Jacqueline↗

NASA NTRS2013

Opto-Mechanical Analyses for Performance Optimization of Lightweight Grazing-Incidence Mirrors

Roche, Jacqueline↗

NASA NTRS2015

Evolving Design Criteria for Very Large Aperture Space-Based Telescopes and Their Influence on the Need for Integrated Tools in the Optimization Process

NASA's Advanced Mirror Technology Development (AMTD) program has been developing the means to design and build the future generations of space based telescopes. With the nearing completion of the James Webb Space Telescope (JWST), the astrophysics community is already starting to define the requirements for follow on observatories. The restrictions of available launch vehicles and the possibilities of planned future vehicles have fueled the competition between monolithic primaries (with better optical quality) and segmented primaries (with larger apertures, but with diffraction, costs and figure control issues). Regardless of the current shroud sizes and lift capacities, these competing architectures share the need for rapid design tools. As part of the AMTD program a number of tools have been developed and tested to speed up the design process. Starting with the Arnold Mirror Modeler (which creates Finite Element Models (FEM) for structural analysis) and now also feeds these models into thermal stability analyses. They share common file formats and interchangeable results. During the development of the program, numerous trade studies were created for 4 meter and 8 meter monolithic primaries, complete with support systems. Evaluation of these results has led to a better understanding of how the specification drives the results. This paper will show some of the early trade studies for typical specification requirements such as lowest mirror bending frequency and suspension system lowest frequency. The results use representative allowable stress values for each mirror substrate material and construction method and generic material properties. These studies lead to some interesting relationships between feasible designs and the realities of actually trying to build these mirrors. Much of the traditional specifications were developed for much smaller systems, where the mass and volume of the primary where a small portion of the overall satellite. JWST shows us that as the aperture grows, the primary takes up the majority of the mass and volume and the established rules need to be adjusted. For example, a small change in lowest frequency requirement can change the cost by millions of dollars.

Space-based telescopes↗

NASA NTRS2015

Evolving Design Criteria for Very Large Aperture Space Based Telescopes and Their Influence on the Need for Integrated Tools in the Optimization Process

NASA's Advanced Mirror Technology Development (AMTD) program has been developing the means to design and build the future generations of space based telescopes. With the nearing completion of the James Webb Space Telescope (JWST), the astrophysics community is already starting to define the requirements for follow-on observatories. The restrictions of available launch vehicles and the possibilities of planned future vehicles have fueled the competition between monolithic primaries (with better optical quality) and segmented primaries (with larger apertures, but with diffraction, costs and figure control issues). Regardless of the current shroud sizes and lift capacities, these competing architectures share the need for rapid design tools. As part of the AMTD program a number of tools have been developed and tested to speed up the design process. Starting with the Arnold Mirror Modeler (which creates Finite Element Models (FEM) for structural analysis) and now also feeds these models into thermal stability analyses. They share common file formats and interchangeable results. During the development of the program, numerous trade studies were created for 4-meter and 8-meter monolithic primaries, complete with support systems. Evaluation of these results has led to a better understanding of how the specification drives the results. This paper will show some of the early trade studies for typical specification requirements such as lowest mirror bending frequency and suspension system lowest frequency. The results use representative allowable stress values for each mirror substrate material and construction method and generic material properties. These studies lead to some interesting relationships between feasible designs and the realities of actually trying to build these mirrors. Much of the traditional specifications were developed for much smaller systems, where the mass and volume of the primary where a small portion of the overall satellite. JWST shows us that as the aperture grows, the primary takes up the majority of the mass and volume and the established rules need to be adjusted. For example, a small change in lowest frequency requirement can change the cost by millions of dollars. The paper uses numerous trade studies created during the software development phase of the Arnold Mirror Modeler to illustrate the influences of system specifications on the design space. The future telescopes will require better performance, stability and documented feasibility to meet the hurdles of today's budget and schedules realities. AMTD is developing the tools, but the basic system planning mentality also has to adopt to the requirements of these very large and complex physical structures.

