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At least 289 records · Page 16

Directing Anisotropic Assembly of Metallic Nanoclusters by Exploiting Linear Trio Interactions and Quantum Size Effects: Au Chains on Ag(100) Thin Films

Discovery and understanding of mechanisms for kinetically controlled growth of metal nanoclusters can be enabled by realistic atomistic-level modeling with ab initio kinetics. KMC simulation of such a model for Au deposition on Ag(100) films reveals the formation of single-atom-wide Au chains below 275 K, even though 2D islands are thermodynamically preferred. Chain formation is shown to reflect a combination of strong linear trio attractions guiding assembly and a weak driving force and slow rate of transformation of 1D chains to 2D islands (or sometimes irreversible rounding of adatoms from chain sides to ends). Behavior can also be tuned by quantum size effects: chain formation predominates on 2-monolayer Ag(100) films supported on NiAl(100) at 250 K for low coverages but not on 1- or 3-monolayer films, and longer chains form than on bulk Ag(100). Finally, our predictive kinetic modeling shows the potential for simulation-guided discovery and analysis of novel self-assembly processes.

ab initio periphery diffusion kinetics↗

Structural and Dynamical Roles of Bound Polymer Chains in Rubber Reinforcement

The addition of nanofillers to rubber matrices is a powerful route to improve the mechanical properties. Here, we focus on a molecular understanding of basic mechanisms that are important for the reinforcement in rubbers. The key role in this process is ascribed to bound rubber (BR) that engages with the matrix as well as with adjacent nanofillers. To date, this understanding has been impeded by the lack of experimental tools to directly probe the BR chains buried in a polymer matrix composed of the same polymer. To tackle this challenge, we combine neutron scattering/spectroscopy techniques with isotope-labeling and molecular dynamics simulations. The system is a simplified carbon-black-filled polybutadiene. The combined experimental and computational results provide new insights into the local structural and dynamical heterogeneities of BR chains and their interactions with the matrix polymer, highlighting (i) the structural partition of the bound chains into three components (i.e., trains, loops, and tails) and their fractions; (ii) their dynamical hierarchies, i.e., the trains that remain immobile on the filler surface, the loops that are fairly large and hence allow the interdigitation of matrix chains, and the tails with their unique characteristics to reach far out into the matrix and entangle with matrix chains. These multiple roles of the constituent components of the BR chains promote the formation of a well-developed adhesive polymer–filler interface, enhancing the elastic property of a filled rubber. Finally, the comprehensive understanding derived and validated by the model rubber will be translatable to many other polymer nanocomposites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving the Electronic Transporting Property for Flexible Field-Effect Transistors with Naphthalene Diimide-Based Conjugated Polymer through Branching/Linear Side-Chain Engineering Strategy

n-Type organic/polymeric semiconductors with high electron mobilities are highly demanded for future flexible organic circuits. Except for developing a new conjugated backbone, recent studies show that side-chain engineering also plays an indispensable role in boosting the charge-transporting property. In this paper, we report a new polymer PNDI2T-DTD with a representative n-type naphthalene diimide (NDI)–bithiophene backbone for high-performance n-type flexible thin-film transistors through branching/linear side-chain engineering strategy. Serving as the flexible side chains, the linear/branching side-chain pattern is found to be effective in tuning the preaggregation behavior in solution and the packing ordering of polymeric chains, resulting in the improvement of thin-film crystallinity. We report the electron mobility of the thin film of PNDI2T-DTD on flexible substrates can reach 1.52 cm 2 V –1 s –1 , which is approximately five times higher than that of PNDI2T-DT with the same conjugated backbone and only branching alkyl chains.

