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All sourcesNASA NTRSDOE OSTI
NASA NTRS1976

PPP effectiveness study

This design note presents a study of the Procedures and Performance Program (PPP) effectiveness. The intent of the study is to determine manpower time savings and the improvements in job performance gained through PPP automated techniques. The discussion presents a synopsis of PPP capabilities and identifies potential users and associated applications, PPP effectiveness, and PPP applications to other simulation/training facilities. Appendix A provides a detailed description of each PPP capability.

Arbet, J. D.↗
DOE OSTI2022

High Activity and Selectivity for Catalytic Alkane–Alkene Transfer (De)hydrogenation by ( tBu PPP)Ir and the Importance of Choice of a Sacrificial Hydrogen Acceptor

The triphosphorus-coordinating pincer iridium fragment ( tBu PPP)Ir was recently reported to be highly active for the catalytic dehydrogenation of n-alkanes. Dehydrogenation is calculated to be highly regioselective for the terminal position of n-alkanes. Here, the extremely high intermolecular selectivity observed in n-alkane/cycloalkane competition experiments supports the prediction of extremely high regioselectivity for dehydrogenation of n-alkanes. The use of sterically unhindered hydrogen acceptors is key to observing the high activity of the ( tBu PPP)Ir fragment. 4,4-Dimethylpent-1-ene (TBP) is found to be particularly convenient for this purpose. With the commonly used hydrogen acceptor 3,3-dimethylbut-1-ene (TBE), ( tBu PPP)Ir affords n-alkane dehydrogenation at a rate no different than that obtained with the well-known fragment ( iPr PCP)Ir. However, with the use of TBP as acceptor, ( tBu PPP)Ir shows much greater activity for n-alkane transfer dehydrogenation than previously reported catalysts, affording appreciable rates even at 50 °C, an unprecedentedly low temperature for catalytic alkane transfer dehydrogenation. Also critical to the identification of ( tBu PPP)Ir as a highly effective catalyst is the use of n-alkane substrate rather than the commonly used “model” dehydrogenation substrate, cyclooctane, with which dehydrogenation rates are much lower than those with n-alkanes.

10 SYNTHETIC FUELS↗
DOE OSTI2016

Crystal structures and mutagenesis of PPP-family ser/thr protein phosphatases elucidate the selectivity of cantharidin and novel norcantharidin-based inhibitors of PP5C

Cantharidin is a natural toxin and an active constituent in a traditional Chinese medicine used to treat tumors. Cantharidin acts as a semi-selective inhibitor of PPP-family ser/thr protein phosphatases. Despite sharing a common catalytic mechanism and marked structural similarity with PP1C, PP2AC and PP5C, human PP4C was found to be insensitive to the inhibitory activity of cantharidin. To explore the molecular basis for this selectivity, in this work we synthesized and tested novel C5/C6-derivatives designed from quantum-based modeling of the interactions revealed in the co-crystal structures of PP5C in complex with cantharidin. Structure–activity relationship studies and analysis of high-resolution (1.25 Å) PP5C-inhibitor co-crystal structures reveal close contacts between the inhibitor bridgehead oxygen and both a catalytic metal ion and a non-catalytic phenylalanine residue, the latter of which is substituted by tryptophan in PP4C. Quantum chemistry calculations predicted that steric clashes with the bulkier tryptophan side chain in PP4C would force all cantharidin-based inhibitors into an unfavorable binding mode, disrupting the strong coordination of active site metal ions observed in the PP5C co-crystal structures, thereby rendering PP4C insensitive to the inhibitors. This prediction was confirmed by inhibition studies employing native human PP4C. Mutation of PP5C (F446W) and PP1C (F257W), to mimic the PP4C active site, resulted in markedly suppressed sensitivity to cantharidin. These observations provide insight into the structural basis for the natural selectivity of cantharidin and provide an avenue for PP4C deselection. The novel crystal structures also provide insight into interactions that provide increased selectivity of the C5/C6 modifications for PP5C versus other PPP-family phosphatases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Reactivity of Iridium Complexes of a Triphosphorus-Pincer Ligand Based on a Secondary Phosphine. Catalytic Alkane Dehydrogenation and the Origin of Extremely High Activity

