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At least 19 records

Engineered enzymatic cascade converts diols to amino alcohols

Aliphatic amino alcohols such as 6-amino-1-hexanol are potential platform chemicals for a variety of advanced materials, but applications are currently limited by reagent costs. Aliphatic amino alcohols can currently be synthesized from biomass-derived diols at elevated temperatures and pressures using Ru-based catalysts that produce a mixture of amino-alcohol, diamine, and cyclic amine products. Replacing chemical amination with an enzymatic cascade would reduce resource needs and enable reactions under milder conditions. In this work, we characterized a two-enzyme cascade that selectively converts C4–C7 diols to the corresponding amino alcohols under aqueous conditions at room temperature and pressure. By engineering the rate-limiting enzyme and optimizing reaction conditions, we increased amino alcohol production nearly 30-fold, achieving a selectivity of 99%. The same enzyme cascade could also be used to convert amino alcohols into cyclic amines through reduction of the corresponding cyclic imine. This engineered cascade provides a green opportunity to sustainably synthesize asymmetric bifunctional platform chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

CAS22 - FORTRAN program for fast design and analysis of shock-free airfoil cascades using fictitious-gas concept

A user-oriented computer program, CAS22, was developed that is applicable to aerodynamic analysis and transonic shock-free redesign of existing two-dimensional cascades of airfoils. This FORTRAN program can be used: (1) as an analysis code for full-potential, transonic, shocked or shock-free cascade flows; (2) as a design code for shock-free cascades that uses Sobieczky's fictitious-gas concept; and (3) as a shock-free design code followed automatically by the analysis in order to confirm that the newly obtained cascade shape provides for an entirely shock-free transonic flow field. A four-level boundary-conforming grid of an O type is generated. The shock-free design is performed by implementing Sobieczky's fictitious-gas concept of elliptic continuation from subsonic into supersonic flow domains. Recomputation inside each supersonic zone is performed by the method of characteristics in the rheograph plane by using isentropic gas relations. Besides converting existing cascade shapes with multiple shocked supersonic regions into shock-free cascades, CAS22 can also unchoke previously choked cascades and make them shock free.

Dulikravich, D. S.

Shockless design and analysis of transonic blade shapes

A fast computer program was developed to eliminate the shocks by slightly altering portions of the contour of a given airfoil in the cascade. The program can be used in two basic modes: (1) An analysis for steady, transonic, potential flow through a given planar cascade of airfoils and (2) a design for converting a given cascade into a shockless transonic cascade. The design mode can automatically be followed by the analysis mode, which confirms that the flow field is shock free. The program generates its own multilevel boundary conforming computational grids and solves a full potential equation in a fully conservative form. The shockless design is performed by implementing Sobieczky's fictitious-gas elliptic continuation concept.

Dulikravich, D. S.

Phenomenological model of nuclear primary air showers

The development of proton primary air showers is described in terms of a model based on a hadron core plus an electromagnetic cascade. The muon component is neglected. The model uses three parameters: a rate at which hadron core energy is converted into electromagnetic cascade energy and a two-parameter sea-level shower-age function. By assuming an interaction length for the primary nucleus, the model is extended to nuclear primaries. Both models are applied over the energy range from 10 to the 13th power to 10 to the 21st power eV. Both models describe the size and age structure (neglecting muons) from a depth of 342 to 2052 g/sq cm.

Tompkins, D. R., Jr.

Submodule-Level Decentralized Control for Cascaded Quadruple Active Bridge-Based Medium-Voltage Converters