36 MATERIALS SCIENCE↗

Material Flow Analysis and Life Cycle Assessment of Polyethylene Terephthalate and Polyolefin Plastics Supply Chains in the United States

Plastics are useful and beneficial materials that contribute to an improved quality of life, yet they generate significant solid wastes and emissions and consume significant energy resources. Systems analysis is incomplete on current linear production systems of plastics supply chains and their associated processes. Our study combines material flow and life cycle assessment data sets of polyethylene terephthalate (PET) and the main polyolefin polymers in the United States, comprising over 70% of plastics flows. This study estimates the total greenhouse gas (GHG) emissions and energy consumption of these supply chains, including transportation and end-of-life processes, lacking in prior studies. Here we calculate annual GHG emissions and energy consumption of these plastic supply chains to be 101 MMT CO 2 -eq and 3248 PJ in 2019, respectively. The GHG emissions of these supply chains represented 1.5% of the total U.S. emissions and 5% of the total U.S. industry-related GHG emissions. The total energy consumption of these supply chains represented 3.1% of the total U.S. energy consumption in 2019. Transportation of PET and polyolefin plastic materials contributes 5% and 2% to the total supply chain GHG emissions and energy consumption, respectively. This baseline study provides a benchmark and enables a comparison to future circular production systems for plastics in the United States.

09 BIOMASS FUELS↗

Energy band modulation of graphane by hydrogen-vacancy chains: A first-principles study

We investigated a variety of configurations of hydrogen-vacancy chains in graphane by first-principles density functional calculation. We found that graphane with two zigzag H-vacancy chains segregated by one or more H chain is generally a nonmagnetic conductor or has a negligible band gap. However, the same structure is turned into a semiconductor and generates a magnetic moment if either one or both of the vacancy chains are blocked by isolated H atoms. If H-vacancy chains are continuously distributed, the structure is similar to a zigzag graphene nanoribbon embedded in graphane. It was also found that the embedded zigzag graphene nanoribbon is antiferromagnetic, and isolated H atoms left in the 2-chain nanoribbon can tune the band gap and generate net magnetic moments. Similar effects are also obtained if bare carbon atoms are present outside the nanoribbon. These results are useful for designing graphene-based nanoelectronic circuits.

36 MATERIALS SCIENCE↗

Formation and structural phase transition in Co atomic chains on a Cu(775) surface

The formation of Co atomic chains on a Cu(775) surface is investigated by the kinetic Monte Carlo method. It is found that the length of Co atomic chains formed as a result of self-organization during epitaxial growth is a random quantity and its mean value depends on the parameters of the experiment. The existence of two structural phases in atomic chains is detected using the density functional theory. In the first phase, the separations between an atom and its two nearest neighbors in a chain are 0.230 and 0.280 nm. In the second phase, an atomic chain has identical atomic spacings of 0.255 nm. It is shown that the temperature of the structural phase transition depends on the length of the atomic chain.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Leveraging Flexible Smart Manufacturing to Accelerate Industrial Supply Chain Recovery

Any major crisis such as the latest coronavirus disease pandemic will have a monumental effect on the worldwide economy and on the international supply chain. Much of the global supply chain relies on China, Germany, and the United States for manufacturing and distribution; this fragile system is subject to failure. Climactic changes in demand and rapid shortages in necessities are the results of the pandemic’s disruption. The recovery forecast for the ongoing pandemic is uncertain and, therefore, any recovery effort will need to be adaptable to build the supply chain resiliency. A wide adoption of flexible smart automated technologies in the manufacturing sector are helping to build robust supply chains and assisting in recovery. Here, a brief discussion of these smart manufacturing technologies is presented, along with a list of potential supply chain issues and corresponding solutions. Such smart manufacturing technologies possess the potential to empower and revolutionize the traditional manufacturing environment by enhancing its resiliency and flexibility. These smart technologies will play a crucial role in accelerating the worldwide supply chain recovery in and after a pandemic.

