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First principles-based multiparadigm, multiscale strategy for simulating complex materials processes with applications to amorphous SiC films
Progress has recently been made in developing reactive force fields to describe chemical reactions in systems too large for quantum mechanical (QM) methods. In particular, ReaxFF, a force field with parameters that are obtained solely from fitting QM reaction data, has been used to predict structures and properties of many materials. Important applications require, however, determination of the final structures produced by such complex processes as chemical vapor deposition, atomic layer deposition, and formation of ceramic films by pyrolysis of polymers. This requires the force field to properly describe the formation of other products of the process, in addition to yielding the final structure of the material. We describe a strategy for accomplishing this and present an example of its use for forming amorphous SiC films that have a wide variety of applications. Extensive reactive molecular dynamics (MD) simulations have been carried out to simulate the pyrolysis of hydridopolycarbosilane. The reaction products all agree with the experimental data. After removing the reaction products, the system is cooled down to room temperature at which it produces amorphous SiC film, for which the computed radial distribution function, x-ray diffraction pattern, and the equation of state describing the three main SiC polytypes agree with the data and with the QM calculations. Extensive MD simulations have also been carried out to compute other structural properties, as well the effective diffusivities of light gases in the amorphous SiC film.
Role of inner solvation sheath within salt–solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries
Functional electrolyte is the key to stabilizing the highly reductive lithium (Li) metal anode (LMA) and high voltage cathode for long life, high energy-density rechargeable Li metal batteries (LMBs). However, fundamental knowledge of the interaction principles between reactive electrodes and electrolytes is still limited. Recently localized high-concentration electrolytes (LHCEs) are emerging as promising electrolyte design strategies for LMBs. They can also serve as an ideal platform for understanding the reactivity characteristics of the inner solvation sheath on electrode surfaces due to their unique solvation structures. Here, we study the effects of a series of LHCEs with model electrolyte solvents (carbonate, sulfone, phosphate and ether) in high voltage LMBs. Varied electrode stabilities exhibited in different LHCEs indicate the intricate synergies between the salt and the solvent on electrode surfaces. Experimental and theoretical analyses reveal an intriguing general rule that the strong interactions between the salt and the solvent in the inner solvation sheath promote their intermolecular proton/charge transfer reactions, which dictates the properties of the electrode/electrolyte interphases and thus the battery performances.
The antimalarial compound ELQ ‐400 is an unusual inhibitor of the bc 1 complex, targeting both Q o and Q i sites
Inhibitors of the mitochondrial respiratory chain cytochrome bc 1 complex, such as the antimalarial atovaquone and ELQ ‐300, and many well‐studied compounds, are classified as either Q o or Q i site inhibitors based on their site of action. Here, we investigated the site of action of ELQ ‐400 that showed an unusual behaviour, being effective against parasites resistant to the Q o site inhibitor atovaquone or to the Q i site inhibitor ELQ ‐300. Analysis of yeast mutants and comparison with atovaquone and other ELQ s strongly suggest that ELQ ‐400 targets both Q o and Q i sites. Dual site inhibition would be particularly efficient as it would lower the risk of acquired resistance. However, such compounds are seldom found, which could be explained by structural and mechanistic differences between the sites.
Highly Efficient Blue OLEDs Based on Metal‐Assisted Delayed Fluorescence Pd(II) Complexes
Abstract A series of metal‐assisted delayed fluorescence (MADF) palladium(II) complexes, PdN1N, PdN1N‐dm, and PdN6N, are studied. Their 77 K photoluminescence emission spectra show a narrow primary emission peak at 464, 466, and 470 nm, respectively, with small vibronic peaks characteristic of many phosphorescent emitters. At room temperature (300 K), the dominant emission peaks for PdN1N, PdN1N‐dm, and PdN6N are slightly redshifted to 472, 470, and 476 nm, respectively. In the meantime, a broad sideband is also shown between 410 and 450 nm due to the MADF process. A blue device employing PdN1N‐dm demonstrates an electroluminescence emission peak at 476 nm and the maximum external quantum efficiency (EQE) of 25.1%. The high maximum EQE of the blue organic light‐emitting diode (OLED) device indicates that both the phosphorescence and the delayed fluorescence are very efficient. In addition, a stable OLED device of PdN1N‐dm gives a maximum EQE of 9.8% and the estimated operational lifetime LT 70 of 350 h at the practical luminance of 100 cd m −2 .
