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At least 559 records · Page 31

Analysis of the interaction between host factor Sam68 and viral elements during foot-and-mouth disease virus infections

Background: The nuclear protein Src-associated protein of 68 kDa in mitosis (Sam68) is known to bind RNA and be involved in cellular processes triggered in response to environmental stresses, including virus infection. Interestingly, Sam68 is a multi-functional protein implicated in the life cycle of retroviruses and picornaviruses and is also considered a marker of virus-induced stress granules (SGs). Recently, we demonstrated the partial redistribution of Sam68 to the cytoplasm in FMDV infected cells, its interaction with viral protease 3C pro , and found a significant reduction in viral titers as consequence of Sam68-specific siRNA knockdowns. Despite of that, details of how it benefits FMDV remains to be elucidated. Methods: Sam68 cytoplasmic localization was examined by immunofluorescent microscopy, counterstaining with antibodies against Sam68, a viral capsid protein and markers of SGs. The relevance of RAAA motifs in the IRES was investigated using electromobility shift assays with Sam68 protein and parental and mutant FMDV RNAs. In addition, full genome WT and mutant or G-luc replicon RNAs were tested following transfection in mammalian cells. The impact of Sam68 depletion to virus protein and RNA synthesis was investigated in a cell-free system. Lastly, through co-immunoprecipitation, structural modeling, and subcellular fractionation, viral protein interactions with Sam68 were explored. Results: FMDV-induced cytoplasmic redistribution of Sam68 resulted in it temporarily co-localizing with SG marker: TIA-1. Mutations that disrupted FMDV IRES RAAA motifs, with putative affinity to Sam68 in domain 3 and 4 cause a reduction on the formation of ribonucleoprotein complexes with this protein and resulted in non-viable progeny viruses and replication-impaired replicons. Furthermore, depletion of Sam68 in cell-free extracts greatly diminished FMDV RNA replication, which was restored by addition of recombinant Sam68. The results here demonstrated that Sam68 specifically co-precipitates with both FMDV 3D pol and 3C pro consistent with early observations of FMDV 3C pro -induced cleavage of Sam68. Conclusion: We have found that Sam68 is a specific binding partner for FMDV non-structural proteins 3C pro and 3D pol and showed that mutations at RAAA motifs in IRES domains 3 and 4 cause a decrease in Sam68 affinity to these RNA elements and rendered the mutant RNA non-viable. Interestingly, in FMDV infected cells re-localized Sam68 was transiently detected along with SG markers in the cytoplasm. These results support the importance of Sam68 as a host factor co-opted by FMDV during infection and demonstrate that Sam68 interact with both, FMDV RNA motifs in the IRES and viral non-structural proteins 3C pro and 3D pol .

3C protease↗

Assessing Simulations of Forest Hurricane Disturbance and Recovery in Puerto Rico by ELM-FATES Using Field Measurements

In the past three decades, Puerto Rico (PR) experienced five hurricanes that met or exceeded category three, and they caused severe forest structural damage and elevated tree mortality. To improve our mechanistic understanding of hurricane impacts on tropical forests and assess hurricane-affected forest dynamics in Earth system models, we use in situ forest measurements at the Bisley Experimental Watersheds in Northeast PR to evaluate the Functionally Assembled Terrestrial Ecosystem Simulator coupled with the Energy Exascale Earth System Model Land Model (ELM-FATES). The observations show that before Hurricane Hugo, 77.3% of the aboveground biomass (AGB) is from the shade-tolerant plant function type (PFT). The Hugo-induced mortality rates are over ~50%, and they induce a ~39% AGB reduction, which recovers to a level like the pre-Hugo condition in 2014, following a second, lower intensity hurricane, Georges. We perform numerical experiments that simulate damage from Hugo and Georges on the forests, including defoliation, sapwood and structural biomass damage, and hurricane-induced mortality. ELM-FATES can reasonably represent coexistence between the two PFTs–light-demanding and shade-tolerant–for both the pre-Hugo and post-Hugo conditions. The model represents a reasonable size distribution of mid-and large-sized trees although it underestimates AGB, likely due to the overestimated nonhurricane mortality. ELM-FATES temporarily stimulated leaf biomass and diameter increment after Georges, an effect that should be tested with observations of future hurricane defoliation events. This research indicates that addressing model-data mismatches in tree mortality and understory dynamics are essential to simulation of more extreme hurricane effects under climate change.