99 GENERAL AND MISCELLANEOUS↗

Resilience Lessons From the Southeast United States Woody Pellet Supply Chain Response to the COVID-19 Pandemic†

The Coronavirus Disease 2019 (COVID-19) instigated a pandemic that impacted economies, employment, and shipping worldwide. This paper reviews how one international supply chain performed and identifies lessons that may be helpful to improve future resilience. Economic and employment data through November 2020 are used to review the effects of COVID-19 on operations of the bioenergy supply chain in the southeastern United States (SE United States) that utilizes wood fiber to fabricate pellets. Conditions associated with the production of pellets in the SE United States changed with the outbreak of COVID-19. Federal and state government programs and classification of workers in this sector as “essential” during the pandemic helped maintain the woody pellet supply chain and other industries during a period of general shut down in 2020. The availability of personal protective equipment, long-term supply contracts, and established safety cultures are among the factors that enhance supply chain resilience while limited availability of skilled workers, inadequate stakeholder engagement, and dependence on external policies are among factors that reduce resilience. The analysis concludes with recommendations for the SE pellet supply chain, and other biomass supply chains, to improve their resilience to future disturbances. When best practices are implemented, SE United States biomass offers opportunities to contribute to post-pandemic economic recovery while incentivizing better forest resource management.

09 BIOMASS FUELS↗

Effects of HLA single chain trimer design on peptide presentation and stability

MHC class I “single-chain trimer” molecules, coupling MHC heavy chain, β 2 -microglobulin, and a specific peptide into a single polypeptide chain, are widely used in research. To more fully understand caveats associated with this design that may affect its use for basic and translational studies, we evaluated a set of engineered single-chain trimers with combinations of stabilizing mutations across eight different classical and non-classical human class I alleles with 44 different peptides, including a novel human/murine chimeric design. While, overall, single-chain trimers accurately recapitulate native molecules, care was needed in selecting designs for studying peptides longer or shorter than 9-mers, as single-chain trimer design could affect peptide conformation. In the process, we observed that predictions of peptide binding were often discordant with experiment and that yields and stabilities varied widely with construct design. We also developed novel reagents to improve the crystallizability of these proteins and confirmed novel modes of peptide presentation.

59 BASIC BIOLOGICAL SCIENCES↗

Oral branched-chain amino acids decrease whole-body proteolysis

BACKGROUND: This study reports the effects of ingesting branched-chain amino acids (leucine, valine, and isoleucine) on protein metabolism in four men. METHODS: To calculate leg protein synthesis and breakdown, we used a new model that utilized the infusion of L-[ring-13C6]phenylalanine and the sampling of the leg arterial-venous difference and muscle biopsies. In addition, protein-bound enrichments provided for the direct calculation of muscle fractional synthetic rate. Four control subjects ingested an equivalent amount of essential amino acids (threonine, methionine, and histidine) to discern the effects of branched-chain amino acid nitrogen vs the effects of essential amino acid nitrogen. Each drink also included 50 g of carbohydrate. RESULTS: Consumption of the branched-chain and the essential amino acid solutions produced significant threefold and fourfold elevations in their respective arterial concentrations. Protein synthesis and breakdown were unaffected by branched-chain amino acids, but they increased by 43% (p < .05) and 36% (p < .03), respectively, in the group consuming the essential amino acids. However, net leg balance of phenylalanine was unchanged by either drink. Direct measurement of protein synthesis by tracer incorporation into muscle protein (fractional synthetic rate) revealed no changes within or between drinks. Whole-body phenylalanine flux was significantly suppressed by each solution but to a greater extent by the branched-chain amino acids (15% and 20%, respectively) (p < .001). CONCLUSIONS: These results suggest that branched-chain amino acid ingestion suppresses whole-body proteolysis in tissues other than skeletal muscle in normal men.

