Modifying Carbon Nitride through Extreme Phosphorus Substitution
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99 GENERAL AND MISCELLANEOUS↗
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An Improved CRISPR Interference Tool to Engineer Rhodococcus opacus
Rhodococcus opacus is a non-model bacterium that is well suited for valorizing lignin. Despite recent advances in our systems-level understanding of its versatile metabolism, studies of its gene functions at a single gene level are still lagging. Elucidating gene functions in non-model organisms is challenging due to limited genetic engineering tools that are convenient to use. To address this issue, we developed a simple gene repression system based on CRISPR interference (CRISPRi). This gene repression system uses a T 7 RNA polymerase system to express a small guide RNA, demonstrating improved repression compared to the previously demonstrated CRISPRi system (i.e., the maximum repression efficiency improved from 58% to 85%). Additionally, our cloning strategy allows for building multiple CRISPRi plasmids in parallel without any PCR step, facilitating the engineering of this GC-rich organism. Using the improved CRISPRi system, we confirmed the annotated roles of four metabolic pathway genes, which had been identified by our previous transcriptomic analysis to be related to the consumption of benzoate, vanillate, catechol, and acetate. Furthermore, we showed our tool’s utility by demonstrating the inducible accumulation of muconate that is a precursor of adipic acid, an important monomer for nylon production. While the maximum muconate yield obtained using our tool was 30% of the yield obtained using gene knockout, our tool showed its inducibility and partial repressibility. In conclusion, our CRISPRi tool will be useful to facilitate functional studies of this non-model organism and engineer this promising microbial chassis for lignin valorization.
09 BIOMASS FUELS↗
Direct preemptive stabilization of $m,n$ = 2,1 neoclassical tearing modes by electron cyclotron current drive in the DIII-D low-torque ITER baseline scenario
We report the first preemptive direct stabilization of $m,n$ = 2,1 neoclassical tearing modes (NTMs) in DIII-D low-torque ITER baseline scenario plasmas by electron cyclotron waves. These experiments strongly support that the observed stabilization is achieved by replacing the missing bootstrap current in the island by electron cyclotron current drive (ECCD). These plasmas (with and without ECCD) are stable to 2,1 NTMs when the differential rotation between the q = 1 and q = 2 surfaces (Δf 1,2 ) is sustained above a critical value (Δf CRIT ≈ 1 kHz), but those evolving to low differential rotation (Δf 1,2 < Δf CRIT ) routinely develop a disruptive 2,1 island at the time and frequency of a sawtooth precursor. Preemptive, local and direct stabilization by ECCD is tested by scanning the current drive amplitude and location inside and outside of the q = 2 rational surface shot by shot. Analysis of only low differential rotation time windows, i.e. when stabilization from Δf 1,2 is absent, shows focused ECCD at q = 2 prevents the onset of 2,1 NTMs. These results are important, as they give the first demonstration of disruptive NTM control by ECCD in the plasma scenario planned for ITER.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Corn stover variability drives differences in bisabolene production by engineered Rhodotorula toruloides
Microbial conversion of lignocellulosic biomass represents an alternative route for production of biofuels and bioproducts. While researchers have mostly focused on engineering strains such as Rhodotorula toruloides for better bisabolene production as a sustainable aviation fuel, less is known about the impact of the feedstock heterogeneity on bisabolene production. Critical material attributes like feedstock composition, nutritional content, and inhibitory compounds can all influence bioconversion. Further, the given feedstocks can have a marked influence on selection of suitable pretreatment and hydrolysis technologies, optimizing the fermentation conditions, and possibly even modifying the microorganism's metabolic pathways, to better utilize the available feedstock. Here, this work aimed to examine and understand how variations in corn stover batches, anatomical fractions, and storage conditions impact the efficiency of bisabolene production by R. toruloides. All of these represent different facets of feedstock heterogeneity. Deacetylation, mechanical refining, and enzymatic hydrolysis of these variable feedstocks served as the basis of this research. The resulting hydrolysates were converted to bisabolene via fermentation, a sustainable aviation fuel precursor, using an engineered R. toruloides strain. This study showed that different sources of feedstock heterogeneity can influence microbial growth and product titer in counterintuitive ways, as revealed through global analysis of protein expression. The maximum bisabolene produced by R. toruloides was on the stalk fraction of corn stover hydrolysate (8.89 ± 0.47 g/L). Further, proteomics analysis comparing the protein expression between the anatomic fractions showed that proteins relating to carbohydrate metabolism, energy production, and conversion as well as inorganic ion transport metabolism were either significantly upregulated or downregulated. Specifically, downregulation of proteins related to the iron–sulfur cluster in stalk fraction suggests a coordinated response by R. toruloides to maintain overall metabolic balance, and this was corroborated by the concentration of iron in the feedstocks.