58 GEOSCIENCES↗

Role of Bifunctional Ru/Acid Catalysts in the Selective Hydrocracking of Polyethylene and Polypropylene Waste to Liquid Hydrocarbons

Hydrogenolysis of C–C bonds over Ru-based catalysts has emerged as a deconstruction strategy to convert single-use polyolefin waste to liquid alkanes at relatively mild conditions, but this approach exhibits limitations, including methane formation resulting from terminal C–C bond scission. In this study, a variety of catalysts were investigated for the reductive deconstruction of polyethylene (PE) and polypropylene (PP) to identify supports that promote nonterminal C–C bond scission. We found that Ru nanoparticles supported on Brønsted-acidic zeolites with the faujasite (FAU) and Beta (BEA) topologies were highly active for the cleavage of C–C bonds in PE and PP, exhibiting improved liquid yields and suppressed methane formation. For the deconstruction of PE, supporting ruthenium nanoparticles (5 wt %) on FAU increased the yields of liquid alkanes to 67% compared to 33% over an inert silica support (5 wt % Ru/SiO 2 ) at 200 °C, 16 h, under 30 bar of H2. A dramatic selectivity enhancement toward liquid hydrocarbons was also observed for PP over Ru/FAU and Ru/BEA compared to Ru/SiO 2 . To understand the origin of this selectivity improvement, a combination of ex situ and operando characterization techniques were used to reveal that both catalyst structure and acidity play key roles in PE and PP conversion. Operando X-ray absorption spectroscopy studies with model polyolefins over Ru-supported catalysts with varying acidity levels revealed that the local chemical environment of Ru [0] during the reaction is consistent across multiple acidic supports, although the onset of reduction during synthesis of the nanoparticles varies across different supports. These results, combined with reactivity data, demonstrate the importance of the acid-noble metal cooperativity in promoting selective C–C bond scission toward liquid alkanes that shifts the mechanism from hydrogenolysis to ideal hydrocracking.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A New Grain Refiner for Ferritic Steels

A new grain refiner, LaB{sub 6}, was identified for ferritic steels based on the crystallographic calculation using the edge-to-edge matching model. Addition of 0.5 wt pct LaB{sub 6} led to a reduction of the average grain size from 765 to 92 μm and the proportion of the columnar structure from 35 to 8 pct in an as-cast Fe-4Si ferritic alloy. Although LaB{sub 6} was supposed to act as an active inoculant for δ-ferrite, thermodynamic calculation indicated that LaB{sub 6} is not thermodynamically stable in the melt of the Fe-4Si alloy. It was subject to decompose into La and B solutes. Consequently, both La and B reacted with Fe, O and S, forming different compounds. Microstructural examination at room temperature observed La{sub 2}SO{sub 2} and La{sub 2}O{sub 3} particles within the ferrite grains and Fe{sub 2}B along the grain boundaries in the samples. Through EBSD analysis, a reproducible orientation relationship between ferrite and La{sub 2}SO{sub 2} was identified. In addition, the edge-to-edge matching calculation also predicted the high potency for La{sub 2}SO{sub 2} to be an effective nucleant for δ-ferrite. It was considered that the grain refinement of LaB{sub 6} was attributed to the enhanced heterogeneous nucleation of δ-ferrite by La{sub 2}SO{sub 2}, and the solute effect of B due to the high Q-value in ferrite.

36 MATERIALS SCIENCE↗

Dosage optimization for reducing tumor burden using a phenotype-structured population model with a drug-resistance continuum

Abstract Drug resistance is a significant obstacle to effective cancer treatment. To gain insights into how drug resistance develops, we adopted a concept called fitness landscape and employed a phenotype-structured population model by fitting to a set of experimental data on a drug used for ovarian cancer, olaparib. Our modeling approach allowed us to understand how a drug affects the fitness landscape and track the evolution of a population of cancer cells structured with a spectrum of drug resistance. We also incorporated pharmacokinetic (PK) modeling to identify the optimal dosages of the drug that could lead to long-term tumor reduction. We derived a formula that indicates that maximizing variation in plasma drug concentration over a dosing interval could be important in reducing drug resistance. Our findings suggest that it may be possible to achieve better treatment outcomes with a drug dose lower than the levels recommended by the drug label. Acknowledging the current limitations of our work, we believe that our approach, which combines modeling of both PK and drug resistance evolution, could contribute to a new direction for better designing drug treatment regimens to improve cancer treatment.

