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At least 1,207 records · Page 67

Bottom-up synthesis of mesoscale nanomeshes of graphene nanoribbons on germanium

The synthesis of functional graphene nanostructures on Ge(001) provides an attractive route toward integrating graphene-based electronic devices onto complementary metal oxide semiconductor-compatible platforms. In this study, we leverage the phenomenon of the anisotropic growth of graphene nanoribbons from rationally placed graphene nanoseeds and their rotational self-alignment during chemical vapor deposition to synthesize mesoscale graphene nanomeshes over areas spanning several hundred square micrometers. Lithographically patterned nanoseeds are defined on a Ge(001) surface at pitches ranging from 50 to 100 nm, which serve as starting sites for subsequent nanoribbon growth. Rotational self-alignment of the nanoseeds followed by anisotropic growth kinetics causes the resulting nanoribbons to be oriented along each of the equivalent, orthogonal Ge < 110 > directions with equal probability. As the nanoribbons grow, they fuse, creating a continuous nanomesh. In contrast to nanomesh synthesis via top-down approaches, this technique yields nanomeshes with atomically faceted edges and covalently bonded junctions, which are important for maximizing charge transport properties. Additionally, we simulate the electrical characteristics of nanomeshes synthesized from different initial nanoseed-sizes, size-polydispersities, pitches, and device channel lengths to identify a parameter-space for acceptable on/off ratios and on-conductance in semiconductor electronics. The simulations show that decreasing seed diameter and pitch are critical to increasing nanomesh on/off ratio and on-conductance, respectively. With further refinements in lithography, nanomeshes obtained via seeded synthesis and anisotropic growth are likely to have superior electronic properties with tremendous potential in a multitude of applications, such as radio frequency communications, sensing, thin-film electronics, and plasmonics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Advances in actinide thin films: synthesis, properties, and future directions

Actinide-based compounds exhibit unique physics due to the presence of 5f electrons, and serve in many cases as important technological materials. Targeted thin film synthesis of actinide materials has been successful in generating high-purity specimens in which to study individual physical phenomena. These films have enabled the study of the unique electron configuration, strong mass renormalization, and nuclear decay in actinide metals and compounds. The growth of these films, as well as their thermophysical, magnetic, and topological properties, have been studied in a range of chemistries, albeit far fewer than most classes of thin film systems. This relative scarcity is the result of limited source material availability and safety constraints associated with the handling of radioactive materials. Here, we review recent work on the synthesis and characterization of actinide-based thin films in detail, describing both synthesis methods and modeling techniques for these materials. Further, we review reports on pyrometallurgical, solution-based, and vapor deposition methods. We highlight the current state-of-the-art in order to construct a path forward to higher quality actinide thin films and heterostructure devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Rotation measure synthesis applied to synthetic SKA images of galaxy clusters

Future observations with next-generation radio telescopes will help us to understand the presence and evolution of magnetic fields in galaxy clusters through determination of the so-called rotation measure (RM). In this work, we applied the RM synthesis technique to synthetic first phase Square Kilometre Array mid frequency element (i.e. the SKA1-MID) radio images of a pair of merging galaxy clusters, measured between 950 and 1750 MHz with a resolution of 10 arcsec and thermal noise of 0.1μJy beam -1 . The results of our RM synthesis analysis are compared with the simulation input parameters. We study two cases: one with radio haloes at the cluster centres and another without. Additionally, we found that the information obtained with RM synthesis is in general agreement with the input information; however, some discrepancies are present. We characterize them in this work, with the final goal of determining the potential impact of SKA1-MID on the study of cluster magnetic fields.