NASA Discipline Number 18-10↗

Reducing supply chain energy use in next-generation vehicle lightweighting

Vehicle lightweighting reduces the amount of fuel consumed in a vehicle's use phase, but depending on what lightweight materials replace the conventional materials, and in what amounts, the manufacturing energy may increase or decrease. For carbon fiber reinforced polymer (CFRP), a next-generation lightweighting material, the increase in vehicle manufacturing energy is greater than the fuel savings, resulting in a net increase in energy consumption over a vehicle's manufacturing and use relative to a standard non-lightweighted car. [1] This work explores ways to reduce the supply chain energy of CFRP lightweighted vehicles through alternative production technologies and energy efficiency improvements. The objective is to determine if CFRP can offer energy savings comparable to or greater than aluminum, a conventional lightweighting material. Results of this analysis can be used to inform additional research and development efforts in CFRP production and future directions in lightweight vehicle production. The CFRP supply chain is modeled using the Material Flows through Industry (MFI) scenario modeling tool, which calculates 'mine to materials' energy consumption, material inventories and greenhouse gas emissions for industrial supply chains. In this analysis, the MFI tool is used to model the supply chains of two lightweighted vehicles, an aluminum intensive vehicle (AIV) and a carbon fiber intensive vehicle (CFV), under several manufacturing scenarios. Vehicle specifications are given in [1]. Scenarios investigated cover alternative carbon fiber (CF) feedstocks and energy efficiency improvements at various points in the vehicle supply chains. The alternative CF feedstocks are polyacrylonitrile, lignin and petroleum-derived mesophase pitch. Scenarios in which the energy efficiency of CF and CFRP production increases are explored using sector efficiency potential values, which quantify the reduction in energy consumption achievable when process equipment is upgraded to the most efficient available. Preliminary analyses indicate that producing CF from lignin instead of polyacrylonitrile, the most commonly used feedstock, reduces energy consumption in the CFRP supply chain by 7.5%, and that implementing energy efficient process equipment produces an additional 8% reduction. Final results will show if these potential reductions are sufficient to make the CFV energy savings comparable with AIV energy savings. [1] Das, S., Graziano, D., Upadhyayula, V. K., Masanet, E., Riddle, M., & Cresko, J. (2016). Vehicle lightweighting energy use impacts in US light-duty vehicle fleet. Sustainable Materials and Technologies, 8, 5-13.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

A Facile Method to Fine‐Tune Polymer Aggregation Properties and Blend Morphology of Polymer Solar Cells Using Donor Polymers with Randomly Distributed Alkyl Chains

Abstract The device performance of polymer solar cells (PSCs) is strongly dependent on the blend morphology. One of the strategies for improving PSC performance is side‐chain engineering, which plays an important role in controlling the aggregation properties of the polymers and thus the domain crystallinity/purity of the donor–acceptor blends. In particular, for a family of high‐performance donor polymers with strong temperature‐dependent aggregation properties, the device performances are very sensitive to the size of alkyl chains, and the best device performance can only be achieved with an optimized odd‐numbered alkyl chain. However, the synthetic route of odd‐numbered alkyl chains is costly and complicated, which makes it difficult for large‐scale synthesis. Here, this study presents a facile method to optimize the aggregation properties and blend morphology by employing donor polymers with a mixture of two even‐numbered, randomly distributed alkyl chains. In a model polymer system, this study suggests that the structural and electronic properties of the random polymers comprising a mixture of 2‐octyldodecyl and 2‐decyltetradecyl alkyl chains can be systematically tuned by varying the mixing ratio, and a high power conversion efficiency (11.1%) can be achieved. This approach promotes the scalability of donor polymers and thus facilitates the commercialization of PSCs.

Yao, Huatong↗

The evolution of symbiotic innovation, water, and agricultural supply chains

Abstract The water literature has mainly investigated the diversion and distribution of water from the source to the end users or the utilization of water at the farm level in crop production. This paper presents a supply chain perspective that links the innovation supply chain of water delivery and irrigation with the complete water supply chain to the crop and the crop supply chains. These supply chains are symbiotic. Changes in the demand for crops, agronomic technology, and knowledge about water will modify the water infrastructure, irrigation technology, land‐use and crop production patterns, and the pricing of water and related commodities. The parameters that guide investment in water innovation and the design of the water supply chain depend on political, economic, and technological considerations that have coevolved over time with water and crop systems. Evidence from California and elsewhere supports the findings of the paper.