Life Sciences & Biomedicine - Other Topics↗

Acceptance and control of aircraft interior noise and vibration

Ride quality criteria for noise, vibration, and their combination in the helicopter cabin environment are discussed. Results are presented of laboratory and field studies of passenger responses to interior noise and vibration during the performance of a listening task and during reverie, as well as to the interaction of noise with multi-frequency and multi-axis vibration. A study of means for reducing helicopter interior noise based on analytical, experimental and flight studies of the near-field noise source characteristics of the aircraft, the transmission of noise through aircraft structures and the attenuation of noise by various noise control treatments is then presented which has resulted in a reduction of 3 dB in helicopter cabin noise. Finally, a model under development to evaluate passenger acceptance of a helicopter noise and vibration environment is indicated which incorporates the observed noise and vibration effects on comfort and is expected to provide insights for more effective noise and vibration control.

Stephens, D. G.↗

Nontangent, Developed Contour Bulkheads for a Single-Stage Launch Vehicle

Dry weights for single-stage launch vehicles that incorporate nontangent, developed contour bulkheads are estimated and compared to a baseline vehicle with 1.414 aspect ratio ellipsoidal bulkheads. Weights, volumes, and heights of optimized bulkhead designs are computed using a preliminary design bulkhead analysis code. The dry weights of vehicles that incorporate the optimized bulkheads are predicted using a vehicle weights and sizing code. Two optimization approaches are employed. A structural-level method, where the vehicle's three major bulkhead regions are optimized separately and then incorporated into a model for computation of the vehicle dry weight, predicts a reduction of4365 lb (2.2 %) from the 200,679-lb baseline vehicle dry weight. In the second, vehicle-level, approach, the vehicle dry weight is the objective function for the optimization. For the vehicle-level analysis, modified bulkhead designs are analyzed and incorporated into the weights model for computation of a dry weight. The optimizer simultaneously manipulates design variables for all three bulkheads to reduce the dry weight. The vehicle-level analysis predicts a dry weight reduction of 5129 lb, a 2.6% reduction from the baseline weight. Based on these results, nontangent, developed contour bulkheads may provide substantial weight savings for single stage vehicles.

Wu, K. Chauncey↗

Nontangent, Developed Contour Bulkheads for a Wing-Body Single Stage Launch Vehicle

Dry weights for a SSTO vehicle which incorporates nontangent, developed contour bulkheads are estimated and compared to a baseline vehicle with 1.41 4 aspect ratio ellipsoidal bulkheads, Weights, volumes and heights of optimized bulkhead designs are computed using a preliminary design bulkhead analysis code. The dry weight of a vehicle which incorporates the optimized bulkheads is predicted using a vehicle weights and sizing code. Two optimization approaches are employed. A structural-level method, where the vehicle s three major bulkhead regions are optimized separately and then incorporated into a model for computation of the vehicle dry weight, predicts a reduction of 4365 Ib (2.2 percent) from the 200,679 Ib baseline vehicle dry weight. In the second, vehicle-level, approach, the vehicle dry weight is the objective function for the optimization. During the vehicle- level analysis, modified bulkhead designs are first analyzed, then incorporated into the weights model for computation of a dry weight. The optimizer simultaneously manipulates design variables for all three bulkheads to reduce the dry weight. The vehicle-level analysis predicts a dry weight reduction of 5129 Ib, a 2.6 percent reduction from the baseline value. These results suggest that nontangent, developed contour bulkheads may provide substantial weight savings for SSTO vehicles.