79 ASTRONOMY AND ASTROPHYSICS↗

N , N , N -Trimethyl-5-[(2,3,5,6-tetrafluorophenoxy)carbonyl]pyridin-2-aminium trifluoromethanesulfonate a precursor for the synthesis of 2,3,5,6-tetrafluorophenyl 6-[ 18 F]-fluoronicotinate

The synthesis, recrystallization, and X-ray deterimination of N , N , N -trimethyl-5-[(2,3,5,6-tetrafluorophenoxy)carbonyl]pyridin-2-aminium trifluoromethanesulfonate (PyTFP-precursor), C 15 H 13 F 4 N 2 O 2 + ·CF 3 SO 3 - , is described. This triflate salt precursor is required for the synthesis of 2,3,5,6-tetrafluorophenyl 6-[ 18 F]-fluoronicotinate ([ 18 F]FPyTFP), a prosthetic group used to radiolabel peptides for positron emission tomography (PET), as peptides are increasingly being used as PET-imaging probes in nuclear medicine. Radiolabeling of peptides is typically done using a `prosthetic group', a small synthon to which the radioisotope is attached in the first step, followed by attachment to the peptide in the second step. During the synthesis of the PyTFP-precursor, displacement of a Cl atom with trimethylamine gas and anion replacement with a triflate counter-ion is critical, as incomplete replacement would hinder radioisotopic incorporation of nucleophilic fluorine-18 and result in diminished radiochemical yields. The structural determination of the PyTFP-precursor by X-ray crystallography helped confirm the anion exchange of chloride with triflate.

Chemistry↗

Invited: Bambu: an Open-Source Research Framework for the High-Level Synthesis of Complex Applications

This paper presents the open-source High-Level Synthesis research framework Bambu. The framework provides an open-source starting point to experiment with new ideas across High-Level Synthesis, high-level verification and debugging, FPGA/ASIC design, design flow space exploration, and parallel hardware accelerator design. The tool accepts as input standard C/C++ specifications and compiler intermediate representations (IRs) coming from the well-known Clang/LLVM and GCC com- pilers. The broad spectrum and flexibility of input formats allow the electronic design automation (EDA) research community to explore and integrate new transformations and optimizations. The easily extendable modular framework already includes many op- timizations and HLS benchmarks. The integration with synthesis and verification backends (commercial and open-source) allows researchers to quickly test any new finding and easily obtain performance and resource usage metrics for a given application. Different FPGA devices are supported from several different vendors: AMD/XILINX, Intel/Altera, Lattice Semiconductor, and NanoXplore. Finally, integration with the OpenRoad open-source end-to-end silicon compiler perfectly fits with the recent push towards open-source EDA.

Ferrandi, Fabrizio↗

High Level Synthesis of RDF Queries for Graph Analytics

In this paper we present a set of techniques that enable the synthesis of efficient custom accelerators for memory intensive, irregular applications. To address irregular applications challenges (large memory footprints, unpredictable fine- grained data accesses, and high synchronization intensity), and exploit their opportunities (thread level parallelism, memory level parallelism), we propose a novel accelerator design which take advantage of an adaptive and Distributed Controller (DC) architecture, and a Memory Interface (MI) that supports parallel memory subsystems. Among the multitude of algorithms that may benefit from our solution, we focus on the acceleration of graph analytics applications, and in particular, on the syn- thesis of SPARQL queries on Resource Description Framework (RDF) databases. We achieve this objective by incorporating the synthesis techniques into Bambu, an Open Source high- level synthesis tools, and interfacing the system with GEMS, the Graph database Engine for Multithreaded Systems. The front- end of GEMS generates optimized C implementations of the input queries, modeled as pattern matching routines, which are then automatically synthesized by Bambu. We validate our approach synthesizing several SPARQL queries from the Lehigh University Benchmark (LUBM).

HLS, FPGA, Convey, RDF, GEMS, Memory-intensive,↗

A cross-biome synthesis of soil respiration and its determinants under simulated precipitation changes