Synthesis and Characterization of a Triphos Ligand Derivative and the Corresponding Pd II Complexes: Triphos Ligand Derivative and Corresponding Pd II Complexes
The synthesis of the new bis(2-(diphenylphosphino)ethyl)methylhydroxyphosphine tridentate phosphine ligand, LCH2OH/Ph, is reported. The ligand reacts with [Pd(Cl)2(PhCN)2 to form [Pd(LCH2OH/Ph)Cl]Cl. Exchange of the chloride ions for triflate (OTf–) using AgOTf yielded pure [Pd(LCH2OH/Ph)OTf]OTf. In addition to spectral characterization the free ligand, LCH2OH/Ph, and Pd(II) complex, [Pd(LCH2OH/Ph)OTf]OTf, are structurally characterized. This research was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences, and Geosciences. Pacific Northwest National Laboratory is a multiprogram national laboratory operated by Battelle for DOE.
Intersubunit communication in the dihydroorotase-aspartate transcarbamoylase complex of Aquifex aeolicus : Intersubunit Communication in a Pyrimidine Biosynthetic Complex
Aspartate transcarbamoylase and dihydroorotase, enzymes that catalyze the second and third step in de novo pyrimidine biosynthesis, are associated in dodecameric complexes in Aquifex aeolicus and many other organisms. The architecture of the dodecamer is ideally suited to channel the intermediate, carbamoyl aspartate from its site of synthesis on the ATC subunit to the active site of DHO, which catalyzes the next step in the pathway, because both reactions occur within a large, internal solvent-filled cavity. Channeling usually requires that the reactions of the enzymes are coordinated so that the rate of synthesis of the intermediate matches its rate of utilization. The linkage between the ATC and DHO subunits was demonstrated by showing that the binding of the bisubstrate analog, N-phosphonacetyl-L-aspartate to the ATC subunit inhibits the activity of the distal DHO subunit. Structural studies identified a DHO loop, loop A, interdigitating between the ATC domains that would be expected to interfere with domain closure essential for ATC catalysis. Mutation of the DHO residues in loop A that penetrate deeply between the two ATC domains inhibits the ATC activity by interfering with the normal reciprocal linkage between the two enzymes. Moreover, a synthetic peptide that mimics that part of the DHO loop that binds between the two ATC domains was found to be an allosteric or noncompletive ATC inhibitor (K i = 22 μM). A model is proposed suggesting that loop A is an important component of the functional linkage between the enzymes.
Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States
Abstract Over the past years, ultrathin films consisting of electron donating and accepting molecules have attracted increasing attention due to their potential usage in optoelectronic devices. Key parameters for understanding and tuning their performance are intermolecular and molecule–substrate interactions. Here, the formation of a monolayer thick blend of triphenylene‐based organic donor and acceptor molecules from 2,3,6,7,10,11‐hexamethoxytriphenylene (HAT) and 1,4,5,8,9,12‐hexaazatriphenylenehexacarbonitrile (HATCN), respectively, on a silver (111) surface is reported. Scanning tunneling microscopy and spectroscopy, valence and core level photoelectron spectroscopy, as well as low‐energy electron diffraction measurements are used, complemented by density functional theory calculations, to investigate both the electronic and structural properties of the homomolecular as well as the intermixed layers. The donor molecules are weakly interacting with the Ag(111) surface, while the acceptor molecules show a strong interaction with the substrate leading to charge transfer and substantial buckling of the top silver layer and of the adsorbates. Upon mixing acceptor and donor molecules, strong hybridization occurs between the two different molecules leading to the emergence of a common unoccupied molecular orbital located at both the donor and acceptor molecules. The donor acceptor blend studied here is, therefore, a compelling candidate for organic electronics based on self‐assembled charge‐transfer complexes.
Stoichiometry of mercury-thiol complexes on bacterial cell envelopes
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