Arnold, William R., Sr.↗

NASA NTRS1999

Stratified Volume Diffractive Optical Elements as Low-Mass Coherent Lidar Scanners

Transmissive scanning elements for coherent laser radar systems are typically optical wedges, or prisms, which deflect the lidar beam at a specified angle and are then rotated about the instrument optical axis to produce a scan pattern. The wedge is placed in the lidar optical system subsequent to a beam-expanding telescope, implying that it has the largest diameter of any element in the system. The combination of the wedge diameter and asymmetric profile result in the element having very large mass and, consequently, relatively large power consumption required for scanning. These two parameters, mass and power consumption, are among the instrument requirements which need to be minimized when designing a lidar for a space-borne platform. Reducing the scanner contributions in these areas will have a significant effect on the overall instrument specifications, Replacing the optical wedge with a diffraction grating on the surface of a thin substrate is a straight forward approach with potential to reduce the mass of the scanning element significantly. For example, the optical wedge that will be used for the SPAce Readiness Coherent Lidar Experiment (SPARCLE) is approximately 25 cm in diameter and is made from silicon with a wedge angle designed for 30 degree deflection of a beam operating at approx. 2 micrometer wavelength. The mass of this element could be reduced by a factor of four by instead using a fused silica substrate, 1 cm thick, with a grating fabricated on one of the surfaces. For a grating to deflect a beam with a 2 micrometer wavelength by 30 degrees, a period of approximately 4 micrometers is required. This is small enough that fabrication of appropriate high efficiency blazed or multi-phase level diffractive optical gratings is prohibitively difficult. Moreover, bulk or stratified volume holographic approaches appear impractical due to materials limitations at 2 micrometers and the need to maintain adequate wavefront quality. In order to avoid the difficulties encountered in these approaches, we have developed a new type of high-efficiency grating which we call a Stratified Volume Diffractive Optical Element (SVDOE). The features of the gratings in this approach can be easily fabricated using standard photolithography and etching techniques and the materials used in the grating can be chosen specifically for a given application, In this paper we will briefly discuss the SVDOE technique and will present an example design of a lidar scanner using this approach. We will also discuss performance predictions for the example design.

Chambers, Diana M.↗

DOE OSTI2022

A catalytic dyad modulates conformational change in the CO 2 -fixing flavoenzyme 2-ketopropyl coenzyme M oxidoreductase/carboxylase

2-Ketopropyl-coenzyme M oxidoreductase/carboxylase (2-KPCC) is a member of the flavin and cysteine disulfide containing oxidoreductase family (DSOR) that catalyzes the unique reaction between atmospheric CO 2 and a ketone/enolate nucleophile to generate acetoacetate. However, the mechanism of this reaction is not well understood. Here, we present evidence that 2-KPCC, in contrast to the well-characterized DSOR enzyme glutathione reductase, undergoes conformational changes during catalysis. Using a suite of biophysical techniques including limited proteolysis, differential scanning fluorimetry, and native mass spectrometry in the presence of substrates and inhibitors, we observed conformational differences between different ligand-bound 2-KPCC species within the catalytic cycle. Analysis of site-specific amino acid variants indicated that 2-KPCC-defining residues, Phe501-His506, within the active site are important for transducing these ligand induced conformational changes. We propose that these conformational changes promote substrate discrimination between H + and CO 2 to favor the metabolically preferred carboxylation product, acetoacetate.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2004

Thin-Film Solar Cells on Metal Foil Substrates for Space Power

Photovoltaic arrays have played a key role in power generation in space. The current technology will continue to evolve but is limited in the important mass specific power metric (MSP or power/weight ratio) because it is based on bulk crystal technology. The objective of this research is to continue development of an innovative photovoltaic technology for satellite power sources that could provide up to an order of magnitude saving in both weight and cost, and is inherently radiation-tolerant through use of thin film technology and thin foil substrates such as 5-mil thick stainless steel foil or 1-mil thick Ti. Current single crystal technology for space power can cost more than $300 per watt at the array level and weigh more than 1 kg/sq m equivalent to specific power of approx. 65 W/kg. Thin film material such as CuIn(1-x),Ga(x)S2, (CIGS2), CuIn(1-x), G(x)Se(2-y),S(y), (CIGSS) or amorphous hydrogenated silicon (a-Si:H) may be able to reduce both the cost and mass per unit area by an order of magnitude. Manufacturing costs for solar arrays are an important consideration for total spacecraft budget. For a medium sized 5kW satellite, for example, the array manufacturing cost alone may exceed $2 million. Moving to thin film technology could reduce this expense to less than $500 K. Previous work at FSEC demonstrated the potential of achieving higher efficiencies from CIGSS thin film solar cells on 5-mil thick stainless steel foil as well as initial stages of facility augmentation for depositing thin film solar cells on larger (6"x 4") substrates. This paper presents further progress in processing on metal foil substrates. Also, previous work at DayStar demonstrated the feasibility of flexible-thin-film copper-indium-gallium-diselenide (CIGS) solar cells with a power-to-weight ratio in excess of 1000 W/kg. We will comment on progress on the critical issue of scale-up of the solar cell absorber deposition process. Several important technical issues need to be resolved to realize the benefits of lightweight technologies for solar arrays, such as: monolithic interconnects, lightweight array structures, and new ultra-light support and deployment mechanisms. Once the technology has gained spaceflight certification it should find rapid acceptance in specific satellite markets.