Soil respiration (R s ) is the second-largest terrestrial carbon (C) flux. Although R s has been extensively studied across a broad range of biomes, there is surprisingly little consensus on how the spatiotemporal patterns of Rs will be altered in a warming climate with changing precipitation regimes. Here, we present a global synthesis Rs data from studies that have manipulated precipitation in the field by collating studies from 113 increased precipitation treatments, 91 decreased precipitation treatments, and 14 prolonged drought treatments. Our meta-analysis indicated that when the increased precipitation treatments were normalized to 28% above the ambient level, the soil moisture, R s ,and the temperature sensitivity (Q 10 ) values increased by an average of 17%, 16%, and 6%, respectively, and the soil temperature decreased by -1.3%. The greatest increases in R s and Q 10 were observed in arid areas, and the stimulation rates decreased with increases in climate humidity. When the decreased precipitation treatments were normalized to 28% below the ambient level, the soil moisture and Rs values decreased by an average of -14% and -17%, respectively, and the soil temperature and Q 10 values were not altered. The reductions in soil moisture tended to be greater in more humid areas. Prolonged drought without alterations in the amount of precipitation reduced the soil moisture and Rs by -12% and -6%, respectively, but did not alter Q 10 . Overall, our synthesis suggests that soil moisture and Rs tend to be more sensitive to increased precipitation in more arid areas and more responsive to decreased precipitation in more humid areas. The responses of R s and Q 10 were predominantly driven by precipitation-induced changes in the soil moisture, whereas changes in the soil temperature had limited impacts. Finally, our synthesis of prolonged drought experiments also emphasizes the importance of the timing and frequency of precipitation events on ecosystem C cycles. Given these findings, we urge future studies to focus on manipulating the frequency, intensity, and seasonality of precipitation with an aim to improving our ability to predict and model feedback between R s and climate change.

54 ENVIRONMENTAL SCIENCES↗

Purple acid phosphatase2 stimulates a futile cycle of lipid synthesis and degradation, and mitigates the negative growth effects of triacylglycerol accumulation in vegetative tissues

Storage lipids (mostly triacylglycerols, TAGs) serve as an important energy and carbon reserve in plants and hyperaccumulation of TAG in vegetative tissues can cause negative effects on plant growth. Purple acid phosphatase2 (PAP2) was shown previously to affect carbon metabolism and boost plant growth. However, the effects of PAP2 on lipid metabolism remain unknown. Here, we demonstrated PAP2 as a factor that can stimulate a futile cycle of fatty acid (FA) synthesis and degradation and mitigate negative growth effects associated with TAG accumulation in vegetative tissues. Constitutive expression of PAP2 in Arabidopsis thaliana enhanced both lipid synthesis and degradation in leaves and led to substantial increase in seed oil yield. Suppressing lipid degradation in a PAP2-overexpressing line by disrupting sugar-dependent1 (SDP1), a predominant TAG lipase, significantly elevated vegetative TAG content and improved plant growth. Diverting FAs from membrane lipids to TAGs in PAP2-overexpressing plants by constitutively expressing phospholipid:diacylglycerol acyltransferase1 (PDAT1) increased TAG contents to up to 6% of dry weight in vegetative tissues without compromising biomass yield. Overall, these results highlight the potential of combining PAP2 with TAG-promoting factors to enhance carbon assimilation, FA synthesis and allocation to TAGs for optimized plant growth and storage lipid accumulation in vegetative tissues.

59 BASIC BIOLOGICAL SCIENCES↗

Ag + reduction and silver nanoparticle synthesis at the plasma–liquid interface by an RF driven atmospheric pressure plasma jet: Mechanisms and the effect of surfactant

Here, the involvement of plasma produced species in the reduction of silver ions at the plasma–liquid interface is investigated using a well-characterized radio-frequency driven atmospheric pressure plasma jet. The absolute gas phase H density was measured using two photon absorption laser induced fluorescence in the free jet. Broadband absorption and transmission electron microscopy were used to study the synthesis of silver nanoparticles (AgNPs). It is shown that fructose, an often used surfactant/stabilizer for AgNP synthesis, also acts as a reducing agent after plasma exposure. Nonetheless, surfactant free AgNP synthesis is observed. Several experimental findings indicate that H plays an important role in the reduction of silver ions for the plasma conditions in this study. Vacuum ultraviolet photons generated by the plasma are able to reduce silver ions in the presence of fructose. Adding H2 to the argon feed gas leads to the production of a large amount of AgNPs having a particle size distribution with a maximum at a diameter of 2–3 nm, which is not observed for argon plasmas. This finding is consistent with a smaller concentration of reducing species at the plasma–liquid interface for Ar with the H2 admixture plasma. The smaller flux of reactive species to the liquid is in this case due to a less strong interaction of the plasma with the liquid. The formation of the nanoparticles was observed even at a distance of 6–7 mm below the tip of the plasma plume, conditions not favoring the injection of electrons.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Catalytic resonance of ammonia synthesis by simulated dynamic ruthenium crystal strain