09 BIOMASS FUELS↗
Ground-based Nuclear Detonation Detection (GNDD) Technology Roadmap
This GNDD Technology Roadmap is intended to provide guidance to potential researchers and help management define research priorities to achieve technology advancements for ground-based nuclear explosion monitoring science being pursued by the Ground-based Nuclear Detonation Detection (GNDD) Team within the Office of Nuclear Detonation Detection in the National Nuclear Security Administration (NNSA) of the U.S. Department of Energy (DOE). Four science-based elements were selected to encompass the entire scope of nuclear monitoring research and development (R&D) necessary to facilitate breakthrough scientific results, as well as deliver impactful products. Promising future R&D is delineated including dual use associated with the Comprehensive Nuclear-Test-Ban Treaty (CTBT). Important research themes as well as associated metrics are identified along with a progression of accomplishments, represented by a selected bibliography, that are precursors to major improvements to nuclear explosion monitoring.
45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
Initiating a Roadmap for Solar Fuels R&D: Imagining Beyond Thermochemical Cycles
Sandia National Laboratories in collaboration with the National Renewable Energy Laboratory outline a framework for developing a solar fuels roadmap based on novel concepts for hybridizing gas-splitting thermochemical cycle s with high-temperature electro chemical steps. We call this concept SoHyTEC, a Solar Hybrid Thermochemical-Electrochemical Cycle. The strategy focuses on transforming purely thermochemical cycles that split water (H 2 O) and carbon dioxide (CO 2 ) to produce hydrogen (H 2 ) and carbon monoxide (CO) , respectively, the fundamental chemical building blocks for diverse fuels and chemicals , by substituting thermochemical reactions with high-temperature electrochemical steps. By invoking high-temperature electrochemistry, the energy required to complete the gas-splitting cycle is divided into a thermal component (process temperature) and an electrical component (applied voltage). These components, sourced from solar energy, are independently variable knobs to maximize overall process efficiency. Furthermore, a small applied voltage can reduce cycle process temperature by hundreds of degrees , opening the door to cost-effective solar concentrators and practical receiver/reactor de signs. Using the SoHyTEC concept as a backdrop, we outline a framework that advocates developing methods for automating information gathering, critically evaluating thermochemical cycles for adapting into SoHyTEC, establishing requirements based on thermodynamic analysis, and developing a model-based approach to benchmarking a SoHyTEC system against a baseline concentrating solar thermal integrated electrolysis plant. We feel these framework elements are a necessary precursor to creating a robust and adaptive technology development roadmap for producing solar fuels using SoHyTEC. In one example, we introduce high-temperature electrochemistry as a method to manipulate a fully stoichiometric two-step metal oxide cycle that circumvents costly separation processes and ultra-high cycle temperatures. We also identify and group water-splitting chemistries that are conceptually amenable to hybridization.
14 SOLAR ENERGY↗
Steam-Assisted Ammonolysis of MoO2 as a Synthetic Pathway to Oxygenated δ-MoN
A common route for the synthesis of molybdenum nitrides is through the temperature-programmed reaction of molybdenum oxides with NH3, or ammonolysis. In this work, the role of precursor phase, gas phase chemistry (impact of H2O), and temperature profile on the reaction outcome (700 °C) was examined, which resulted in varying amounts of MoO2, H2MoO5, and the nitride phases—cubic γ (nominally Mo2N) and hexagonal δ (nominally MoN). The phase fraction of the δ phase increased with precursor in the sequence MoO2 > MoO3 > H2MoO5. Steam in the reaction gas also favored the production of δ over γ, but with too much steam, MoO2 was obtained in the product. Synthesis conditions for obtaining nearly phase-pure δ were identified: MoO2 as the precursor, 2% H2O in the gas stream, and a moderate heating rate (3 °C/min). In situ X-ray diffraction provided insights into the reaction pathway. Extensive physico-chemical analysis of the δ phase, including synchrotron X-ray and neutron diffraction, electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and prompt gamma activation analysis, revealed its stoichiometry to be MoO0.108(8)N0.892(8)H0.012(5), indicating non-trivial oxygen incorporation. The presence of N/O ordering and an impurity phase Mo5N6 were also revealed, detectable only by neutron diffraction. Notably, a computationally predicted MoON phase (doi: 10.1103/PhysRevLett.123.236402), of interest due to its potential to display a metal-insulator transition, did not appear under any reaction condition examined.