High-power, low-voltage DC (LVDC) loads, such as AI data centers, electric vehicle fast-charging hubs, and hydrogen electrolyzers, are accelerating the deployment of solid-state transformers (SSTs) that directly interface medium-voltage AC (MVAC) to LVDC, streamlining power delivery. This paper proposes a submodule-level decentralized control strategy for an SST comprising a cascaded H-bridge (CHB) active rectifier on the MVAC side and per-module quadruple-active-bridge (QAB) converters on the LVDC side with local controllers. The proposed strategy eliminates the need for high-fidelity, real-time cross-isolation communication by synchronizing all active bridges to a common heartbeat signal and enabling the primary- and secondary-side controllers to generate independent local control signals (phase shifts). The resultant phase shifts naturally govern average and double-line frequency power transfer between active bridges, enabling each side to meet its control objectives using only local measurements. Detailed controller design considerations are presented based on a stability analysis. Comprehensive electromagnetic-transient simulations demonstrate tight DC-link voltage regulation, high-quality grid currents, and robust operation under load transients and grid disturbances, without real-time communication among the submodule controllers. These results indicate that the proposed scheme can significantly enhance the reliability, scalability, and flexibility of cascaded bridge-based medium-voltage converters.

24 POWER TRANSMISSION AND DISTRIBUTION

Submodule-Level Decentralized Control for Cascaded Quadruple Active Bridge-Based Medium-Voltage Converters: Preprint

High-power, low-voltage DC (LVDC) loads, such as AI data centers, electric vehicle fast-charging hubs, and hydrogen electrolyzers, are accelerating the deployment of solid-state transformers (SSTs) that directly interface medium-voltage AC (MVAC) to LVDC, streamlining power delivery. This paper proposes a submodule-level decentralized control strategy for an SST comprising a cascaded H-bridge (CHB) active rectifier on the MVAC side and per-module quadruple-active-bridge (QAB) converters on the LVDC side with local controllers. The proposed strategy eliminates the need for high-fidelity, real-time cross-isolation communication by synchronizing all active bridges to a common heartbeat signal and enabling the primary- and secondary-side controllers to generate independent local control signals (phase shifts). The resultant phase shifts naturally govern average and double-line frequency power transfer between active bridges, enabling each side to meet its control objectives using only local measurements. Detailed controller design considerations are presented based on a stability analysis. Comprehensive electromagnetic-transient simulations demonstrate tight DC-link voltage regulation, high-quality grid currents, and robust operation under load transients and grid disturbances, without real-time communication among the submodule controllers. These results indicate that the proposed scheme can significantly enhance the reliability, scalability, and flexibility of cascaded bridge-based medium-voltage converters.

24 POWER TRANSMISSION AND DISTRIBUTION

Per-Phase Control for CHB Converters with Negative-Sequence Current and DC Voltage Balancing Control

This paper presents a per-phase controller for a grid-connected Cascaded H-Bridge (CHB) converter featuring negative sequence current regulation and DC bus voltage balancing capabilities. Unlike conventional three-phase controllers, each phase of the CHB can be separately and controlled to regulate the DC voltage and reactive power flow. per-phase negative sequence current control strategy is incorporated into the proposed controller to ensure compliance with IEEE Standard 2800-2022, which requires the absorption of negative-sequence reactive current during grid voltage disturbances. Furthermore, a feed-forward control-based DC bus voltage balancing method is employed, which eliminates the need for the integrator commonly used in traditional approaches. The performance of the proposed controller is validated under various unbalanced grid scenarios and DC bus voltage imbalances through electromagnetic transient (EMT) simulation using a three-phase, three-level grid-connected CHB–Dual Active Bridge (DAB) converter testbed developed on MATLAB/Simulink. Additionally, the performance of the negative-sequence current regulation is investigated through simulation under different unbalanced grid voltage scenarios.

negative sequence current

Modelling, analyses and design of switching converters

A state-space averaging method for modelling switching dc-to-dc converters for both continuous and discontinuous conduction mode is developed. In each case the starting point is the unified state-space representation, and the end result is a complete linear circuit model, for each conduction mode, which correctly represents all essential features, namely, the input, output, and transfer properties (static dc as well as dynamic ac small-signal). While the method is generally applicable to any switching converter, it is extensively illustrated for the three common power stages (buck, boost, and buck-boost). The results for these converters are then easily tabulated owing to the fixed equivalent circuit topology of their canonical circuit model. The insights that emerge from the general state-space modelling approach lead to the design of new converter topologies through the study of generic properties of the cascade connection of basic buck and boost converters.