The selective functionalization of alkanes and alkyl groups is a major goal of chemical catalysis. Toward this end, a bulky triphosphine with a central secondary phosphino group, bis(2-di-t-butyl-phosphinophenyl)phosphine ( tBu P H PP), has been synthesized. When complexed to iridium, it adopts a meridional (“pincer”) configuration. The secondary phosphino H atom can undergo migration to iridium to give an anionic phosphido-based–pincer ( tBu PPP) complex. Stoichiometric reactions of the ( tBu PPP)Ir complexes reflect a distribution of steric bulk around the iridium center in which the coordination site trans to the phosphido group is quite crowded; one coordination site cis to the phosphido is even more crowded; and the remaining site is particularly open. The ( tBu PPP)Ir precursors are the most active catalysts reported to date for dehydrogenation of n-alkanes, by about 2 orders of magnitude. The electronic properties of the iridium center are similar to that of well-known analogous ( R PCP)Ir catalysts. Accordingly, DFT calculations predict that ( tBu PPP)Ir and ( tBu PCP)Ir are, intrinsically, comparably active for alkane dehydrogenation. While dehydrogenation by ( R PCP)Ir proceeds through an intermediate trans-(PCP)IrH 2 (alkene), ( tBu PPP)Ir follows a pathway proceeding via cis-(PPP)IrH 2 (alkene), thereby circumventing unfavorable placement of the alkene at the bulky site trans to phosphorus. ( tBu PPP)Ir and ( tBu PCP)Ir, however, have analogous resting states: square planar (pincer)Ir(alkene). Alkene coordination at the crowded trans site is therefore unavoidable in the resting states. Furthermore, the resting state of the ( tBu PPP)Ir catalyst is destabilized by the architecture of the ligand, and this is largely responsible for its unusually high catalytic activity.

02 PETROLEUM↗
DOE OSTI2023

Shear-aligned large-area organic semiconductor crystals through extended π–π interaction

Small molecule-based organic semiconductors are of broad interest in organic field-effect transistors (OFETs) due to their potential for high crystallinity and electrical performance. The 2D molecule, TIPS-peri-pentacenopentacene (TIPS-PPP), which is the vertical extension of the 1D TIPS-pentacene (TIPS-PEN) molecule, offers a lower bandgap, higher aromaticity, and an enhanced π–π interaction with neighboring molecules in the solid state when compared to TIPS-PEN. However, an in-depth understanding of the relationship between the molecule structure, solid-state molecular packing, and the electronic properties has not been reported due to poor control over the TIPS-PPP crystallite size. In this work, we successfully engineered highly oriented large-area TIPS-PPP crystals through the solution shear coating technique. Additionally, compared with narrow ribbon-like TIPS-PEN crystals, TIPS-PPP crystals can grow centimeters long and over 500 μm wide. TIPS-PPP molecules are less susceptible to forming metastable polymorphs than TIPS-PEN molecules upon fast evaporation. The crystal structure of TIPS-PPP is also thermally stable at 250 °C. Notably, the anisotropic charge carrier mobility of TIPS-PPP crystals is resolved through fabricating bottom-gate top-contact devices, with a hole mobility of 3.1 cm 2 V -1 s -1 along the preferred packing direction. Further device optimization using top-gate bottom-contact devices improved the mobility up to 6.5 cm 2 V -1 s -1 , which is among the highest for pentacene-derivative-based organic semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Multiport Control with Partial Power Processing in Solid-State Transformer for PV, Storage, and Fast-Charging Electric Vehicle Integration