Ammonia affords dense storage for renewable energy as a fungible liquid fuel, provided it can be efficiently synthesized from hydrogen and nitrogen. In this work, the catalysis of ammonia synthesis was computationally explored beyond the Sabatier limit by dynamically straining a ruthenium crystal (±4%) at the resonant frequencies (10 2 to 10 5+ Hz) of N 2 surface dissociation and hydrogenation. Density functional theory calculations at different strain conditions indicated that the energies of NH x surface intermediates and transition states scale linearly, allowing the description of ammonia synthesis at a continuum of strain conditions. A microkinetic model including multiple sites and surface diffusion between step and Ru(0001) terrace sites of varying ratios for nanoparticles of differing size revealed that dynamic strain yields catalytic ammonia synthesis conversion and turnover frequency comparable to industrial reactors (400°C, 200 atm) but at lower temperature (320°C) and an order of magnitude lower pressure (20 atm).

10 SYNTHETIC FUELS↗

Direct HCN synthesis via plasma-assisted conversion of methane and nitrogen

Hydrogen cyanide (HCN) is synthesized from ammonia (NH 3 ) and methane (CH 4 ) at ~1200°C over a Pt catalyst. Ammonia synthesis entails several complex, highly emitting processes. Plasma-assisted HCN synthesis directly from CH 4 and nitrogen (N 2 ) could be pivotal for on-demand HCN production. Here, we evaluate the potential of dielectric barrier discharge (DBD) N 2 /CH 4 plasma for decentralized catalyst-free selective HCN production. We demonstrate a single-step conversion of methane and nitrogen to HCN with a 72% yield at <300°C. HCN is favored at low CH 4 concentrations with ethane (C 2 H 6 ) as the secondary product. We propose a first-principles microkinetic model with few electron impact reactions. The model accurately predicts primary product yields and elucidates that methyl radical (·CH 3 ) is a common intermediate in HCN and C 2 H 6 synthesis. Compared to current industrial processes, N 2 /CH 4 DBD plasma can achieve minimal CO 2 emissions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microbial rRNA Synthesis and Growth Compared through Quantitative Stable Isotope Probing with H 2 18 O

Growing bacteria have a high concentration of ribosomes to ensure sufficient protein synthesis, which is necessary for genome replication and cellular division. To elucidate whether metabolic activity of soil microorganisms is coupled with growth, we investigated the relationship between rRNA and DNA synthesis in a soil bacterial community using quantitative stable isotope probing (qSIP) with H 2 18 O. Most soil bacterial taxa were metabolically active and grew, and there was no significant difference between the isotopic composition of DNA and RNA extracted from soil incubated with H 2 18 O. The positive correlation between 18 O content of DNA and rRNA of taxa, with a slope statistically indistinguishable from 1 (slope = 0.96; 95% confidence interval [CI], 0.90 to 1.02), indicated that few taxa made new rRNA without synthesizing new DNA. There was no correlation between rRNA-to-DNA ratios obtained from sequencing libraries and the atom percent excess (APE) 18 O values of DNA or rRNA, suggesting that the ratio of rRNA to DNA is a poor indicator of microbial growth or rRNA synthesis. Our results support the notion that metabolic activity is strongly coupled to cellular division and suggest that nondividing taxa do not dominate soil metabolic activity. IMPORTANCE: Utilizing quantitative stable isotope probing of microbial RNA and DNA with H 2 18 O, we show that most soil taxa are metabolically active and grow because their nucleic acids are significantly labeled with 18 O. A majority of the populations that make new rRNA also grow, which argues against the common paradigm that most soil taxa are dormant. Moreover, our results indicate that relative sequence abundance-based RNA-to-DNA ratios, which are frequently used for identifying active microbial populations in the environment, underestimate the number of metabolically active taxa within soil microbial communities.