Pandey, Shobhit↗
A HELIOSEISMIC SURVEY OF NEAR-SURFACE FLOWS AROUND ACTIVE REGIONS AND THEIR ASSOCIATION WITH FLARES
We use helioseismic holography to study the association of shallow flows with solar flare activity in about 250 large sunspot groups observed between 2010 and 2014 with the Helioseismic and Magnetic Imager on the Solar Dynamics Observatory. Four basic flow parameters: horizontal speed, horizontal component of divergence, vertical component of vorticity, and a vertical kinetic helicity proxy, are mapped for each active region (AR) during its passage across the solar disk. Flow indices are derived representing the mean and standard deviation of these parameters over magnetic masks and compared with contemporary measures of flare X-ray flux. A correlation exists for several of the flow indices, especially those based on the speed and the standard deviation of all flow parameters. However, their correlation with X-ray flux is similar to that observed with the mean unsigned magnetic flux density over the same masks. The temporal variation of the flow indices are studied, and a superposed epoch analysis with respect to the occurrence to 70 M and X-class flares is made. While flows evolve with the passage of the ARs across the disk, no discernible precursors or other temporal changes specifically associated with flares are detected.
79 ASTRONOMY AND ASTROPHYSICS↗
BETO 2021 Peer Review - Improving Formate Upgrading by Cupriavidus Necator 2.3.2.111
Formate can be generated by electrocatalytic reduction of CO2 and has been proposed as a soluble intermediate for the storage of carbon and energy. Biological systems capable of assimilating formate could enable conversion of formate generated from low-cost renewable energy and waste CO2 to myriad fuels and chemicals. To that end, the goal of this project is to develop the natural formatotroph Cupriavidus necator as a robust microbial chassis for efficient conversion of formate to value-added products. Using a combination of laboratory evolution and rational engineering, we have identified mutations and genetic deletions that improve its growth rate and biomass yield on formate by 1.2X. Using RNA-seq transcriptomics, we are elucidating the mechanisms that underly these improvements and anticipate this will contribute to our understanding of formate conversion. We have also engineered C. necator to convert formate to the potential polymer precursor 2-hydroxymuconate semialdehyde (2HMS) by introducing an exogenous pathway and deleting competing pathways and demonstrated production and robust growth using a pH-stat bioreactor. Final techno-economic analysis and life-cycle assessment on biological production of 2HMS from formate will enable the DOE and other stake holders to evaluate the economic and environmental impact of this project and related technologies.
29 ENERGY PLANNING, POLICY, AND ECONOMY↗
Shape-preserving amorphous-to-crystalline transformation of CaCO3 revealed by in situ TEM
Organisms use inorganic ions and macromolecules to regulate crystallization from amorphous- precursors, endowing natural biominerals with complex morphologies and enhanced properties. The mechanisms by which modifiers enable these shape preserving transformations are poorly understood. We used in situ liquid-phase transmission electron microscopy to follow the evolution from amorphous calcium carbonate to calcite in the presence of additives. A combination of contrast analysis and infrared spectroscopy shows that Mg ions, which are widely present in seawater and biological fluids, alter the transformation pathway in a concentration-dependent manner. The ions bring excess (structural) water into the amorphous bulk so that a direct transformation is triggered by dehydration in the absence of morphological changes. Molecular dynamics simulations suggest Mg-incorporated water induces structural fluctuations, allowing transformation without the need to nucleate a separate crystal. Thus, the obtained calcite retains the original morphology of the amorphous state, biomimetically achieving the morphological control of crystals seen in biominerals
crystallization, biomineralization, calcium carbon↗
Preparation of aluminum hydroxide and oxide nanostructures with controllable morphology by wet oxidation of AlN/Al nanoparticles
Highlights: • Aluminum hydroxide nanoparticles were synthesized by wet oxidation methods. • The oxidation conditions of AlN/Al affect the morphologies of the reaction products. • No changes in the synthesized materials morphology occurred up to 1000 °C. • The maxima specific surface areas for the nanostructures were achieved at 500 °C. - Abstract: A simple and environmentally friendly method to prepare aluminum oxyhydroxide and trihydroxide nanostructures by wet oxidation of AlN/Al composite nanoparticles was developed. The AlN/Al nanoparticles used were produced by electrical explosion of an aluminum wire in nitrogen atmosphere. The obtained nanostructures were characterized employing X-ray diffraction (XRD), transmission and high-resolution scanning electron microscopy (TEM and HRSEM), thermogravimetric analysis (TGA) and N{sub 2} adsorption-desorption technique (BET). By changing the wet oxidation conditions, aluminum hydroxides with different phase composition, morphology and texture characteristics were synthesized. After calcination at different temperatures, a range of transition and stable alumina nanostructures were obtained that preserved the morphology of the aluminum hydroxide precursors - agglomerated nanosheets, nanoplates or hexagonal nanorods, up to 1000 °C. Optimal process parameters for maximum surface area development for all the precursor materials have been established.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Synthesis and characterization of the La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}} system and the fluorinated phases La{sub 1-x}Sr{sub x}FeO{sub 3-x}F{sub x}