This article proposes a multiport control method to enable partial power processing (PPP) in a medium-voltage (MV) multiport solid-state transformer (SST). MV multiport SSTs are promising in integrating low-voltage DC sources or loads such as solar photovoltaic, energy storage, and electric vehicles into smart grids without bulky line-frequency transformers. Compared to voltage-source SST, current-source (CS) SST features single-stage isolated bidirectional AC/AC, AC/DC, or DC/DC conversion using an inductive DC link. For a multiport CS SST, it is revealed in this article that the PPP capability can be enabled through the proposed control without extra hardware, different from the case of voltage-source converters where special hardware architecture is required for the PPP. With the PPP, most power exchange between LV ports is processed by only a fraction of the entire conversion stage, leading to reduced DC-link current, volume, loss, and improved efficiency. The proposed multiport PPP control scheme is analyzed to verify the advantages across a wide voltage and power range against conventional full power processing (FPP) multiport control, using the soft-switching solid-state transformer (S4T) with reduced conduction loss as an example. Comparative experimental results based on a SiC three-port S4T prototype verify the effectiveness of the proposed PPP scheme against the FPP scheme under both steady state and dynamic conditions. Here, the DC-link current reduction is measured to be more than 36%. Significantly, the proposed multiport PPP control scheme is generic and applicable to any hard-switching or soft-switching CS SSTs without extra hardware.

14 SOLAR ENERGY↗
DOE OSTI2018

Magnify: A Final Technical Report of the American Energy and Manufacturing Competitiveness Partnership

The energy landscape has undergone profound transformation, with dramatic shifts having an impact on U.S. productivity, global investment, manufacturing operations, and job creation. The sense of urgency for a tighter linkage between clean technologies, energy and advanced manufacturing has only grown. Prior to 2009, the tone of the nation’s energy conversation was centered on how to deal with long-standing energy security challenges and scarcity. Today, the tone is focused on seizing emerging energy growth opportunities to transform America’s industrial base and job creation outlook—centering on energy abundance and strength. In this context, the Council on Competitiveness and the Department of Energy’s Office of Energy Efficiency & Renewable Energy (EERE) teamed in the American Energy & Manufacturing Competitiveness (AEMC) Partnership to tackle two major goals via a multi-year partnership. The AEMC Partnership identified means to: • Increase U.S. competitiveness in the production of clean energy products • Increase U.S. manufacturing competitiveness across the board by increasing energy productivity The AEMC Partnership has engaged hundreds of leaders from industry, academia, labor and government in a series of 9 regional, progressive dialogues; original research; and 4 national summits. The AEMC dialogues and summits spanned the United States—taking place in our nation’s greatest manufacturing, research, technology and innovation hotspots. The goals of the AEMC Partnership have been straightforward: • State and define key barriers, challenges, and problems in U.S. competitiveness in manufacturing of clean energy products, energy efficiency products, and advanced manufacturing products. • Dive deeply into these problems and generate policies, solutions, concepts and models where the U.S. public and private sectors can work together to solve these problems. • Catalyze policy solutions—including models for public-private partnership (PPP) pilots—to increase competitive manufacturing of clean energy and energy efficiency products in the USA. • Elevate and increase awareness of the importance and benefits of competitive clean energy manufacturing. • Understand how energy game-changers, like breakthrough technologies, impact U.S. clean energy and energy efficient manufacturing. The Council on Competitiveness worked with its stakeholder network to generate potential PPP concepts and proposals to advance the goals of the AEMC Partnership. Magnify outlines 2 PPP concepts—honed by dialogues, conversations, interviews and research—that could be carried out by EERE and/or the Council to increase the competitive production of clean energy products, energy efficient products, and advanced manufacturing in the USA. Magnify’s 2 PPP concepts aim to bridge very specific gaps in the nation’s innovation ecosystem: • Clean Energy Materials Accelerator: This PPP concept focuses on reducing the risks associated with deploying newly developed materials in commercial products and processes by creating a platform to identify and address common challenges; increasing access to existing materials qualification and characterization tools; and creating standards for advanced materials with leaders in industry, academic, government, and other organizations. Why accelerate materials production? As the AEMC Partnership Dialogue and supporting research from the public and private sectors have documented, countries that lead in making next-generation materials will gain significant competitive advantage by unleashing a new wave of manufacturing innovation. • Manufacturing and Energy Technology Accelerator: This PPP concept is a new, physical and virtual collaborative resource platform designed to connect the nation’s world-class innovation institutions—SMEs, large multinational companies, universities, national laboratories, etc.—to facilitate the transition of cutting-edge clean energy technologies into products, processes, or services that are manufactured in the United States. Why should public and private sector leaders in innovation partner to co-create a scale-up platform? The United States is already a mecca for the world’s greatest minds in science and technology—drawn to our shores by world-class universities and opportunities to work with global leaders in innovation. Unfortunately, when it comes time to bring their ideas to market, technologists and entrepreneurs often choose, or are forced, to locate manufacturing overseas. The United States must regain its position in the world as a national scale-up platform for next-generation technologies. A thorough explanation of these PPP concepts and the rationale behind these recommendations is provided in Part 3 of Magnify. Magnify is an important step on the critical journey to define barriers, challenges and problems in the manufacturing of clean energy products and energy efficient products—and further honing concepts for scalable, public-private partnerships—to increase the competitive manufacturing of clean energy and energy efficient products, and the energy productivity throughout the U.S. manufactur¬ing sector. The rest of the world is waking up to the opportunities associated with a strategic focus on manufacturing and energy competitiveness. Global competition is on the rise, and the stakes are high for the United States to act now, to act decisively, and to leverage inherent strengths to ensure a more prosperous, competitive future for decades to come.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2021