environmental microbiology↗

Extending High-Level Synthesis with AI/ML Methods

Artificial Intelligence (AI) and Machine Learning (ML) methods provide significant opportunities of improving quality of results when performing high-level synthesis (HLS). For example, they can be used to model and predict metrics of the final design (e.g., area, considering aspects such as interconnect overhead for different device technologies), facilitating exploration when searching for the best design trade-offs. They can also enable identifying hidden correlations across the various phases of the synthesis and the various optimizations performed, identifying the most effective pipelines. Finally, in more general terms, bio-inspired heuristic algorithms can improve the design space exploration for the synthesis process in terms of time and quality of the result. This paper discusses opportunities and challenges to augment HLS with AI/ML using as example flow the SODA Synthesizer, an open-source hardware generation toolchain which includes SODA-OPT, a hardware/software partitioning and pre-optimization tool developed with the MLIR framework, and PandA-Bambu, a state-of-the art HLS tool. SODA interfaces with OpenROAD to provide a complete end-to-end toolchain.

artificial intelligence↗

Molybdenum Carbide Electrocatalysts for Electrochemical Synthesis of Ammonia from Nitrogen: Activity and Stability

Ammonia production has increased from few thousand tons in 1908 to above 200 million tons per year today, revolutionizing the fertilizer industry thanks to the Haber-Bosch (HB) process. However, the HB process is highly energy intensive consuming about 1.4% of fossil energy generated worldwide and releasing 1.87 tons of CO 2 per ton of ammonia produced. This further reduces ammonia’s scope as a carrier fuel for the hydrogen economy. Hence, finding alternative energy efficient ways to synthesize ammonia is important from more than one perspective. Ammonia synthesis from its constituent nitrogen and hydrogen gases is mainly hampered by the nitrogen reduction reaction (NRR) due to the strong N≡N bond (945 kJ mol −1 ). Electrochemical synthesis (ES) routes in this regard offer a milder approach. However, ES of ammonia under different temperatures, utilizing different electrolytes and catalysts has not yet reliably produced ammonia at viable rates and efficiencies. We report an origami-like Mo 2 C cathode catalyst for NRR that achieved a maximum synthesis rate of 2.16 × 10 −11 mol cm −2 s −1 and a faradaic efficiency of 1.8% at 30 °C using Nafion-212 as electrolyte. Origami-like morphology containing numerous kinks appears to improve electrocatalytic activity and show a promising route for fabricating NRR catalysts with higher catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Monitoring of the Growth of Nickel, Manganese, and Cobalt Hydroxide Precursors during Co-Precipitation Synthesis of Li-Ion Cathode Materials

The electrochemical performance of cathode materials for Li-ion batteries depends on the morphology of the material, which, in turn, depends on the synthesis conditions. Very few studies have focused on the impact of process conditions on the final morphology of the cathode particles and analyzed the growth during synthesis. In this paper, the evolution of nickel, manganese, and cobalt hydroxide precursor, Ni 1/3 Mn 1/3 Co 1/3 (OH) 2 , is investigated using a combination of in situ and ex situ techniques during the commonly-used coprecipitation process. These include in situ wide angle X-ray scattering, in-situ ultra-small angle X-ray scattering and ex situ particle size analysis. The growth rate of crystalline Ni 1/3 Mn 1/3 Co 1/3 (OH) 2 primary particle is found to be almost constant, consistent with a mathematical analysis of process. The growth of the Ni 1/3 Mn 1/3 Co 1/3 (OH) 2 secondary particle and its particle size distribution revealed different growth stages for samples prepared at different pH. These techniques are complimented with scanning electron microscopy and electrochemical testing to track the morphology and performance of the hydroxide particle and the subsequent calcined LiNi 1/3 Mn 1/3 Co 1/3 O 2 cathode active material. This study presents insights into the synthesis process and provides a deeper understanding to aid in process optimization.