The oxyfluorides La{sub 1-x}Sr{sub x}FeO{sub 3-x}F{sub x} have been prepared by fluorination of the precursor oxides La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}} via a low temperature route using poly(vinylidene fluoride) (PVDF). The structures of the oxides and oxyfluorides were investigated in detail by the Rietveld analysis of powder diffraction data. The oxyfluorides crystallize in the space group Pnma for 0<x{<=}0.9 (SrFeO{sub 2}F itself is cubic, space group Pm-3m) and show a sort of two-step structural distortion for decreasing x. Furthermore, a structural comparison of the oxyfluorides with the oxides is given, revealing an increase of the volume per La{sub 1-x}Sr{sub x}FeX{sub 3} unit during fluorination, of which the magnitude highly depends on the value of x. - Graphical abstract: The crystal structures of the perovskites La{sub 1-x}Sr{sub x}FeO{sub 3-x}F{sub x} for x=0.8 (a), 0.5 (b) and 0.1 (c). Highlights: > Oxyfluorides La{sub 1-x}Sr{sub x}FeO{sub 3-x}F{sub x} were prepared via low temperature fluorination using PVDF. > A structural investigation of the compounds La{sub 1-x}Sr{sub x}FeO{sub 3-x}F{sub x} is presented in detail. > Differences in structure are discussed in comparison with the precursor oxides La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}}.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Fabrication and Analysis of Tri-layer YBa{sub 2}Cu{sub 3}O{sub 7−δ} Thick Films by Low-Fluorine MOD Method
Improving the thickness of superconducting layer in coated conductors is an effective way to enhance its critical current. In this work, tri-layer YBCO/YBCO/YDyBCO films were successfully deposited on buffered Hastelloy substrate using the multi-coating lowfluorine metal-organic decomposition (LF-MOD) method and the thickness of the films can be up to 2.4 μ m. The effects of high-temperature annealing time on microstructures and superconducting properties of the films were systematically studied. Energy dispersive X-ray spectroscopy (EDS) results reveal that there remains a large amount of F element in the upper layer of the film when the annealing time is too short. With increasing the annealing time, the fluoride-containing precursor converts to YBCO grains completely. But the coarsening of grains appeared, and the critical current density (J{sub c}) of the film dropped slightly when the annealing time is too long. The cross-sectional scanning electron microscope (SEM) image and EDS plane analysis were applied to investigate the microstructure and element distribution of the final triple-layer YBCO films, respectively. The critical current of the final YBCO superconducting film could reach 316 A (77 k, self-field) for 1.2-cm-wide tapes with the optimal annealing conditions.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Performance and Economic Analysis of Organosolv Softwood and Herbaceous Lignins to Activated Carbons as Electrode Materials in Supercapacitors
In this work, yellow pine (YP, softwood) and switchgrass (SG, grass) lignins were extracted as a coproduct of an organosolv γ-valerolactone (GVL) biorefinery that also produces biofuels and furfural. The extracted lignins were converted to carbon precursors for synthesizing porous activated carbon electrodes for high energy-density supercapacitors. This research details the impact of lignin composition on the derived porous structures and electrochemical properties of activated carbons. Lignin precursors with various syringyl (S) to guaiacyl (G) contents were characterized using 31 P nuclear magnetic resonance (NMR) and two-dimensional 1 H‒ 13 C NMR. A two-step activation process, using steam and carbon dioxide as the activating agents, enabled the formation of porous carbons structures with high surface area. The capacitive behavior of supercapacitors was systematically characterized by cyclic voltammetry, charge-discharge cycling, and electrochemical impedance spectroscopy. The specific capacitance of YP and SG capacitors reached 367 and 221 F g −1 , respectively. Both types of capacitors demonstrated remarkably stable capacitance (capacitance retention >90%) along with excellent Coulombic efficiency (>99%) over 10,000 cycles. Compared to SG electrode, the better electrochemical performance achieved with YP electrodes was mainly due to shorter diffusion path, improved ionic mobility, and increased active surface area. The inexpensive lignin-based porous electrodes synthesized in this work can be used for various electrochemical devices for improved performance, decreased cost, and enhanced durability. This work also demonstrates that the selection of feedstock and appropriate processing conditions can tailor the structure of carbon composites for targeted applications. Techno-economic analysis indicates that YP and SG activated carbons can be produced at a minimum selling price of $8,493 and $6,670 per ton, respectively, which is competitive with the commercially available supercapacitor-grade activated carbons.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Chemical insights into the larger sooting tendency of 2-methyl-2-butene compared to n -pentane