Wu, K. Chauncey↗

Acceleration and Velocity Sensing from Measured Strain

A simple approach for computing acceleration and velocity of a structure from the strain is proposed in this study. First, deflection and slope of the structure are computed from the strain using a two-step theory. Frequencies of the structure are computed from the time histories of strain using a parameter estimation technique together with an Autoregressive Moving Average model. From deflection, slope, and frequencies of the structure, acceleration and velocity of the structure can be obtained using the proposed approach. shape sensing, fiber optic strain sensor, system equivalent reduction and expansion process.

shape sensing↗

Methodologies for Verification and Validation of Space Launch System (SLS) Structural Dynamic Models: Appendices

Verification and validation (V&V) is a highly challenging undertaking for SLS structural dynamics models due to the magnitude and complexity of SLS subassemblies and subassemblies. Responses to challenges associated with V&V of Space Launch System (SLS) structural dynamics models are presented in Volume I of this paper. Four methodologies addressing specific requirements for V&V are discussed. (1) Residual Mode Augmentation (RMA). (2) Modified Guyan Reduction (MGR) and Harmonic Reduction (HR, introduced in 1976). (3) Mode Consolidation (MC). Finally, (4) Experimental Mode Verification (EMV). This document contains the appendices to Volume I.

Coppolino, Robert N.↗

TPSAS-NF1676L-13638-DND

Dry weights for single-stage launch vehicles that incorporate nontangent, developed contour bulkheads are estimated and compared to a baseline vehicle with 1.414 aspect ratio ellipsoidal bulkheads. Weights, volumes, and heights of optimized bulkhead designs are computed using a preliminary design bulkhead analysis code. The dry weights of vehicles that incorporate the optimized bulkheads are predicted using a vehicle weights and sizing code. Two optimization approaches are employed. A structural-level method, where the vehicle's three major bulkhead regions are optimized separately and then incorporated into a model for computation of the vehicle dry weight, predicts a reduction of 4365 Ib (2.2%) from the 200,679-lb baseline vehicle dry weight. In the second, vehicle-level, approach, the vehicle dry weight is the objective function for the optimization. For the vehicle-level analysis, modified bulkhead designs are analyzed and incorporated into the weights model for computation of a dry weight. The optimizer simultaneously manipulates design variables for all three bulkheads to reduce the dry weight. The vehicle- level analysis predicts a dry weight reduction of 5129 Ib, a 2.6% reduction from the baseline weight. Based on these results, nontangent, developed contour bulkheads may provide substantial weight savings for single stage vehicles.

K Chauncey Wu↗

Evaluation of Model-Based Training for Vertical Guidance Logic

This paper will summarize the results of a study which introduces a structured, model based approach to learning how the automated vertical guidance system works on a modern commercial air transport. The study proposes a framework to provide accurate and complete information in an attempt to eliminate confusion about 'what the system is doing'. This study will examine a structured methodology for organizing the ideas on which the system was designed, communicating this information through the training material, and displaying it in the airplane. Previous research on model-based, computer aided instructional technology has shown reductions in the amount of time to a specified level of competence. The lessons learned from the development of these technologies are well suited for use with the design methodology which was used to develop the vertical guidance logic for a large commercial air transport. The design methodology presents the model from which to derive the training material, and the content of information to be displayed to the operator. The study consists of a 2 X 2 factorial experiment which will compare a new method of training vertical guidance logic and a new type of display. The format of the material used to derive both the training and the display will be provided by the Operational Procedure Methodology. The training condition will compare current training material to the new structured format. The display condition will involve a change of the content of the information displayed into pieces that agree with the concepts with which the system was designed.

Feary, Michael↗

Vibration of a cryomodule’s coupler during road transportation: Multibody analysis and experimental validation

The road transportation of critical components for cryogenic cryomodules is a challenging task. Indeed, the shipping and the handling of fundamental sub-assemblies can expose these components to harmful dynamic loads that can jeopardize their structural integrity. This article has the purpose of developing a finite element multibody model capable of assessing the acceleration on a test coupler for a cavity of the Single Spoke Resonator 1 subjected to a typical road transportation trip. A multibody model consisting of rigid bodies and finite element–imported flexible bodies has been created allowing a comparison of the simulated and experimental acceleration. Afterwards, an experimental on-road test, whose set-up is described in this article, has been carried out at Fermilab with instrumented components. Being able to effectively simulate and validate the dynamic effects on such sub-assemblies makes it possible, for the future, to simulate more complex structures subject to dynamic loadings, such as the entire cryomodules during shipping. Furthermore, the results from the simulations can be used to guide the design of new suspension systems suitable for the reduction mitigation of structural vibration during the road transportation of cryomodules.