Pentose Phosphate Pathway Reactions in Photosynthesizing Cells

The pentose phosphate pathway (PPP) is divided into an oxidative branch that makes pentose phosphates and a non-oxidative branch that consumes pentose phosphates, though the non-oxidative branch is considered reversible. A modified version of the non-oxidative branch is a critical component of the Calvin–Benson cycle that converts CO2 into sugar. The reaction sequence in the Calvin–Benson cycle is from triose phosphates to pentose phosphates, the opposite of the typical direction of the non-oxidative PPP. The photosynthetic direction is favored by replacing the transaldolase step of the normal non-oxidative PPP with a second aldolase reaction plus sedoheptulose-1,7-bisphosphatase. This can be considered an anabolic version of the non-oxidative PPP and is found in a few situations other than photosynthesis. In addition to the strong association of the non-oxidative PPP with photosynthesis metabolism, there is recent evidence that the oxidative PPP reactions are also important in photosynthesizing cells. These reactions can form a shunt around the non-oxidative PPP section of the Calvin–Benson cycle, consuming three ATP per glucose 6-phosphate consumed. A constitutive operation of this shunt occurs in the cytosol and gives rise to an unusual labeling pattern of photosynthetic metabolites while an inducible shunt in the stroma may occur in response to stress.

13C↗
DOE OSTI2016

Structural basis for m7G recognition and 2'-O-methyl discrimination in capped RNAs by the innate immune receptor RIG-I

RNAs with 5'-triphosphate (ppp) are detected in the cytoplasm principally by the innate immune receptor Retinoic Acid Inducible Gene-I (RIG-I), whose activation triggers a Type I IFN response. It is thought that self RNAs like mRNAs are not recognized by RIG-I because 5'ppp is capped by the addition of a 7-methyl guanosine (m7G) (Cap-0) and a 2'-O-methyl (2'-OMe) group to the 5'-end nucleotide ribose (Cap-1). Here we provide structural and mechanistic basis for exact roles of capping and 2'-O-methylation in evading RIG-I recognition. Surprisingly, Cap-0 and 5'ppp double-stranded (ds) RNAs bind to RIG-I with nearly identical K d values and activate RIG-I’s ATPase and cellular signaling response to similar extents. On the other hand, Cap-0 and 5'ppp single-stranded RNAs did not bind RIG-I and are signaling inactive. Three crystal structures of RIG-I complexes with dsRNAs bearing 5'OH, 5'ppp, and Cap-0 show that RIG-I can accommodate the m7G cap in a cavity created through conformational changes in the helicase-motif IVa without perturbing the ppp interactions. In contrast, Cap-1 modifications abrogate RIG-I signaling through a mechanism involving the H830 residue, which we show is crucial for discriminating between Cap-0 and Cap-1 RNAs. Furthermore, m7G capping works synergistically with 2'-O-methylation to weaken RNA affinity by 200-fold and lower ATPase activity. Interestingly, a single H830A mutation restores both high-affinity binding and signaling activity with 2'-O-methylated dsRNAs. Our work provides new structural insights into the mechanisms of host and viral immune evasion from RIG-I, explaining the complexity of cap structures over evolution.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1968