Cuk, S. M.

Spatiotemporal Energy Cascade in Three-Dimensional Magnetohydrodynamic Turbulence

We present a new scale decomposition method to investigate turbulence in wavenumber-frequency space. Using 3D magnetohydrodynamic turbulence simulations, we show that magnetic fluctuations with time scales longer than the nonlinear time exhibit an inverse cascade toward even smaller frequencies. Low frequency magnetic fluctuations support turbulence, acting as an energy reservoir that is converted into plasma kinetic energy, the latter cascading toward large wavenumbers and frequencies, where it is dissipated. Our results shed new light on the spatiotemporal properties of turbulence, potentially explaining the origin and role of low frequency turbulent fluctuations in the solar wind.

79 ASTRONOMY AND ASTROPHYSICS

Insights from designing an artificial cascade catalysis system using principles from substrate channeling in enzymes

Generalizing the key requirements of highly-selective, multi-step chemical conversions involving spatially separated reaction centers remains one of the grand challenges of chemistry. Much work towards this effort has focused on decomposing multi-step conversions into their constituent reactions, whose intermediates are successively upgraded in a chemical cascade via diffusion from center to center. This approach for synthesizing more complex molecules takes its cues from biochemical networks, where near-unit conversion of even complex carbohydrates is achieved by upgrading chemical precursors via enzymatic cascades. In this computational study we examine a simple cascade involving coupled Ag and Cu catalysts that sequentially converts CO2 to CO and then CO2 and CO to reduced products, generically named CO2Product and COProduct. The system architecture is inspired by the phenomenon of biological substrate channeling, and components are examined to evaluate their effects on conversion efficiency in the cascade. Aside from a substrate channel linking two reaction centers, we find efficient cascades must also incorporate directional substrate diffusion, compartmentalization of the reaction centers, and proper timing of substrate arrival at the active center. We make explicit linkages between these requirements and chemical conversion in known biological systems, revealing additional control elements that could be incorporated.

CO 2 reduction

Spatially Patterned Architectures to Modulate CO 2 Reduction Cascade Catalysis Kinetics

Electrochemical CO 2 reduction using renewable sources of electrical energy holds promise for converting CO 2 into fuels and chemicals. The complex interactions among chemical/electrochemical reactions and mass transport make it difficult to analyze the effect of an individual process on electrode performance based only on experimental methods. Here, we developed a generalized steady-state simulation to describe an electrode surface in which sequential cascade catalysts are patterned in a periodic trench design. If appropriately constructed, this trench geometry is hypothesized to be able to yield a higher net current density for a CO 2 reduction (CO 2 R) cascade reaction. We have used realistic experimental reaction kinetics to investigate the role of trench geometry in mass transport, local microenvironments, and selectivity for a model CO 2 R cascade reaction. The model considers local concentration gradients of bicarbonate species at quasi-equilibrium and catalytic surface reactions based on concentration-dependent Butler–Volmer kinetics. Our results suggest that varying the spatial distribution of active sites plays a significant role in facilitating effective mass transport between active sites, modulating selectivity for the cascade reaction, and enhancing the yield of desirable cascade products. Moreover, we observe that this trench geometry significantly alters the cascade reaction rate by affecting the local pH, which can cause inadvertent depletion of available aqueous CO 2 to limit the CO 2 R cascade kinetics and modest suppression of the hydrogen evolution reaction (HER). The results highlight the trade-offs between mass transport, pH, and reaction kinetics that become apparent only when considering the coupled physics of all processes at the electrode surface. Here, this model can thus serve as a primary tool to build more selective and efficient patterned architectures for the CO 2 R cascade catalysis.