Raffaelle, Ryne P.↗

NASA NTRS2003

Prebiotic Synthesis of Autocatalytic Products From Formaldehyde-Derived Sugars as the Carbon and Energy Source

Our research objective is to understand and model the chemical processes on the primitive Earth that generated the first autocatalytic molecules and microstructures involved in the origin of life. Our approach involves: (a) investigation of a model origin-of-life process named the Sugar Model that is based on the reaction of formaldehyde- derived sugars (trioses and tetroses) with ammonia, and (b) elucidation of the constraints imposed on the chemistry of the origin of life by the fixed energies and rates of C,H,O-organic reactions under mild aqueous conditions. Recently, we demonstrated that under mild aqueous conditions the Sugar Model process yields autocatalytic products, and generates organic micropherules (2-20 micron dia.) that exhibit budding, size uniformity, and chain formation. We also discovered that the sugar substrates of the Sugar Model are capable of reducing nitrite to ammonia under mild aqueous conditions. In addition studies done in collaboration with Sandra Pizzarrello (Arizona State University) revealed that chiral amino acids (including meteoritic isovaline) catalyze both the synthesis and specific handedness of chiral sugars. Our systematic survey of the energies and rates of reactions of C,H,O-organic substrates under mild aqueous conditions revealed several general principles (rules) that govern the direction and rate of organic reactions. These reactivity principles constrain the structure of chemical pathways used in the origin of life, and in modern and primitive metabolism.

Weber, Arthur L.↗

NASA NTRS2003

Method for printing functional protein microarrays

Piezoelectric dispensing of proteins from borosilicate glass capillaries is a popular method of protein biochip fabrication that offers the advantages of sample recovery and noncontact with the printing substrate. However, little regard has been given to the quantitative aspects of dispensing minute volumes (1 nL or less) at the low protein concentrations (20 micrograms/mL or less) typically used in microprinting. Specifically, loss of protein sample due to nonspecific adsorption to the glass surface of the dispensing capillaries can limit the amount of protein delivered to the substrate. We demonstrate the benefits of a low ionic strength buffer containing the carrier protein BSA that effectively minimizes the ionic strength-dependent phenomenon of nonspecific protein adsorption to borosilicate glass. Over the concentration range of 20-2.5 micrograms/mL, the dispensing of a reference IgG in 10 mM PBS including 0.1% BSA resulted in the deposition of 3.6- to 44-fold more IgG compared to the deposition of IgG in standard 150 mM PBS in the absence of BSA. Furthermore, when the IgG was dispensed with carrier protein, the resulting spots exhibited a more uniform morphology. In a direct immunoassay for cholera toxin, capture antibody spots dispensed in 10 mM PBS containing 0.1% BSA produced fluorescent signals that were 2.8- to 4.3-fold more intense than antibody spots that were dispensed in 150 mM PBS without BSA. Interestingly, no differences were observed in the specific activities of the capture antibodies as a result of printing in the different buffers. The implications of these results on the future development of protein biochips are discussed.

Evaluation Studies↗

DOE OSTI2019

Photo-generated reactive oxygen species assisted tandem amine homocoupling and amine-alcohol cross-coupling reaction on mesoporous spinel cobalt oxide

Mesoporous spinel cobalt oxide (Co 3 O 4 ) with fine-tuned pore size distributions (9.6–17.6 nm) and different surface areas (33–85 m 2 /g) were synthesized using a series of nonionic surfactants. A direct influence of the chemical composition of the surfactants and calcination temperature on crystallite size, morphology, pore size/volume, surface area, valance band edge, and Co 2+ /Co 3+ ratio was recognized. Correlation between the aforementioned factors, transition metal ion incorporation and benzylamine homocoupling reaction was discussed. Shape-specific binding of amine on the cobalt oxide active sites was proposed based on substrate scope study. Tandem synthesis strategy to selectively synthesize amine (aliphatic/aromatic) homo-coupled imines and amine-alcohol cross-coupled imines was introduced. Low-intensity light-induced singlet oxygen and hydroxyl radical-mediated reaction mechanism was proposed based on the EPR, XPS, photoreactor, and reactive oxygen species scavenger tests. Selective and switchable synthesis of homo-coupled (yield 85%) and cross-coupled (yield 87%) products was achieved with sodium azide and mannitol additives.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

Microstrip patch antenna for simultaneous temperature sensing and superstrate characterization