Cathode precursor↗

Myocardial Oxidative Metabolism and Protein Synthesis during Mechanical Circulatory Support by Extracorporeal Membrane Oxygenation

Extracorporeal membrane oxygenation (ECMO) provides mechanical circulatory support essential for survival in infants and children with acute cardiac decompensation. However, ECMO also causes metabolic disturbances, which contribute to total body wasting and protein loss. Cardiac stunning can also occur which prevents ECMO weaning, and contributes to high mortality. The heart may specifically undergo metabolic impairments, which influence functional recovery. We tested the hypothesis that ECMO alters oxidative. We focused on the amino acid leucine, and integration with myocardial protein synthesis. We used a translational immature swine model in which we assessed in heart (i) the fractional contribution of leucine (FcLeucine) and pyruvate (FCpyruvate) to mitochondrial acetyl-CoA formation by nuclear magnetic resonance and (ii) global protein fractional synthesis (FSR) by gas chromatography-mass spectrometry. Immature mixed breed Yorkshire male piglets (n = 22) were divided into four groups based on loading status (8 hours of normal circulation or ECMO) and intracoronary infusion [13C6,15N]-L-leucine (3.7 mM) alone or with [2-13C]-pyruvate (7.4 mM). ECMO decreased pulse pressure and correspondingly lowered myocardial oxygen consumption (~ 40%, n = 5), indicating decreased overall mitochondrial oxidative metabolism. However, FcLeucine was maintained and myocardial protein FSR was marginally increased. Pyruvate addition decreased tissue leucine enrichment, FcLeucine, and Fc for endogenous substrates as well as protein FSR. Conclusion: The heart under ECMO shows reduced oxidative metabolism of substrates, including amino acids, while maintaining (i) metabolic flexibility indicated by ability to respond to pyruvate, and (ii) a normal or increased capacity for global protein synthesis, suggesting an improved protein balance.

Environmental Molecular Sciences Laboratory↗

Effects of Dopant Metal Variation and Material Synthesis Method on the Material Properties of Mixed Metal Ferrites in Yttria Stabilized Zirconia for Solar Thermochemical Fuel Production

Mixed metal ferrites have shown much promise in two-step solar-thermochemical fuel production. Previous work has typically focused on evaluating a particular metal ferrite produced by a particular synthesis process, which makes comparisons between studies performed by independent researchers difficult. A comparative study was undertaken to explore the effects different synthesis methods have on the performance of a particular material during redox cycling using thermogravimetry. This study revealed that materials made via wet chemistry methods and extended periods of high temperature calcination yield better redox performance. Differences in redox performance between materials made via wet chemistry methods were minimal and these demonstrated much better performance than those synthesized via the solid state method. Subsequently, various metal ferrite samples (NiFe 2 O 4 , MgFe 2 O 4 , CoFe 2 O 4 , and MnFe 2 O 4 ) in yttria stabilized zirconia (8YSZ) were synthesized via coprecipitation and tested to determine the most promising metal ferrite combination. It was determined that 10 wt.% CoFe 2 O 4 in 8YSZ produced the highest and most consistent yields of O 2 and CO. By testing the effects of synthesis methods and dopants in a consistent fashion, those aspects of ferrite preparation which are most significant can be revealed. More importantly, these insights can guide future efforts in developing the next generation of thermochemical fuel production materials.

Leonard, Jeffrey↗

Plasmon assisted synthesis of TiN-supported single-atom nickel catalysts

We report the deposition of single atom nickel catalyst on refractory plasmonic titanium nitride (TiN) nanomaterials supports using the wet synthesis method under visible light irradiation. TiN nanoparticles efficiently absorb visible light to generate photoexcited electrons and holes. Photoexcited electrons reduce nickel precursor to deposit Ni atoms on TiN nanoparticles’ surface. The generated hot holes are scavenged by the methanol. We studied the Ni deposition on TiN nanoparticles by varying light intensity, light exposure time, and metal precursor concentration. These studies confirmed the photodeposition method is driven by hot electrons and helped us to find optimum synthesis conditions for single atoms deposition. We characterized the nanocatalysts using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). We used density functional theory (DFT) calculations to predict favorable deposition sites and aggregation energy of Ni atoms on TiN. Surface defect sites of TiN are most favorable for single nickel atoms depositions. Interestingly, the oxygen sites on native surface oxide layer of TiN also exhibit strong binding with the single Ni atoms. Plasmon enhanced synthesis method can facilitate photodeposition of single atom catalysts on a wide class of metallic supports with plasmonic properties.

36 MATERIALS SCIENCE↗