42 ENGINEERING↗

Approximate Green’s Function Coupled Cluster A Method Employing Effective Dimension Reduction

The Green’s function coupled cluster (GFCC) method, originally proposed in the early 1990s, is a powerful many-body tool for computing and analyzing the electronic structures of molecular structures and periodic systems, especially when electrons are strongly correlated. However, in order for the GFCC method to become an approach that can be routinely used in the electronic structure calculations, more robust linear algebraic techniques and approximations need to be employed to reduce its extremely high computational overhead. In our recent studies, we showed that the GFCC equation can be numerically solved by seeking solutions of multiple linear systems in the frequency regime of interest, which can be easily distributed in a massively parallel environment, and broaden the avenue for more state-of-the-art numerical linear algebraic tools associated with multiple linear systems to be kicked in to this field. In the present pursuit of this practice, we show a successful application of model order reduction (MOR) techniques in the GFCC framework. Briefly speaking, for a frequency regime of interest that requires a high resolution of spectral function, instead of solving GFCC linear equation in the original dimension for every single frequency point, an easily-solvable linear system model with reduced dimension can be built upon projecting the original GFCC linear system into a subspace, from which the interpolation and extrapolation can give a reasonable approximation to the results of the original GFCC linear equations. Here, we show that the subspace can be properly constructed in an iterative manner from the auxiliary vectors of the GFCC linear equations at some select frequencies inside the frequency regime. During the iterations, the quality of the subspace, as well as the linear system model, can be systematically improved. The approach is tested in this work in terms of the efficiency and accuracy of computing spectral functions for some typical molecular systems including carbon monoxide, 1,3-butadiene, benzene, and adenine molecules. As a byproduct, the high quality linear system model is also found to be able to provide high quality initial guess for the existing linear solver to improve the convergence performance.

Peng, Bo↗

A Vehicle Management End-to-End Testing and Analysis Platform for Validation of Mission and Fault Management Algorithms to Reduce Risk for NASAs Space Launch System