This paper investigates a microstrip patch antenna for measuring the thickness and dielectric constant of the medium above the antenna (i.e. the superstrate) as well as the temperature. The intended application is simultaneous sensing of ash accumulation and temperature inside a boiler, with the aim of enhancing safety, improving efficiency, and reducing downtime associated with maintenance. A patch antenna, consisting of a dielectric substrate, a radiation patch, and a ground plane, functions as an electromagnetic resonator with specific fundamental frequencies. A dielectric medium placed above the patch antenna changes its effective dielectric constant and thus its resonant frequencies. Meanwhile, temperature also influences the antenna frequencies because of the thermal expansion of the conductors (i.e. the radiation patch and ground plane), and the dielectric constant of dielectric materials due to their temperature dependency. Since a rectangular patch antenna has two fundamental frequencies, it enables determining these two parameters simultaneously. Once the temperature and superstrate thickness are determined, the dielectric constant of the superstrate and its temperature dependency can also be extracted. To demonstrate this capability, a dual-frequency patch antenna was designed, fabricated, and characterized with a superstrate of various thicknesses and at different temperatures. By fitting the antenna resonant frequencies as functions of the superstrate thickness and temperature, these two parameters were inversely determined from the measured antenna frequencies. Using ash from charcoal briquettes as a superstrate, the measurement uncertainties were determined to be ±0.58 °C and ±58.05 μ m for the temperature and the superstrate thickness respectively. The dielectric constant of the ash was found to be 2.64 at room temperature and its thermal coefficient of dielectric constant (TCD k ) was found to be 918 ppm °C –1 .

36 MATERIALS SCIENCE↗

NASA NTRS1992

Aberration-corrected aspheric grating designs for the Lyman/Far-Ultraviolet Spectroscopic Explorer high-resolution spectrograph - A comparison

Two approaches to reducing the optical aberrations of concave diffraction gratings have been studied to obtain candidate grating designs for the Lyman/Far-Ultraviolet Spectroscopic Explorer mission. The first approach involves shaping the grating substrate while using straight and equally spaced grooves. The second approach involves using a gating substrate with a relatively simple figure and holographically controlling the groove curvature and spacing. Specific designs derived from both approaches are analyzed and compared.

Trout, Catherine↗

NASA NTRS1993

LUTE primary mirror materials and design study report

The major objective of the Lunar Ultraviolet Telescope Experiment (LUTE) Primary Mirror Materials and Design Study is to investigate the feasibility of the LUTE telescope primary mirror. A systematic approach to accomplish this key goal was taken by first understanding the optical, thermal, and structural requirements and then deriving the critical primary mirror-level requirements for ground testing, launch, and lunar operations. After summarizing the results in those requirements which drove the selection of material and the design for the primary mirror are discussed. Most important of these are the optical design which was assumed to be the MSFC baseline (i.e. 3 mirror optical system), telescope wavefront error (WFE) allocations, the telescope weight budget, and the LUTE operational temperature ranges. Mechanical load levels, reflectance and microroughness issues, and options for the LUTE metering structure were discussed and an outline for the LUTE telescope sub-system design specification was initiated. The primary mirror analysis and results are presented. The six material substrate candidates are discussed and four distinct mirror geometries which are considered are shown. With these materials and configurations together with varying the location of the mirror support points, a total of 42 possible primary mirror designs resulted. The polishability of each substrate candidate was investigated and a usage history of 0.5 meter and larger precision cryogenic mirrors (the operational low end LUTE temperature of 60 K is the reason we feel a survey of cryogenic mirrors is appropriate) that were flown or tested are presented.

Ruthven, Greg↗

NASA NTRS2012

Reconfigurable Wave Velocity Transmission Lines for Phased Arrays

This presentation discussed a novel phased array with an emphasis to simplify the array feed. Specifically, we will demonstrate a simple, low cost feeding approach by mechanically controlling the substrate thickness. The array feed lines are constructed from parallel plate transmission lines whose thickness are adjusted to control their effective dielectric constant (Epsilon_eff). As a result the phase delay/excitation at each array element will be adjusted per desired beam direction. The proposed antenna elements will be overlapping dipoles operating over a 2:1 bandwidth in the Ku-Band spectrum. Preliminary simulation and experimental demonstration of such an array will be presented.