A comprehensive, chemically detailed mechanism for the combustion of 2-methyl-2-butene and n-pentane is presented to provide insights into the different sooting tendencies of these two structurally different C5 hydrocarbons. A hierarchically assembled mechanism has been developed to specifically target speciation data from low-pressure premixed flames of 2-methyl-2-butene and newly measured mole fraction data for a fuel-rich (Φ = 1.8) n -pentane flame, in which species profiles up to phenol were quantified. The partially isomer-resolved chemical composition of this flame was determined using flame-sampling molecular-beam mass spectrometry with single-photon ionization by tunable, synchrotron-generated vacuum-ultraviolet radiation. The presented model, which includes a newly determined, consistent set of the thermochemistry data for the C5 species, presents overall satisfactory capabilities to predict the mole fraction profiles of common combustion intermediates. The analysis of the model predictions revealed the fuel-structure dependencies (i.e. saturated vs. unsaturated and linear vs. branched) of the formation of small aromatic species that are considered as soot precursors. Here, the propensity of the 2-methyl-2-butene flame to form larger concentrations of aromatic species was traced back to the readily available formation routes of several small precursor molecules and the efficient formation of “first aromatic rings” beyond benzene.
2-Methyl-2-butene↗
Highly c-axis oriented GaN films grown on free-standing diamond substrates for high-power devices
Highlights: {yields} GaN films are deposited on diamond substrates by ECR-PEMOCVD. {yields} Influence of deposition temperature on the properties of samples is investigated. {yields} Properties of GaN films are dependent on the deposition temperature. -- Abstract: GaN films with highly c-axis preferred orientation are deposited on free-standing thick diamond films by low temperature electron cyclotron resonance plasma enhanced metal organic chemical vapor deposition (ECR-PEMOCVD). The TMGa and N{sub 2} are applied as precursors of Ga and N, respectively. The quality of as-grown GaN films are systematically investigated as a function of deposition temperature by means of X-ray diffraction (XRD) analysis, Hall Effect measurement (HL), room temperature photoluminescence (PL) and atomic force microscopy (AFM). The results show that the dense and uniformed GaN films with highly c-axis preferred orientation are successfully achieved on free-standing diamond substrates under optimized deposition temperature of 400 {sup o}C, and the room temperature PL spectra of the optimized GaN film show a intense ultraviolet near band edge emission and a weak yellow luminescence. The obtained GaN/diamond structure has great potential for the development of high-power semiconductor devices due to its excellent heat dissipation nature.
36 MATERIALS SCIENCE↗
Controlled Single-Crystalline Polymerization of C[subscript 10]H[subscript 8]·C[subscirpt 10]F[subscript 8] under Pressure
Abstract not provided
Ward, Matthew D.↗
Evidence of Aerosols as a Media for Rapid Daytime HONO Production over China
Current knowledge of daytime HONO sources remains incomplete. A large missing daytime HONO source has been found in many places around the world, including polluted regions in China. Conventional understanding and recent studies attributed this missing source mainly to ground surface processes or gas-phase chemistry, while assuming aerosols to be an insignificant media for HONO production. We analyze in situ observations of HONO and its precursors at an urban site in Beijing, China, and report an apparent dependence of the missing HONO source strength on aerosol surface area and solar ultraviolet radiation. Based on extensive correlation analysis and process-modeling, we propose that the rapid daytime HONO production in Beijing can be explained by enhanced hydrolytic disproportionation of NO2 on aqueous aerosol surfaces due to catalysis by dicarboxylic acid anions. The combination of high abundance of NO2, aromatic hydrocarbons, and aerosols over broad regions in China likely leads to elevated HONO levels, rapid OH production, and enhanced oxidizing capacity on a regional basis. Our findings call for attention to aerosols as a media for daytime heterogeneous HONO production in polluted regions like Beijing. This study also highlights the complex and uncertain heterogeneous chemistry in China, which merits future efforts of reconciling regional modeling and laboratory experiments, in order to understand and mitigate the regional particulate and O3 pollutions over China.
Liu, Zhen↗