Phased Project Planning Guidelines

NHB 7121.2 is the initial publication of the guidelines for implementation of the Phased Project Planning (PPP) concept prescribed by NPD 7121,1A. These guidelines are applicable to the planning and approval activities which lead to the implementation of major new research and development projects as defined in NPD 7121.1A as well as to major modifications or extensions of approved projects. They should, therefore, be reflected in the Project Approval Documents which serve as the basic documentation for project definition, guidance and control throughout NASA. The purpose of PPP is to provide, through defined phases, an adequate basis for management decisions on the extent to which project activities can be properly undertaken and commitments made. However, these guidelines do not prescribe detailed format and content of plans and other documents and reports used to apply the PPP concept. Similarly, the work content of phases and the information requirements described herein are not checklists. They are included to assist in understanding the intent of the PPP concept and should not be viewed as rigid or inflexible. PPP, as a concept for orderly planning and definition of new major R&D undertakings, must be adapted to the peculiarities of each individual case. However, the flexibility permitted for adaptation should not be considered as a license for major variation which would compromise the objectives that underlie the concept. Cognizant NASA officials are expected to pursue their project planning and definition activities in reasonable conformance with these guidelines and to request only those exceptions or deviations which are clearly necessary and justified. These guidelines will be modified as determined necessary on the basis of experience. Comments or suggestions for changes should be directed to the Office of Organization and Management.

Source record↗
NASA NTRS1999

Deep Space One High-Voltage Bus Management

The design of the High Voltage Power Converter Unit on DS1 allows both the spacecraft avionics and ion propulsion to operate in a stable manner near the PPP of the solar array. This approach relies on a fairly well-defined solar array model to determine the projected PPP. The solar array voltage set-points have to be updated every week to maintain operation near PPP. Stable operation even to the LEFT of the Peak Power Point is achievable so long as you do not change the operating power level of the ion engine. The next step for this technology is to investigate the use of onboard autonomy to determine the optimum SA voltage regulation set-point (i.e. near the PPP); this is for future missions that have one or more ion propulsion subsystems.

Rachocki, Ken↗
NASA NTRS2002

Numerical Simulation of Flow Field Within Parallel Plate Plastometer

Parallel Plate Plastometer (PPP) is a device commonly used for measuring the viscosity of high polymers at low rates of shear in the range 10 4 to 10 9 poises. This device is being validated for use in measuring the viscosity of liquid glasses at high temperatures having similar ranges for the viscosity values. PPP instrument consists of two similar parallel plates, both in the range of 1 inch in diameter with the upper plate being movable while the lower one is kept stationary. Load is applied to the upper plate by means of a beam connected to shaft attached to the upper plate. The viscosity of the fluid is deduced from measuring the variation of the plate separation, h, as a function of time when a specified fixed load is applied on the beam. Operating plate speeds measured with the PPP is usually in the range of 10 -3 cm/s or lower. The flow field within the PPP can be simulated using the equations of motion of fluid flow for this configuration. With flow speeds in the range quoted above the flow field between the two plates is certainly incompressible and laminar. Such flows can be easily simulated using numerical modeling with computational fluid dynamics (CFD) codes. We present below the mathematical model used to simulate this flow field and also the solutions obtained for the flow using a commercially available finite element CFD code.

Basil N. Antar↗
DOE OSTI2017

A Plug-and-Play Priors Approach for Solving Nonlinear Imaging Inverse Problems

In the past two decades, nonlinear image reconstruction methods have led to substantial improvements in the capabilities of numerous imaging systems. Such methods are traditionally formulated as optimization problems that are solved iteratively by simultaneously enforcing data consistency and incorporating prior models. Recently, the Plug-and-Play Priors (PPP) framework suggested that by using more sophisticated denoisers, not necessarily corresponding to an optimization objective, it is possible to improve the quality of reconstructed images. Here in this letter, we show that the PPP approach is applicable beyond linear inverse problems. In particular, we develop the fast iterative shrinkage/thresholding algorithm variant of PPP for model-based nonlinear inverse scattering. The key advantage of the proposed formulation over the original ADMM-based one is that it does not need to perform an inversion on the forward model. We show that the proposed method produces high quality images using both simulated and experimentally measured data.

97 MATHEMATICS AND COMPUTING↗