Host, Nicholas Keith↗

NASA NTRS2014

Open Circuit Resonant (SansEC) Sensor Technology for Lightning Mitigation and Damage Detection and Diagnosis for Composite Aircraft Applications

Traditional methods to protect composite aircraft from lightning strike damage rely on a conductive layer embedded on or within the surface of the aircraft composite skin. This method is effective at preventing major direct effect damage and minimizes indirect effects to aircraft systems from lightning strike attachment, but provides no additional benefit for the added parasitic weight from the conductive layer. When a known lightning strike occurs, the points of attachment and detachment on the aircraft surface are visually inspected and checked for damage by maintenance personnel to ensure continued safe flight operations. A new multi-functional lightning strike protection (LSP) method has been developed to provide aircraft lightning strike protection, damage detection and diagnosis for composite aircraft surfaces. The method incorporates a SansEC sensor array on the aircraft exterior surfaces forming a "Smart skin" surface for aircraft lightning zones certified to withstand strikes up to 100 kiloamperes peak current. SansEC sensors are open-circuit devices comprised of conductive trace spiral patterns sans (without) electrical connections. The SansEC sensor is an electromagnetic resonator having specific resonant parameters (frequency, amplitude, bandwidth & phase) which when electromagnetically coupled with a composite substrate will indicate the electrical impedance of the composite through a change in its resonant response. Any measureable shift in the resonant characteristics can be an indication of damage to the composite caused by a lightning strike or from other means. The SansEC sensor method is intended to diagnose damage for both in-situ health monitoring or ground inspections. In this paper, the theoretical mathematical framework is established for the use of open circuit sensors to perform damage detection and diagnosis on carbon fiber composites. Both computational and experimental analyses were conducted to validate this new method and system for aircraft composite damage detection and diagnosis. Experimental test results on seeded fault damage coupons and computational modeling simulation results are presented. This paper also presents the shielding effectiveness along with the lightning direct effect test results from several different SansEC LSP and baseline protected and unprotected carbon fiber reinforced polymer (CFRP) test panels struck at 40 and 100 kiloamperes following a universal common practice test procedure to enable damage comparisons between SansEC LSP configurations and common practice copper mesh LSP approaches. The SansEC test panels were mounted in a LSP test bed during the lightning test. Electrical, mechanical and thermal parameters were measured during lightning attachment and are presented with post test nondestructive inspection comparisons. The paper provides correlational results between the SansEC sensors computed electric field distribution and the location of the lightning attachment on the sensor trace and visual observations showing the SansEC sensor's affinity for dispersing the lightning attachment.

Szatkowski, George N.↗

NASA NTRS2007

Electrochemically Controlled Reconstitution of Immobilized Ferritins for Bioelectronic Applications

Site-specific reconstituted nanoparticles were fabricated via electrochemically-controlled biomineralization through the immobilization of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, and the electrocatalytic reduction of oxygen on the reconstituted Pt-cored ferritins. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of site-specific electrochemical biomineralization with a protein cage loads ferritins with different core materials. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This first demonstration of electrochemically controlled site-specific reconstitution of biomolecules provides a new tool for biomineralization and opens the way to produce the bio-templated nanoparticles by electrochemical control. The nanosized platinum-cored ferritins on gold displayed good catalytic activity for the electrochemical reduction of oxygen, which is applicable to biofuel cell applications. This results in a smaller catalyst loading on the electrodes for fuel cells or other bioelectronic devices.

Kim, Jae-Woo↗

DOE OSTI2026

Tunable Multisite Proton-Coupled Electron Transfer Mediators: Distinct Pathways for Substrate Reduction Versus Competing Hydrogen Evolution

Proton-coupled electron transfer (PCET) reagents have emerged as powerful tools for transferring net H atoms to organic substrates from relatively weak X–H bonds. One advantage of employing PCET reagents is the tunability of the X–H bond strength by independently varying their redox potential and/or p K a for selective substrate reductions; however, the rational development of modular catalytic PCET reagents based on these features remains underdeveloped. In this work, we address important mechanistic questions relevant to a dimethylaniline-appended cobaltocene PCET mediator that our lab has previously introduced. Specifically, we examine where protonation occurs within the reactive Co(II, NH) + intermediate of a Brønsted-base modified cobaltocene mediator, whether substrate reduction and hydrogen evolution reaction (HER) proceed by a common or bifurcated mechanistic pathway, and how the redox, acid–base, and structural properties of PCET mediators can dictate their reactivity and selectivity. We show that substrate compatibility can be tuned and, via a model study with N -aryl imine substrates, provide data pointing to a multisite PCET (MS-PCET) pathway. Moreover, we rigorously characterize the site of protonation in the reactive reduced, protonated form of the mediator, and through kinetic analysis establish that the pathway for undesired competing HER is fundamentally different and involves Cp-ring protonation. Our findings point to a high degree of flexibility in the design of reductive PCET mediators.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