The engineering development of the National Aeronautics and Space Administration's (NASA) new Space Launch System (SLS) requires cross discipline teams with extensive knowledge of launch vehicle subsystems, information theory, and autonomous algorithms dealing with all operations from pre-launch through on orbit operations. The nominal and off-nominal characteristics of SLS's elements and subsystems must be understood and matched with the autonomous algorithm monitoring and mitigation capabilities for accurate control and response to abnormal conditions throughout all vehicle mission flight phases, including precipitating safing actions and crew aborts. This presents a large and complex systems engineering challenge, which is being addressed in part by focusing on the specific subsystems involved in the handling of off-nominal mission and fault tolerance with response management. Using traditional model-based system and software engineering design principles from the Unified Modeling Language (UML) and Systems Modeling Language (SysML), the Mission and Fault Management (M&FM) algorithms for the vehicle are crafted and vetted in Integrated Development Teams (IDTs) composed of multiple development disciplines such as Systems Engineering (SE), Flight Software (FSW), Safety and Mission Assurance (S&MA) and the major subsystems and vehicle elements such as Main Propulsion Systems (MPS), boosters, avionics, Guidance, Navigation, and Control (GNC), Thrust Vector Control (TVC), and liquid engines. These model-based algorithms and their development lifecycle from inception through FSW certification are an important focus of SLS's development effort to further ensure reliable detection and response to off-nominal vehicle states during all phases of vehicle operation from pre-launch through end of flight. To test and validate these M&FM algorithms a dedicated test-bed was developed for full Vehicle Management End-to-End Testing (VMET). For addressing fault management (FM) early in the development lifecycle for the SLS program, NASA formed the M&FM team as part of the Integrated Systems Health Management and Automation Branch under the Spacecraft Vehicle Systems Department at the Marshall Space Flight Center (MSFC). To support the development of the FM algorithms, the VMET developed by the M&FM team provides the ability to integrate the algorithms, perform test cases, and integrate vendor-supplied physics-based launch vehicle (LV) subsystem models. Additionally, the team has developed processes for implementing and validating the M&FM algorithms for concept validation and risk reduction. The flexibility of the VMET capabilities enables thorough testing of the M&FM algorithms by providing configurable suites of both nominal and off-nominal test cases to validate the developed algorithms utilizing actual subsystem models such as MPS, GNC, and others. One of the principal functions of VMET is to validate the M&FM algorithms and substantiate them with performance baselines for each of the target vehicle subsystems in an independent platform exterior to the flight software test and validation processes. In any software development process there is inherent risk in the interpretation and implementation of concepts from requirements and test cases into flight software compounded with potential human errors throughout the development and regression testing lifecycle. Risk reduction is addressed by the M&FM group but in particular by the Analysis Team working with other organizations such as S&MA, Structures and Environments, GNC, Orion, Crew Office, Flight Operations, and Ground Operations by assessing performance of the M&FM algorithms in terms of their ability to reduce Loss of Mission (LOM) and Loss of Crew (LOC) probabilities. In addition, through state machine and diagnostic modeling, analysis efforts investigate a broader suite of failure effects and associated detection and responses to be tested in VMET to ensure reliable failure detection, and confirm responses do not create additional risks or cause undesired states through interactive dynamic effects with other algorithms and systems. VMET further contributes to risk reduction by prototyping and exercising the M&FM algorithms early in their implementation and without any inherent hindrances such as meeting FSW processor scheduling constraints due to their target platform - the ARINC 6535-partitioned Operating System, resource limitations, and other factors related to integration with other subsystems not directly involved with M&FM such as telemetry packing and processing. The baseline plan for use of VMET encompasses testing the original M&FM algorithms coded in the same C++ language and state machine architectural concepts as that used by FSW. This enables the development of performance standards and test cases to characterize the M&FM algorithms and sets a benchmark from which to measure their effectiveness and performance in the exterior FSW development and test processes. This paper is outlined in a systematic fashion analogous to a lifecycle process flow for engineering development of algorithms into software and testing. Section I describes the NASA SLS M&FM context, presenting the current infrastructure, leading principles, methods, and participants. Section II defines the testing philosophy of the M&FM algorithms as related to VMET followed by section III, which presents the modeling methods of the algorithms to be tested and validated in VMET. Its details are then further presented in section IV followed by Section V presenting integration, test status, and state analysis. Finally, section VI addresses the summary and forward directions followed by the appendices presenting relevant information on terminology and documentation.

Trevino, Luis↗

Complexity Reduction in Large Quantum Systems: Fragment Identification and Population Analysis via a Local Optimized Minimal Basis

We present, within Kohn-Sham Density Functional Theory calculations, a quantitative method to identify and assess the partitioning of a large quantum mechanical system into fragments. We then introduce a simple and efficient formalism (which can be written as generalization of other well-known population analyses) to extract, from first principles, electrostatic multipoles for these fragments. The corresponding fragment multipoles can in this way be seen as reliable (pseudo-) observables. By applying our formalism within the code BigDFT, we show that the usage of a minimal set of in-situ optimized basis functions is of utmost importance for having at the same time a proper fragment definition and an accurate description of the electronic structure. With this approach it becomes possible to simplify the modeling of environmental fragments by a set of multipoles, without notable loss of precision in the description of the active quantum mechanical region. Furthermore, this leads to a considerable reduction of the degrees of freedom by an effective coarsegraining approach, eventually also paving the way towards efficient QM/QM and QM/MM methods coupling together different levels of accuracy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Critical thickness of atomically ordered III-V alloys

The critical thickness model is modified with a general boundary energy that describes the change in bulk energy as a dislocation regularly alters the atomic structure of an ordered material. The model is evaluated for dislocations gliding through CuPt-ordered GaInP and GaInAs, where the boundary energy is negative and the boundary is stable. With ordering present, the critical thickness is significantly lowered and remains finite as the mismatch strain approaches zero. The reduction in critical thickness is most significant when the order parameter is greatest and the amount of misfit energy is low. The modified model is experimentally validated for low-misfit GaInP epilayers with varying order parameters using in situ wafer curvature and ex situ cathodoluminescence. With strong ordering, relaxation begins at a lower thickness and occurs at a greater rate, which is consistent with a lower critical thickness and increased glide force. Thus, atomic ordering is an important consideration for the stability of lattice-mismatched devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

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↗