54 ENVIRONMENTAL SCIENCES↗

Is a Malleable Active Site Loop the Key to High Substrate Promiscuity? Hybrid, Biocatalytic Route to Structurally Diverse Taxoid Side Chains with Remarkable Dual Stereocontrol

Abstract These studies reveal the first structure ofClostridium acetobutylicumalcohol dehydrogenase (CaADH), a protein exhibiting remarkable substrate promiscuity and stereochemical fidelity. The CaADH enzyme is utilized here for synthesizing 20 potential aryl isoserine side chains for the Taxotere family of tubulin‐binding chemotherapeutics. The approach involves dynamic reductive kinetic resolution (DYRKR) upon the corresponding α‐chloro‐β‐keto esters, showing high D‐synstereoselectivity, including those leading to the clinically relevant milataxel (Ar = 2‐furyl) and simotaxel (Ar = 2‐thienyl) side chains. Furthermore, various cross‐coupling chemistries performed on thep‐bromophenyl isoserine side chain significantly enhance the structural diversity of the taxoid side chain library obtained (16 additional taxoid side chains). The CaADH structure is notable: (i) the nicotinamide cofactor is bound in ananti‐conformation, with the amide carbonyl occupying the ketone binding pocket, and (ii) a flexible loop near the active site likely contributes to the remarkable substrate promiscuity observed in CaADH. We present our perspective on the dynamic nature of the CaADH active site through molecular dynamics simulation, proposing a halogen bonding model as a potential mechanism for the remarkable selectivity for an (S)‐configured C─Cl bond, in addition to the D‐facial selectivity, demonstrated across 20 diverse substrates by this remarkable short‐chain dehydrogenase enzyme.

Chemistry↗

Structural insight into the substrate specificity of acyl-CoA oxidase1 from Yarrowia lipolytica for short-chain dicarboxylyl-CoAs

Highlights: • The crystal structure of acyl-CoA oxidase1 from Yarrowia lipolytica (YlACOX1) was determined. • The substrate binding tunnel of YlACOX1 was elucidated. • Substrate specificity for short-chain dicarboxylyl-CoA of YlACOX1 was elucidated. Acyl-CoA oxidase (ACOX) plays an important role in fatty acid degradation. The enzyme catalyzes the first reaction in peroxisomal fatty acid β-oxidation by reducing acyl-CoA to 2-trans-enoyl-CoA. The yeast Yarrowia lipolytica is able to utilize fatty acids, fats, and oil as carbon sources to produce valuable bioproducts. We determined the crystal structure of ACOX1 from Y. lipolytica (YlACOX1) at a resolution of 2.5 Å. YlACOX1 forms a homodimer, and the monomeric structure is composed of four domains, the Nα, Nβ, Cα1, and Cα2. The FAD cofactor is bound at the dimerization interface between the Nβ- and Cα1-domains. The substrate-binding tunnel formed by the interface between the Nα-, Nβ-, and Cα1-domains is located proximal to FAD. Amino acid and structural comparisons of YlACOX1 with other ACOXs show that the substrate-binding pocket of YlACOX1 is much smaller than that of the medium- or long-chain ACOXs but is rather similar to that of the short-chain ACOXs. Moreover, the hydrophilicity of residues constituting the end region of the substrate-binding pocket in YlACOX1 is quite similar to those in the short-chain ACOXs but different from those of the medium- or long-chain ACOXs. These observations provide structural insights how YlACOX1 prefers short-chain dicarboxylyl-CoAs as a substrate.

60 APPLIED LIFE SCIENCES↗

Effect of Microstructure on Chain Flexibility and Glass Transition Temperature of Polybenzofulvene

Polybenzofulvene (PBF) is a polydiene with a very high glass transition temperature (T g ), which makes it a potential candidate for use as the hard block for high-temperature thermoplastic elastomer applications. The T g s of polydienes are known to be related to chain flexibility. However, no studies have been reported that correlate the chain flexibility to the microstructure of PBF. Herein, we present a study of solution properties of linear PBFs with narrow molecular weight dispersity and having 1,2-addition ranging from 23% to 99%. The materials were prepared by living anionic polymerization under different conditions. Specifically, the chain flexibility as defined by the Flory's characteristic ratio, , and dependence of chain flexibility on microstructure by combined measurements of intrinsic viscosity and molecular weight using triple-detector size exclusion chromatography (SEC) is studied. The persistence lengths (l p ) and chain diameters (d B ) were also estimated using the touched-bead wormlike chain model. To the best of our knowledge, the characteristic ratio of PBF is found to be the highest of all polydienes that have been reported so far.