CO2 reduction

A Novel Three-Phase Isolated LLC and Non-Isolated LCL-T Resonant Converter for Fuel Cell Applications

In this paper, a novel three-phase isolated LLC and non-isolated LCL−T resonant converter topologies are introduced for fuel cell applications. In order to improve the fuel cell DC/DC converter efficiency, the current amplitude should be reduced in the power stage components. Cascaded connections of fuel cell blocks through a controllable system enable using higher voltage amplitude and bring the current amplitude lower at the target power. In this way, power losses in the passive components can be reduced, and maximum energy transfer can be established, improving the DC/DC converter efficiency from the fuel cell to the load. The introduced new converter also achieves soft switching (ZVS), minimizing the switching losses in all input and output load conditions. The presented three-phase isolated LLC and non-isolated LCL−T resonant converter systems, fed by three fuel cell modules with an output range of 190380 V, deliver 580−730 V at 450 kW maximum output power. The results reveal that the proposed systems have the advantage of reducing the size, volume, and weight and increasing the overall DC/DC converter system efficiency compared to the single-phase systems.

Asa, Erdem [ORNL] (ORCID:0000000190884812)

Substituent effect on napthodithiophene-fused porphyrins: Understanding the unusual trend of fluorescence quantum yield quenching

A series of π-extended porphyrins containing thiophene units was prepared to investigate an unusual trend observed in the fluorescence quantum yield of naphtho[2,1-b:3,4-b']dithiophene-fused porphyrins. Monobenzoporphyrins carrying 2-thiophenyl (vinyl thiophene porphyrin) groups (2VTP, 2VTBr and Br2VTP) (numbering 2 and 3 refers to the position of sulfur on the thiophene ring) were synthesized through a Heck-based cascade reaction followed by a newly developed bromination method. These were converted to naphtho[2,1-b:3,4-b']dithiophene-fused porphyrin derivatives (FBr2VTP and F2VTBr) via ring closure with an intramolecular Scholl reaction. Increasingly larger Stokes shifts with a higher number of bromo groups were observed in the unfused π-extended molecular systems, reflecting the heavy atom effect. Fluorescence spectroscopy further confirmed the unusual trend seen in the previous work: structural rigidification in naphtho[2,1-b:3,4-b']dithiophene-fused porphyrins leads to longer fluorescence lifetimes but unexpectedly lowers the quantum yield. Adding one bromo group to the naphtho[2,1-b:3,4-b']dithiophene unit does not change this trend. Furthermore, the presence of two bromo groups prevents the quantum yield from dropping. DFT, TDDFT, and NICS analyses suggest a drastic change in aromaticity in the pyrrole ring where the naphtho[2,1-b:3,4-b']dithiophene is fused in FBr2VTP, which might contribute to the quantum yield reductions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Solid state Ku-band spacecraft transmitters

A transmitter is considered that consists of GaAs IMPATT and Read diodes operating in a microstrip circuit environment to provide amplification with a minimum of 63 db small signal gain and a minimum compressed gain at 5 W output of 57 db. Reported are Schottky-Read diode design and fabrication, microstrip and circulator optimization, preamplifier development, power amplifier development, dc-to-dc converter design, and integration of the breadboard transmitter modules. A four-stage power amplifier in cascade with a three-stage preamplifier had an overall gain of 56.5 db at 13.5 GHz with a power output of 4.5 W. A single-stage Read amplifier delivered 5.9 W with 4 db gain at 22% efficiency.

Wisseman, W. R.

The NASA program in Space Energy Conversion Research and Technology

The considered Space Energy Conversion Program seeks advancement of basic understanding of energy conversion processes and improvement of component technologies, always in the context of the entire power subsystem. Activities in the program are divided among the traditional disciplines of photovoltaics, electrochemistry, thermoelectrics, and power systems management and distribution. In addition, a broad range of cross-disciplinary explorations of potentially revolutionary new concepts are supported under the advanced energetics program area. Solar cell research and technology are discussed, taking into account the enhancement of the efficiency of Si solar cells, GaAs liquid phase epitaxy and vapor phase epitaxy solar cells, the use of GaAs solar cells in concentrator systems, and the efficiency of a three junction cascade solar cell. Attention is also given to blanket and array technology, the alkali metal thermoelectric converter, a fuel cell/electrolysis system, and thermal to electric conversion.

Mullin, J. P.