36 MATERIALS SCIENCE↗

Inducing Ferrimagnetic Exchange in 1D-FeSe 2 Chains Using Heteroleptic Amine Complexes: [Fe(en)(tren)][FeSe 2 ] 2

[Fe(en)(tren)][FeSe 2 ] 2 (en = ethylenediamine, C 2 H 8 N 2 , tren = tris(2-aminoethyl)amine, C 6 H 18 N 4 ) has been synthesized by a mixed-ligand solvothermal method. Its crystal structure contains heteroleptic [Fe(en)(tren)] 2+ complexes with distorted octahedral coordination, incorporated between 1D-FeSe 2 chains composed of edge–sharing FeSe 4 tetrahedra. The twisted octahedral coordination environment of the Fe–amine complex leads to partial dimerization of Fe–Fe distances in the FeSe 2 chains so that the FeSe 4 polyhedra deviate strongly from the regular tetrahedral geometry. 57 Fe Mössbauer spectroscopy reveals oxidation states of +3 for the Fe chain atoms and +2 for the Fe complex atoms. The close proximity of Fe atoms in the chains promotes ferromagnetic nearest neighbor interactions, as indicated by a positive Weiss constant, θ = +53.8(6) K, derived from the Curie–Weiss fitting. Magnetometry and heat capacity reveal two consecutive magnetic transitions below 10 K. DFT calculations suggest that the ordering observed at 4 K is due to antiferromagnetic intrachain interactions in the 1D-FeSe 2 chains. The combination of two different ligands creates an asymmetric coordination environment that induces changes in the structure of the Fe–Se fragments. Finally, this synthetic strategy opens new ways to explore the effects of ligand field strength on the structure of both Fe-amine complexes and surrounding Fe–Se chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unveiling the Finite Temperature Physics of Hydrogen Chains via Auxiliary Field Quantum Monte Carlo

The ability to accurately predict the finite temperature properties and phase diagrams of realistic quantum solids is central to uncovering new phases and engineering materials with novel properties ripe for device applications. Nonetheless, there remain comparatively few many-body techniques capable of elucidating the finite temperature physics of solids from first principles. Here, we take a significant step toward developing such a technique by generalizing our previous, exact fully ab initio finite temperature Auxiliary Field Quantum Monte Carlo (FT-AFQMC) method to model periodic solids and employing it to uncover the finite temperature physics of periodic hydrogen chains. Our chains’ unit cells consist of 10 hydrogen atoms modeled in a minimal basis, and we sample 5 k-points from the first Brillouin zone to arrive at a supercell consisting of 50 orbitals and 50 electrons. Based upon our calculations of these chains’ many-body energies, free energies, entropies, heat capacities, double and natural occupancies, and charge and spin correlation functions, we outline their metal–insulator and magnetic ordering as a function of both H–H bond distance and temperature. At low temperatures approaching the ground state, we observe both metal–insulator and ferromagnetic–antiferromagnetic crossovers at bond lengths between 0.5 and 0.75 Å. We then demonstrate how this low-temperature ordering evolves into a metallic phase with decreasing magnetic order at higher temperatures. In order to contextualize our results, we compare the features we observe to those previously seen in one-dimensional, half-filled Hubbard models at finite temperature and in ground state hydrogen chains. Interestingly, we identify signatures of the Pomeranchuk effect in hydrogen chains for the first time and show that spin and charge excitations that typically arise at distinct temperatures in the Hubbard model are indistinguishably coupled in these systems. Beyond qualitatively revealing the many-body phase behavior of hydrogen chains in a numerically exact manner without invoking the phaseless approximation, our efforts shed light on the further theoretical developments that will be required to construct the phase diagrams of the more complex transition metal, lanthanide, and actinide solids of longstanding interest to physicists.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